Polymer comprising repeat units with photoacid-generating functionality and base-solubility-enhancing functionality, and associated photoresist composition and electronic device forming method
View Patent ↗A polymer includes repeat units, most of which are photoacid-generating repeat units. Each of the photoacid-generating repeat units includes photoacid-generating functionality and base-solubility-enhancing functionality. Each of the photoacid-generating repeat units comprises an anion and a photoacid-generating cation that collectively have structure (I) wherein q, r, R 1 , m, X, and Z − are defined herein. The polymer is useful as a component of a photoresist composition that further includes a second polymer that exhibits a change in solubility in an alkali developer under action of acid.
1. A polymer comprising, based on 100 mole percent of total repeat units, 50 to 100 mole percent of photoacid-generating repeat units; wherein each of the photoacid-generating repeat units comprises an anion, a photoacid-generating cation, and base-solubility-enhancing functionality; wherein the base-solubility-enhancing functionality resides in the photoacid-generating cation and comprises two functional groups selected from the group consisting of tertiary carboxylic acid esters, secondary carboxylic acid esters wherein the secondary carbon is substituted with at least one unsubstituted or substituted C 6-40 aryl, acetals, ketals, lactones, sultones, alpha-fluorinated esters, beta-fluorinated esters, alpha,beta-fluorinated esters, polyalkyleneglycols, alpha-fluorinated alcohols, and combinations thereof; and wherein each of the photoacid-generating repeat units independently has the structure
wherein
q is independently in each photoacid-generating repeat unit 1, 2, 3, 4, or 5;
r is independently at each occurrence in each photoacid-generating repeat unit 0, 1, 2, 3, or 4;
R 1 is independently at each occurrence in each photoacid-generating repeat unit halogen, unsubstituted or substituted C 1-40 hydrocarbyl, or unsubstituted or substituted C 1-40 hydrocarbylene; provided that at least one occurrence of R 1 comprises base-solubility-enhancing functionality, and the base-solubility-enhancing functionality on the at least one occurrence of R 1 comprises two of the functional groups selected from the group consisting of tertiary carboxylic acid esters, secondary carboxylic acid esters wherein the secondary carbon is substituted with at least one unsubstituted or substituted C 6-40 aryl, acetals, ketals, lactones, sultones, alpha-fluorinated esters, beta-fluorinated esters, alpha,beta-fluorinated esters, polyalkyleneglycols, alpha-fluorinated alcohols, and combinations thereof;
R 3 is independently in each of the repeat units H, F, —CN, C 1-10 alkyl, or C 1-10 fluoroalkyl;
m is independently in each photoacid-generating repeat unit 0 or 1;
n is independently in each of the repeat units 0 or 1;
L 1 and L 3 are each independently in each of the repeat units an unsubstituted or substituted C 1-20 hydrocarbylene, wherein the substituted C 1-20 hydrocarbylene can, optionally, comprise one or more in-chain divalent heteroatom-containing groups that is —O—, —S—, —N(R 4 )—, —P(R 4 )—, —C(O)—, —OC(O)—, —OC(O)O—, —N(R 4 )C(O)—, —C(O)N(R 4 )—, —OC(O)N(R 4 )—, —N(R 4 )C(O)O—, —S(O)—, —S(O) 2 —, —N(R 4 )S(O) 2 —, —S(O) 2 N(R 4 )—, —OS(O) 2 —, or —S(O) 2 O—, wherein R 4 is H or C 1-12 hydrocarbyl;
L 2 is independently in each of the repeat units —O—, —C(O)—, or —N(R 5 )—, wherein R 5 is H or C 1-12 hydrocarbyl; and
X is independently in each photoacid-generating repeat unit a single bond, —O—, —S—, —C(═O)—, —C(R 2 ) 2 —, —C(R 2 )(OH)—, —C(═O)O—, —C(═O)N(R 2 )—, —C(═O)C(═O)—, —S(═O)—, or —S(═O) 2 —, wherein R 2 is independently at each occurrence hydrogen or C 1-12 hydrocarbyl.
2. The polymer of claim 1 , comprising 95 to 100 mole percent of the photoacid-generating repeat units.
3. The polymer of claim 1 , wherein the photoacid-generating repeat units are derived from a single monomer.
4. The polymer of claim 1 , wherein the photoacid-generating repeat units are derived from at least two different monomers.
5. The polymer of claim 1 , wherein the base-solubility-enhancing functionality on the at least one occurrence of R 1 comprises two functional groups selected from the group consisting of tertiary carboxylic acid esters, acetals, ketals, and lactones.
6. The polymer of claim 1 , wherein the base-solubility-enhancing functionality on the at least one occurrence of R 1 comprises two functional groups selected from the group consisting of tertiary carboxylic acid esters, and lactones.
7. A photoresist composition comprising the polymer of claim 1 and a solvent.
8. A method of forming an electronic device, comprising:
(a) applying a layer of the photoresist composition of claim 7 on a substrate;
(b) pattern-wise exposing the photoresist composition layer to activating radiation; and
(c) developing the exposed photoresist composition layer to provide a resist relief image.