Thermally cured undercoat for lithographic application

1. A thermally curable undercoat composition comprising

a) a polymer of Structure I comprising repeating units of Structure II, III, and IV

wherein each R 1 is independently selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, and a halogen atom; L is selected from the group consisting of

(1) a single bond and a —CON(R 2 )— group wherein R 2 is selected from the group consisting of a hydrogen atom and an alkyl group having from 1 to 3 carbon atoms when M is a C 5-7 cycloalkylene group, W is selected from the group consisting of a single bond, a —COO— group, —O—, —(C═O)—, and —(SO 2 )—, and R 3 is selected from the group consisting of a hydrogen atom, a linear unsubstituted or substituted alkyl having from 5 to 30 carbon atoms, an unsubstituted or substituted cycloalkyl group having from 5 to 30 carbon atoms, a bridged unsubstituted or substituted alicyclic hydrocarbon group having from 5 to 25 carbon atoms, an unsubstituted or substituted aryl group having from 6 to 18 carbon atoms and an arylalkyl group having from 7 to 18 carbon atoms; n is an integer from 1 to 3, q is an integer from 0 to 3, the sum of n and q being no greater than 5;

(2) a —CON(R 2 )— group wherein R 2 is selected from the group consisting of a hydrogen atom and an alkyl group having from 1 to 3 carbon atoms, when M is an arylene group having from 6 to 18 carbon atoms, W is selected from the group consisting of a —COO— group, —O—, —(C═O)—, and —(SO 2 )—, and R 3 is selected from the group consisting of a hydrogen atom, a linear unsubstituted or substituted alkyl having from 5 to 30 carbon atoms, an unsubstituted or substituted cycloalkyl group having from 5 to 30 carbon atoms, a bridged unsbstituted or substituted alicyclic hydrocarbon group having from 5 to 25 carbon atoms, an unsubstituted or substituted aryl group having from 6 to 18 carbon atoms and an arylalkyl group having from 7 to 18 carbon atoms; n is an integer from 1 to 3, q is an integer from 0 to 3, the sum of n and q being no greater than 5;

(3) a —COO— group when M is cycloalkylene, W is selected from the group consisting of —COO—, —O—, —C═O— and —(SO 2 )— and R 3 is selected from the group consisting of a hydrogen atom, a linear unsubstituted or substituted alkyl having from 5 to 30 carbon atoms, an unsubstituted or substituted cycloalkyl group having from 5 to 30 carbon atoms, a bridged unsubstituted or substituted alicyclic hydrocarbon group having from 5 to 25 carbon atoms, an unsubstituted or substituted aryl group having from 6 to 18 carbon atoms and an arylalkyl group having from 7 to 18 carbon atoms; n is an integer from 1 to 3, q is an integer from 0 to 3, the sum of n and q being no greater than 5; and

(4) a —COO— group when M is cycloalkylene, W is a single bond and R 3 is selected from the group consisting of a linear unsubstituted or substituted alkyl having from 5 to 30 carbon atoms, an unsubstituted or substituted cycloalkyl group having from 5 to 30 carbon atoms, a bridged unsubstituted or substituted alicyclic hydrocarbon group having from 5 to 25 carbon atoms, an unsubstituted or substituted aryl group having from 6 to 18 carbon atoms and an arylalkyl group having from 7 to 18 carbon atoms; n is an integer from 1 to 3, q is an integer from 0 to 3, the sum of n and q being no greater then 5;

R 4 is selected from the group consisting of a linear or branched or cyclic C 1 -C 10 alkyl and a halogen group; R 5 is selected from the group consisting of a linear, branched or cyclic alkyl and an unsubstituted or substituted alicyclic group, having 5 to 30 carbon atoms, and a (R 6 O) t R 7 group where R 6 is a C 1-10 linear or branched alkylene group and R 7 is selected from the group consisting of a linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group and an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms and t is an integer from 1 to 4;

b) a phenolic crosslinker having Structure V

wherein p is an integer of about 2 to 6; R 8 is a —CH 2 OR 12 group; R 9 is selected from the group consisting of a hydrogen atom, —CH 2 OR 12 group, C 1 -C 5 alkyl group, and aryl; R 10 , R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, and a C 1 -C 5 alkyl group; X is a di- tri-, tetra-, penta- or hexa-valent alkyl or arylalkyl moiety;

c) a thermal acid generator (TAG) of Structure VI

wherein A is selected from the group consisting of a phenyl and a naphthyl group, R 20 is selected from the group consisting of an alkyl or a cyclic alkyl and an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms; when A is phenyl, x is an integer of from 1 to 3, y is an integer of from 0 to 5, the sum of x and y being no greater than 6, and z is 6−x−y; when A is naphthyl, x is an integer from 1 to 3, y is an integer from 0 to 7, the sum of x and y being no greater than 8, and z is 8−x−y; B is a primary, secondary, or tertiary unsubstituted or substituted alkyl or carbocyclic or heterocyclic amine having 4 to 30 carbon atoms; and

d) a solvent.

2. A thermally curable undercoat composition comprising

a) a polymer of Structure I comprising repeating units selected from the group consisting of Structures VII, VIII, and X

wherein R 1 is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms and a halogen atom; R 24 is selected from the group consisting of a hydrogen atom and a methyl group; R 21 is an unsubstituted or substituted aromatic group having C 6 -C 30 carbon atoms; R 25 is an unsubstituted or substituted aromatic group having C 6 -C 30 carbon atoms; R 29 is a substituted or unsubstituted C 5 -C 7 cyclalky group; R 22 is selected from the group consisting of a hydrogen and a C 1 -C 4 alkyl group, R 23 , R 26 , and R 28 are selected from the group consisting of cyclic alkyl, an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms, and (R 30 O) t R 7 group where R 30 is a C 2-4 linear or branched alkylene group and R 7 is selected from the group consisting of linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms; n is an integer of about 1 to 2 and t is an integer about 1 to 4;

b) a phenolic crosslinker having Structure V

wherein p is an integer of about 2 to 6; R 8 is a —CH 2 OR 12 group; R 9 is selected from the group consisting of a hydrogen atom, —CH 2 OR 12 group, C 1 -C 5 alkyl group, and aryl; R 10 , R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, and a C 1 -C 5 alkyl group; X is a di- tri-, tetra-, penta- or hex valent or arylalkyl moiety;

c) a thermal acid generator (TAG) of Structure VI

wherein A is selected from the group consisting of a phenyl and a naphthyl group, R 20 is selected from the group consisting of an alkyl or a cyclic alkyl and an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms; when A is phenyl, x is an integer of from 1 to 3, y is an integer of from 0 to 5, the sum of x and y being no greater then 6, and z is 6−x−y; when A is naphthyl, x is an integer from 1 to 3, y is an integer from 0 to 7, the sum of x and y being no greater then 8, and z is 8−x−y; b is a primary, secondary, or tertiary unsubstituted or substituted alkyl or carbocyclic or heterocyclic amine having 4 to 30 carbon atoms; and

d) a solvent.

3. A thermally curable undercoat composition according to claim 2 wherein the polymer of Structure I is a polymer of Structure VII

wherein R 1 is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms and a halogen atom; R 21 is an unsubstituted or substituted aromatic group having C 6 -C 30 carbon atoms; R 22 is selected from the group consisting of a hydrogen atom and a C 1 -C 4 alkyl group, R 23 is selected from the group consisting of cyclic alkyl, an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms, and (R 30 O) t R 7 group where R 30 is a C 2-4 linear or branched alkylene group and R 7 is selected from the group consisting of linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group, and an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms; n is an integer of 1 to 2 and t is an integer 1 to 4.

4. A thermally curable undercoat composition according to claim 2 wherein the polymer of Structure I is a polymer of Structure VIII

wherein R 24 is selected from the group consisting of a hydrogen atom and a methyl group; R 25 is an unsubstituted or substituted aromatic group having C 6 -C 30 carbon atoms; R 26 is selected from the group consisting a cyclic alkyl or an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms and a (R 30 O) t R 7 group where R 30 is a C 2-4 linear or branched alkylene group and R 7 is selected from the group consisting a linear, branched or cyclic alkyl group, an unsubstituted or substituted alicyclic group, and unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms and t is an integer of about 1 to 4; and n is an integer of 1 to 2.

5. A thermally curable undercoat composition comprising:

a) a polymer if Structure IX

wherein R 1 is selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, and a halogen atom; R 22 is selected from the group consisting of a hydrogen atom, and a C1-C4 alkyl group; R 27 is a substituted or unsubstituted C 5 -C 7 cycloalkyl; R 28 is selected from the group consisting of a cyclic alkyl, an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms and (R 30 O) t R 7 group where R 30 is a C 2-4 linear or branched alkylene group and R 7 is selected from the group consisting of a linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group, and an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms and t is an integer of 1 to 4, and n is an integer of 1 to 3.

b) a phenolic crosslinker having Structure V

wherein p is an integer of about 2 to 6; R 8 is a —CH 2 OR 12 group; R 9 is selected from the group consisting of a hydrogen atom, —CH 2 OR 12 group, C 1 -C 5 alkyl group, and aryl; R 10 , R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, and a C 1 -C 5 alkyl group; X is a di- tri-, tetra-, penta- or hexa- valent alkyl or arylalkyl moiety;

c) a thermal acid generator (TAG) of Structure VI

wherein A is selected from the group consisting of a phenyl and a naphthyl group, R 20 is selected from the group consisting of an alkyl or a cyclic alkyl and an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms; when A is phenyl, x is an integer of from 1 to 3, y is an integer of from 0 to 5, the sum of x and y being no greater then 6, and z is 6−x−y; when A is naphthyl, x is an integer from 1 to 3, y is an integer from 0 to 7, the sum of x and y being no greater than 8, and z is 8−x−y; B is a primary, secondary, or tertiary unsubstituted or substituted alkyl or carbocyclic or heterocyclic amine having 4 to 30 carbon atoms; and

d) a solvent.

6. A thermally curable undercoat composition according to claim 2 wherein the polymer of Structure I is a polymer is Structure X

wherein R 24 is selected from the group consisting of a hydrogen atom and a methyl group; R 28 is selected from the group consisting of a cyclic alkyl, an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms and (R 30 O) t R 7 group where R 30 is a C 2-4 linear or branched alkylene group and R 7 is selected from the group consisting of a linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group, and an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms and t is an integer of 1 to 4; R 29 is a substituted or unsubstituted C 5 -C 7 cycloalkyl group; and n is an integer of 1 to 2.

7. A thermally curable undercoat composition according to claim 1 wherein, in repeating unit of Structure II, R 1 is selected from the group consisting of hydrogen and methyl; W is a single bond; and wherein when M is a C 5 -C 7 cycloalkylene group and L is a single bond.

8. A thermally curable undercoat composition comprising

a) a polymer of Structure I comprising repeating units of Structure II, III, and IV

wherein each R 1 is independently selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms, and a halogen atom; L is selected from the group consisting of

(1) a single bond, a —COO— group, and a —CON(R 2 )— group; wherein R 2 is selected from the group consisting of a hydrogen atom and an alkyl group having from 1 to 3 carbon atoms; when M is a C 5-7 cycloalkylene group, and W is selected from the group consisting of a single bond, a —COO— group, —O—, —(C═O)—, and —(SO 2 )—; and

(2) a —COO— group, and a —CON(R 2 )— group wherein R 2 is selected from the group consisting of a hydrogen atom and an alkyl group having from 1 to 3 carbon atoms, when M is an arylene group having from 6 to 18 carbon atoms, W is selected from the group consisting of a —COO— group, —O—, —(C═O)—, and —(SO 2 )—;

R 3 is selected from the group consisting of a cyclopentyl, cyclohexyl, adamantyl, bicycle[2.2.1]heptyl, tricycle[5.2.1.0 2,6 ]decyl, phenyl and naphthyl; n is an integer from 1 to 3, q is an integer from 0 to 3, the sum of n and q being no greater then 5; R 4 is selected from the group consisting of a linear or branched or cyclic C 1 -C 10 alkyl and a halogen group; R 5 is selected from the group consisting of a linear, branched or cyclic alkyl and an unsubstituted or substituted alicyclic group, having 5 to 30 carbon atoms, and a (R 6 O) t R 7 group where R 6 is a C 1-10 linear or branched alkylene group and R 7 is selected from the group consisting of a linear, branched or cyclic alkyl, an unsubstituted or substituted alicyclic group and an unsubstituted or substituted aromatic or alkyl aromatic group having 1 to 30 carbon atoms and t is an integer from 1 to 4;

b) a phenolic crosslinker having Structure V

wherein p is an integer of about 2 to 6; R 8 is a —CH 2 OR 12 group; R 9 is selected from the group consisting of a hydrogen atom, —CH 2 OR 12 group, C 1 -C 5 alkyl group, and aryl; R 10 , R 11 and R 12 are each independently selected from the group consisting of a hydrogen atom, and a C 1 -C 5 alkyl group; X is a di- tri-, tetra-, penta- or hexa-valent alkyl or arylalkyl moiety;

c) a thermal acid generator (TAG) of Structure VI

wherein A is selected from the group consisting of a phenyl and a naphthyl group, R 20 is selected from the group consisting of an alkyl or a cyclic alkyl and an unsubstituted or substituted alicyclic group having 5 to 30 carbon atoms; when A is phenyl, x is an integer of from 1 to 3, y is an integer of from 0 to 5, the sum of x and y being no greater than 6, and z is 6−x−y; when A is naphthyl, x is an integer from 1 to 3, y is an integer from 0 to 7, the sum of x and y being no greater than 8, and z is 8−x−y; B is a primary, secondary, or tertiary unsubstituted or substituted alkyl or carbocyclic or heterocyclic amine having 4 to 30 carbon atoms; and

d) a solvent.

9. A thermally curable undercoat composition according to claim 1 wherein, in the repeating unit of Structure III, wherein R 1 is selected from the group consisting of hydrogen and methyl; R 4 is selected from the group consisting of a hydrogen atom, a halogen group and a C 1 -C 4 linear or branched group.

10. A thermally curable undercoat composition according to claim 1 wherein, in repeating unit of Structure II, R 1 is selected from the group consisting of hydrogen and methyl; W is a single bond; and wherein when M is a C 5 -C 7 cycloalkylene group L is selected from the group consisting of a single bond and a —COO— group; and R 3 is selected from the group consisting of cyclopentyl, cyclohexyl, adamantyl, bicycle[2.2.1.]heptyl, tricycle[5.2.1.0 2,6 ]decyl, phenyl and naphthyl; in the repeating unit of Structure III, wherein R 1 is selected from the group consisting of hydrogen and methyl; R 4 is selected from the group consisting of a hydrogen atom, a halogen group and a C 1 -C 4 linear or branched alkyl group; and, in the repeating unit of Structure IV, wherein R 1 is selected from the group consisting of a cyclohexyl, bicysle[2.2.1]heptyl, adamantly, adamantylmethyl, tricycle[5.2.1.02,6]decanemethyl, and ethoxydicyclopentenyl.

11. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 1 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

12. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 3 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

13. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 4 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

14. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 5 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

15. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 6 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

16. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 7 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

17. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 8 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

18. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 9 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

19. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 10 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

20. A bilayer relief image produced by the process of claim 11 .

21. A coated substrate comprising a semiconductor substrate coated by the composition of claim 1 wherein the composition of claim 1 is further coated with a photoresist.

22. A process for forming a pattern on a substrate comprising the following process steps:

a. providing a substrate,

b. coating in a first coating step said substrate with a thermally curable undercoat composition of claim 2 ,

c. curing said undercoat composition,

d. coating in a second coating step a photoresist over the undercoat to produce a bilayer photoresist stack,

e. exposing the bilayer photoresist stack to provide a photosensitive composition portion of the bilayer photoresist stack,

f. developing the photosensitive composition portion of the bilayer photoresist stack making a portion of the underlying undercoat visible,

g. rinsing the bilayer photoresist stack, and

h. etching the visible undercoat in an oxidizing plasma to produce a bilayer relief image.

23. A bilayer relief image produced by the process of claim 22 .

24. A coated substrate comprising a semiconductor substrate coated by the composition of claim 2 wherein the composition of claim 1 is further coated with photoresist.