Resist underlayer compositions and pattern formation methods using such compositions

1 . A coated substrate, comprising:

a substrate;

a resist underlayer formed from a resist underlayer composition; and

a photoresist layer over the resist underlayer,

wherein the resist underlayer composition comprises:

a polymer comprising a polymer backbone and a substituted or unsubstituted C 50 to C 120 fullerene group pendant to the polymer backbone, and

a solvent in an amount of from 50 to 99.9 weight % based on the total resist underlayer composition,

wherein the resist underlayer composition is free of additive crosslinking compounds,

wherein the polymer further comprises a linking group bonded to the fullerene group and to the polymer backbone, wherein the linking group comprises a ring structure that utilizes two or more atoms on the fullerene group, and

wherein the polymer is a polyalkylene, a polyalkylene oxide, a polyarylene, a Novolac polymer, a vinyl aromatic polymer, a (meth)acrylate polymer, a polyester, a norbornene polymer, a polyimide, a combination thereof, or a copolymer thereof.

2 . The coated substrate of claim 1 , wherein the polymer is self-crosslinkable, wherein the self-crosslinkable polymer refers to a polymer capable of undergoing a crosslinking reaction between units thereof without an aid of an additive catalyst or a crosslinking agent.

3 . The coated substrate of claim 1 , wherein the polymer further comprises an arylcyclobutene group pendant to the polymer backbone.

4 . The coated substrate of claim 1 , wherein the linking group comprises:

a substituted or unsubstituted C 3-20 alicyclic group or a C 2-20 heteroalicyclic group that forms a fused ring with the fullerene group, and

a C 6-20 aromatic group or a C 3-20 heteroaromatic group that is fused to the C 3-20 alicyclic group or the C 2-20 heteroalicyclic group.

5 . The coated substrate of claim 1 , wherein the polymer comprises the reaction product of a substituted or unsubstituted fullerene with a substituted or unsubstituted arylcyclobutene group that is pendant to a precursor polymer backbone.

6 . The coated substrate of claim 1 , wherein the linking group is represented by Formula 1:

wherein,

R 1 to R 5 are each independently hydrogen, deuterium, a substituted or unsubstituted C 1-20 linear or branched alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-20 arylalkyl group, a substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 3-30 heteroarylalkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 3-30 heterocycloalkyl group, a C 1-20 alkoxy group, a hydroxy group, —NH 2 ; —NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group, an isocyanate group, a halogen, —ROR′ (wherein R is a substituted or unsubstituted C 1-20 alkylene group and R′ is hydrogen or a C 1-20 linear or branched alkyl group, —RC(═O)X (wherein R is a substituted or unsubstituted alkylene group and X is a halogen), —C(═O)OR′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —OC(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —CN, —OC(═O)NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group), —S(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), and —S(═O) 2 R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), provided that each R 5 is not hydrogen,

any two adjacent groups selected from R 1 to R 5 are optionally connected to form a ring;

n1 is 0, 1, 2, or 3;

** indicates a point of attachment directly or indirectly to the polymer backbone; and

* indicates a point of attachment to the fullerene group.

7 . The coated substrate of claim 1 , wherein the linking group is represented by Formula 2:

wherein,

R 2 to R 5 are each independently hydrogen, deuterium, a substituted or unsubstituted C 1-20 linear or branched alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-20 arylalkyl group, a substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 3-30 heteroarylalkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 3-30 heterocycloalkyl group, a C 1-20 alkoxy group, a hydroxy group, —NH 2 ; —NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group, an isocyanate group, a halogen, —ROR′ (wherein R is a substituted or unsubstituted C 1-20 alkylene group and R′ is hydrogen or a C 1-20 linear or branched alkyl group, —RC(═O)X (wherein R is a substituted or unsubstituted alkylene group and X is a halogen), —C(═O)OR′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —OC(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —CN, —OC(═O)NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group), —S(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), and —S(═O) 2 R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), provided that each R 5 is not hydrogen,

any two adjacent groups selected from R 2 to R 5 are optionally connected to form a ring;

n1 is 0, 1, 2, or 3;

** indicates a point of attachment directly or indirectly to the polymer backbone; and

* indicates a point of attachment to the fullerene group.

8 . The coated substrate of claim 1 , wherein the linking group comprises a substituted or unsubstituted C 3-20 alicyclic group or a substituted or unsubstituted C 2-20 heteroalicyclic group, and wherein the C 3-20 alicyclic group or the C 2-20 heteroalicyclic group is attached to the polymer backbone through a single bond or a group selected from a C 1-10 alkylene group, an ether group, a carbonyl group, an ester group, a carbonate group, an amine group, an amide group, a urea group, a sulfate group, a sulfone group, a sulfoxide group, an N-oxide group, a sulfonate group, a sulfonamide group, or a combination of at least two of the foregoing.

9 . The coated substrate of claim 1 , wherein the polymer is a Novolac polymer, a vinyl aromatic polymer, or a copolymer thereof.

10 . The coated substrate of claim 1 , wherein the polymer backbone comprises carbon atoms only.

11 . A polymer for a resist underlayer composition, comprising

a polymer backbone,

a substituted or unsubstituted C 50 to C 120 fullerene group pendent to the polymer backbone, and

a linking group bonded to the polymer backbone and the fullerene group, wherein the linking group comprises a ring structure that utilizes two or more atoms on the fullerene group,

wherein the polymer is self-crosslinkable, wherein the self-crosslinkable polymer refers to a polymer capable of undergoing a crosslinking reaction between units thereof without an aid of an additive catalyst or a crosslinking agent, and

wherein the polymer is a polyalkylene, a polyalkylene oxide, a polypyrene, a Novolac polymer, a vinyl aromatic polymer, a (meth)acrylate polymer, a polyester, a norbornene polymer, a polyimide, a polymer comprising a group represented by Formula 3, a combination thereof, or a copolymer thereof:

wherein,

R 6 and R 7 are each independently deuterium, a substituted or unsubstituted C 1-20 linear or branched alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-20 arylalkyl group, a substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 3-30 heteroarylalkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 3-30 heterocycloalkyl group, a C 1-20 alkoxy group, a hydroxy group, —NRR′ (wherein R and R′ are each independently hydrogen or a C 1-20 linear or branched alkyl group), an isocyanate group, a halogen, —ROR′ (wherein R is a substituted or unsubstituted C 1-20 alkylene group and R′ is hydrogen or a C 1-20 linear or branched alkyl group), —RC(═O)X (wherein R is a substituted or unsubstituted alkylene group and X is a halogen), —C(═O)OR′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —CN, —OC(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —OC(═O)NRR′ (wherein R and R′ are each independently hydrogen or a C 1-20 linear or branched alkyl group), —S(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), or —S(═O) 2 R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group),

any two adjacent groups selected from R 6 are optionally connected to form a ring,

any two adjacent groups selected from R 7 are optionally connected to form a ring,

n2 and n3 are each independently 0, 1, 2, 3, or 4,

* indicates a point of direct or indirect attachment to the fullerene group, and

** indicates a point of attachment to a polymer backbone.

12 . The polymer of claim 11 , wherein the polymer backbone comprises carbon atoms only.

13 . The polymer of claim 11 , wherein the linking group is represented by Formula 1 or Formula 2:

wherein, in Formula 1,

R 1 to R 5 are each independently hydrogen, deuterium, a substituted or unsubstituted C 1-20 linear or branched alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-20 arylalkyl group, a substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 3-30 heteroarylalkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 3-30 heterocycloalkyl group, a C 1-20 alkoxy group, a hydroxy group, —NH 2 ; —NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group, an isocyanate group, a halogen, —ROR′ (wherein R is a substituted or unsubstituted C 1-20 alkylene group and R′ is hydrogen or a C 1-20 linear or branched alkyl group, —RC(═O)X (wherein R is a substituted or unsubstituted alkylene group and X is a halogen), —C(═O)OR′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —OC(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —CN, —OC(═O)NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group), —S(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), and —S(═O) 2 R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), provided that each R 5 is not hydrogen,

any two adjacent groups selected from R 2 to R 5 are optionally connected to form a ring;

n1 is 0, 1, 2, or 3;

** indicates a point of attachment directly or indirectly to the polymer backbone; and

* indicates a point of attachment to the fullerene group;

wherein, in Formula 2,

R 2 to R 5 are each independently hydrogen, deuterium, a substituted or unsubstituted C 1-20 linear or branched alkyl group, a substituted or unsubstituted C 6-20 aryl group, a substituted or unsubstituted C 7-20 arylalkyl group, a substituted or unsubstituted C 3-20 heteroaryl group, a substituted or unsubstituted C 3-30 heteroarylalkyl group, a substituted or unsubstituted C 3-30 cycloalkyl group, a substituted or unsubstituted C 3-30 heterocycloalkyl group, a C 1-20 alkoxy group, a hydroxy group, —NH 2 ; —NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group, an isocyanate group, a halogen, —ROR′ (wherein R is a substituted or unsubstituted C 1-20 alkylene group and R′ is hydrogen or a C 1-20 linear or branched alkyl group, —RC(═O)X (wherein R is a substituted or unsubstituted alkylene group and X is a halogen), —C(═O)OR′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —OC(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), —CN, —OC(═O)NRR′ (wherein R and R′ are independently hydrogen or a C 1-20 linear or branched alkyl group), —S(═O)R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), and —S(═O) 2 R′ (wherein R′ is hydrogen or a C 1-20 linear or branched alkyl group), provided that each R 5 is not hydrogen,

any two adjacent groups selected from R 2 to R 5 are optionally connected to form a ring;

n1 is 0, 1, 2, or 3;

** indicates a point of attachment directly or indirectly to the polymer backbone; and

* indicates a point of attachment to the fullerene group.

14 . A method of forming a pattern, the method comprising: (a) applying a layer of the resist underlayer composition over a substrate; (b) curing the applied resist underlayer composition to form a resist underlayer; and (c) forming a photoresist layer over the resist underlayer,

wherein the resist underlayer composition comprises:

a polymer comprising a polymer backbone and a substituted or unsubstituted C 50 to C 120 fullerene group pendant to the polymer backbone, and

a solvent in an amount of from 50 to 99.9 weight % based on the total resist underlayer composition,

wherein the resist underlayer composition is free of additive crosslinking compounds,

wherein the polymer further comprises a linking group bonded to the fullerene group and to the polymer backbone, wherein the linking group comprises a ring structure that utilizes two or more atoms on the fullerene group, and

wherein the polymer is a polyalkylene, a polyalkylene oxide, a polyarylene, a Novolac polymer, a vinyl aromatic polymer, a (meth)acrylate polymer, a polyester, a norbornene polymer, a polyimide, a combination thereof, or a copolymer thereof.

15 . The method of claim 14 , further comprising forming a silicon-containing layer and/or an organic antireflective coating layer above the resist underlayer prior to forming the photoresist layer.

16 . The method of claim 14 , further comprising patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the resist underlayer and to a layer below the resist underlayer.