Photosensitive compositions
View Patent ↗Provided are radiation-sensitive polymers and compositions which may be used in photolithographic processes. The polymers and compositions provide enhanced sensitivity to activating radiation.
1. A polymer comprising a polymer backbone and a monomeric photoacid generator covalently attached to the polymer backbone, wherein the monomeric photoacid generator is derived from one or more sulfonium salt or iodonium salt having a polymerizable sulfonate anion represented by formula (1a) or formula (1b), respectively:
wherein: Y is hydrogen, alkyl, fluorinated alkyl or fluorine; R 1 , R 2 , R 3 , R 4 and R 5 are independently chosen from substituted and unsubstituted aryl; and Z is a substituted aromatic group covalently bonded to the sulfonate anion via a straight or branched perfluorinated-alkyl chain comprising a terminal CF 2 , C(F)(CF 3 ) or C(CF 3 ) 2 .
2. The polymer of claim 1 , further comprising a repeat unit comprising a photoacid-labile group.
3. The polymer of claim 1 , further comprising polymerized units chosen from one or more of 2-methyladamantanyl methacrylate, 2-methyladamantanyl acrylate, hydroxyadamantylacrylate, hydroxyadamantylmethacrylate, maleic anhydride, norbornene, 3,4-dihydropyran, optionally substituted phenyl and optionally substituted naphthyl.
4. The polymer of claim 1 , further comprising one or more polar monomer attached to the polymer backbone, wherein the polar monomer is represented by one or both of the following formulae:
5. A positive-tone photoresist composition comprising a polymer of claim 1 .
6. The positive-tone photoresist composition of claim 5 , further comprising a second polymer comprising: a polymer backbone which is free of monomeric photoacid generators covalently attached thereto; and a photoacid-labile group.
7. 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 positive-tone photoresist composition of claim 5 over the one or more layers to be patterned.
8. A method of forming an electronic device, comprising:
(a) applying a layer of a positive-tone photoresist composition of claim 5 on a substrate;
(b) patternwise exposing the photoresist composition layer to activating radiation; and
(c) developing the exposed photoresist composition layer to provide a resist relief image.
9. The method of claim 8 , wherein the activating radiation is extreme-ultraviolet or e-beam radiation.
10. The polymer of claim 1 , wherein the monomeric photoacid generator is derived from a sulfonium salt having a polymerizable sulfonate anion represented by formula (1a).
11. The polymer of claim 1 , wherein the monomeric photoacid generator is derived from an iodonium salt having a polymerizable sulfonate anion represented by formula (1b).