Base reactive photoacid generators and photoresists comprising same

1. A photoacid generator compound of formula (I)

R 5 M + R 6 R 7 r − O 3 S—R 1 p —X y —(R 2 Z w R 3 ) x   (I)

wherein each R 1 is chosen from (C 1 -C 10 )alkyl, heteroatom-containing (C 1 -C 10 )alkyl, fluoro(C 1 -C 10 )alkyl, heteroatom-containing fluoro (C 1 -C 10 )alkyl, (C 6 -C 10 )aryl, and fluoro(C 6 -C 10 )aryl; each R 2 is a chemical bond or a (C 1 -C 30 )hydrocarbyl group; each R 3 is H or a (C 1 -C 30 )hydrocarbyl group; R 5 , R 6 and R 7 independently are chosen from an optionally substituted carbocylic aryl group, an allyl group, and an optionally substituted (C 1 -C 20 )alkyl group; X is a chemical bond or a divalent linking group; Z is chosen from an acetoacetoxy ester, —C(O)—O—C(O)—R 1 —, —C(CF 3 ) 2 —, —COO—R f —, —SO 3 —R f —, —OCH 3-z (CH 2 OC(═O)—R f —) z , and a (C 5 -C 30 )cyclohydrocarbyl group comprising a base-reactive group chosen from fluoroalkyl esters, fluorosulfonate esters, and —C(CF 3 ) 2 O—; each R f is independently a fluoro(C 1 -C 10 )alkyl; p=0-6; w=1-3; x=1-4; y=0-5; z=1-2; r=0-1; M is S or I; wherein when M=I, r=0, and when M=S, r=1.

2. The photoacid generator compound of claim 1 wherein X is chosen from —C(O)O—, —C(O)S—, —SO 3 —, —S(O)—, —SO 2 —,

and combination thereof.

3. A photoresist composition comprising a photoacid generator compound of claim 1 .

4. A method for forming a photoresist relief image on a substrate comprising: (a) applying a coating layer of a photoresist composition of claim 3 on a substrate; and (b) exposing the photoresist coating layer to patterned activating radiation and developing the exposed photoresist layer to provide a relief image.

5. The method of claim 4 further comprising developing the exposed photoresist layer with aqueous alkaline developer whereby the one or more base-reactive groups undergo a bond-breaking reaction to provide one or more polar groups.

6. The photoacid generator compound of claim 1 wherein R 1 is (CR a 2 ) n , wherein each R a is chosen from H, F, (C 1 -C 10 )alkyl and fluoro(C 1 -C 10 )alkyl; and n=0-6.

7. The photoacid generator compound of claim 1 wherein R 3 is chosen from H, (C 1 -C 30 )alkyl, fluoro(C 1 -C 30 )alkyl and (C 6 -C 20 )aryl.

8. The photoacid generator compound of claim 1 wherein X is a divalent linking group of the formula —X 2 t1 —(Y 2 ═X 3 )X 3 t2 —, wherein X 2 ═O, S, or NR; Y 2 ═C, S, or S═O, X 3 ═O or S; t1=0 or 1; and t2=0 or 1.

9. The photoacid generator compound of claim 1 wherein the photoacid generator of formula (I) has a structure

10. The photoacid generator compound of claim 1 wherein Z is —C(CF 3 ) 2 O— or a (C 5 -C 30 )cyclohydrocarbyl group comprising —C(CF 3 ) 2 O—; and R 3 is H.