Nanoparticle-polymer resists

1. A composite, which is a blend comprising:

a nanoparticle comprising a core and a coating surrounding the core; and

a polymer,

wherein the coating of the nanoparticle comprises a ligand, wherein the ligand is a substituted or unsubstituted C 1 -C 16 carboxylic acid or a salt thereof, a substituted or unsubstituted C 1 -C 16 amino acid or a salt thereof, a substituted or unsubstituted C 1 -C 16 dialkyl phosphonate, or a combination thereof; and

wherein the polymer is a polymerization product of a group of reactants consisting of

a photoacid generator comprising a polymerizable group,

a monomer of formula (IV-A):

wherein,

R a is independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl; and

R b is independently H, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl, wherein each R b is separate or at least one R b is bonded to an adjacent R b to form a cyclic structure, and optionally,

a monomer selected from the group consisting of a base-soluble monomer of formula (V) or a lactone-containing monomer of formula (VI), but not both:

wherein,

W is a base-reactive group comprising —C(═O)—OH; —C(CF 3 ) 2 OH; —NH—SO 2 —Y 1 where Y 1 is F or C 1-4 perfluoroalkyl; an aromatic —OH; or an adduct of any of the foregoing with a vinyl ether,

a is an integer of 1 to 3, and

L is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group; and

a chain transfer agent of formula (I);

wherein:

Z is a y valent C 1-20 organic group,

x is 0 or 1, and

R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl.

2. The composite of claim 1 , wherein the core of the nanoparticle comprises ZrO 2 , HfO 2 , TiO 2 , or a combination thereof.

3. The composite of claim 1 , wherein the ligand is a substituted or unsubstituted C 1 -C 16 carboxylic acid or a salt thereof.

4. The composite of claim 1 , wherein a median diameter of the nanoparticle is 10 nanometers or less.

5. The composite of claim 1 , wherein photoacid generator comprising a polymerizable group is a monomer represented by formula (II):

wherein

each R a is independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl;

Q 2 is a single bond or an ester-containing or non-ester containing, fluorinated or non-fluorinated group selected from C 1-20 alkylene, C 3-20 cycloalkylene, C 6-20 arylene, and C 7-20 aralkylene group;

A is an ester-containing or non ester-containing, fluorinated or non-fluorinated group selected from C 1-20 alkylene, C 3-20 cycloalkylene, C 6-20 arylene, and C 7-20 aralkylene;

Z is an anionic moiety comprising sulfonate, an anion of a sulfonamide, or an anion of a sulfonimide; and

G + has formula (III):

wherein X is S or I, each R c is halogenated or non-halogenated and is independently a C 1-30 alkyl group; a polycyclic or monocyclic C 3-30 cycloalkyl group; a polycyclic or monocyclic C 4-30 aryl group, wherein when X is S, one of the R c groups is optionally attached to one adjacent R c group by a single bond, and z is 2 or 3, wherein when X is I, z is 2, or when X is S, z is 3.

6. The composite of claim 5 , wherein G + has formula (VII), (VIII), or (IX):

wherein

X is I or S,

R h , R i , R j , and R k are each independently hydroxy, nitrile, halogen, C 1-10 alkyl, C 1-10 fluoroalkyl, C 1-10 alkoxy, C 1-10 fluoroalkoxy, C 6-20 aryl, C 6-20 fluoroaryl, C 6-20 aryloxy, or C 6-20 fluoroaryloxy,

Ar 1 and Ar 2 are independently C 10-30 fused or singly bonded polycyclic aryl groups;

R l is a lone pair of electrons where X is I, or a C 6-20 aryl group where X is S; p is an integer of 2 or 3, wherein when X is I, p is 2, and where X is S, p is 3,

q and r are each independently an integer from 0 to 5, and

s and t are each independently an integer from 0 to 4.

7. The composite of claim 1 , wherein the organic group Z is bonded to the polymer to form an end group having the structure shown below:

wherein Z is a v valent C 1-20 organic group,

x is 0 or 1, and

R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl.

8. The composite of claim 1 , wherein the chain transfer agent of formula (I) has the structure of formula (X):

wherein

R m is a C 1-10 alkyl, C 1-10 alkoxy, C 3-10 cycloalkyl, C 6-10 aryl, or C 7-10 aralkyl group, and

R c is substituted or unsubstituted and is a C 1-10 alkyl or C 6-10 aryl group.

9. A photoresist composition comprising the composite of claim 1 .

10. A coated substrate, comprising: (a) a substrate having one or more layers to be patterned on a surface thereof; and (b) a layer of a photoresist composition of claim 9 over the one or more layers to be patterned.

11. A method of forming an electronic device comprising:

(a) applying a layer of the photoresist composition of claim 9 on a surface of the substrate;

(b) pattern-wise exposing the photoresist composition layer to activating radiation; and

(c) developing the exposed photoresist composition layer with a solvent to provide a resist relief image.

12. The composite of claim 11 , wherein the resist relief image is a negative image.

13. The method of claim 11 , wherein the solvent is a mixture of an alcohol and a ketone.

14. A method of making a composite, comprising contacting

a nanoparticle comprising a core and a coating surrounding the core; and

a polymer,

wherein the coating of the nanoparticle comprises a ligand, wherein the ligand is a substituted or unsubstituted C 1 -C 16 carboxylic acid or a salt thereof, a substituted or unsubstituted C 1 -C 16 amino acid or a salt thereof, a substituted or unsubstituted C 1 -C 16 dialkyl phosphonate, or a combination thereof; and

wherein the polymer is a polymerization product of a group of reactants consisting of

a photoacid generator comprising a polymerizable group,

a monomer of formula (IV-A):

wherein,

R a is independently H, F, C 1-10 alkyl, or C 1-10 fluoroalkyl; and

R b is independently H, C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl, wherein each R b is separate or at least one R b is bonded to an adjacent R b to form a cyclic structure, and optionally

a monomer selected from the group consisting of a base-soluble monomer of formula (V) or a lactone-containing monomer of formula (VI), but not both:

wherein,

W is a base-reactive group comprising —C(═O)—OH; —C(CF 3 ) 2 OH; —NH—SO 2 —Y 1 where Y 1 is F or C 1-4 perfluoroalkyl; an aromatic —OH; or an adduct of any of the foregoing with a vinyl ether,

a is an integer of 1 to 3,

L is a monocyclic, polycyclic, or fused polycyclic C 4-20 lactone-containing group; and

a chain transfer agent of formula (I);

wherein:

Z is a y valent C 1-20 organic group,

x is 0 or 1, and

R d is a substituted or unsubstituted C 1-20 alkyl, C 3-20 cycloalkyl, C 6-20 aryl, or C 7-20 aralkyl.