US 12,276,909 B2
Novolak/DNQ based, chemically amplified photoresist
Medhat A. Toukhy, Flemington, NJ (US); Weihong Liu, Branchburg, NJ (US); Takanori Kudo, Bedminster, NJ (US); Hung-Yang Chen, Somerset, NJ (US); and Jian Yin, Bridgewater, NJ (US)
Assigned to Merck Patent GmbH, Darmstadt (DE)
Appl. No. 17/056,773
Filed by Merck Patent GmbH, Darmstadt (DE)
PCT Filed May 22, 2019, PCT No. PCT/EP2019/063216
§ 371(c)(1), (2) Date Nov. 19, 2020,
PCT Pub. No. WO2019/224248, PCT Pub. Date Nov. 28, 2019.
Claims priority of provisional application 62/675,939, filed on May 24, 2018.
Prior Publication US 2021/0382390 A1, Dec. 9, 2021
Int. Cl. G03F 7/023 (2006.01); C08G 59/14 (2006.01); C09D 163/04 (2006.01); G03F 7/022 (2006.01); G03F 7/30 (2006.01); G03F 7/38 (2006.01)
CPC G03F 7/023 (2013.01) [C08G 59/1477 (2013.01); C09D 163/04 (2013.01); G03F 7/0226 (2013.01); G03F 7/0236 (2013.01); G03F 7/30 (2013.01); G03F 7/38 (2013.01)] 17 Claims
 
1. A composition comprising a polymer component, a photoacid generator component (PAG), a photoactive diazonaphthoquinone compound (PAC) component, a base component, a solvent component, and an optional heterocyclic thiol component, wherein;
said polymer component is selected from the group consisting of Polymer Component C, Polymer Component D, Polymer Component E, and Polymer Component H,
Polymer Component C comprising repeat units having structures (I), (II), and (VI), where structure (VI) is an acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety;
wherein Ra, Rc and Rp are independently a C-1 to C-4 alkyl; Rb, Rd, and Rq are independently a —X-Phenol, wherein X is —O—, —C(CH3)2—, —(C═O)— or —SO2—, and na, nc, and np, independently, are 0 to 3; nb, nd, and nq, independently are 0 or 1, and the sum of na and nb, the sum of nc and nd, and the sum of np and nq, respectively, do not exceed 3;
Re, Rf, and Rr are independently selected from a C-1 to C-4 alkyl, PACb is a PAC component in the repeat unit having structure (VI) attached through a linking group Xd, wherein Xd is selected from the group consisting of,
a direct valence bond,
an alkylene moiety,
an alkyleneoxy moiety, wherein the alkylene end is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the oxy end of the alkyleneoxy moiety is attached to the PACb moiety, and
a moiety comprising an acetal selected from the group consisting of the following;
an alkyleneacetal moiety (-alkylene-O—CH(CH3)—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH3)—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene)x-O—CH(CH3)—O—),
wherein x is 2 to 6, and further wherein, in each of said acetal comprising moiety,
the alkylene end of this moiety is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the acetal portion of said moiety comprising an acetal is attached to the PACb moiety;

OG Complex Work Unit Chemistry
Polymer Component D comprising repeat units having structures (I), (III), (IV) and (VI), where structure (VI) is an acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety;
wherein the repeat units having structures (III) and (IV) are attached together through the positions designated by custom character, forming a di-functional acetal comprising moiety, forming a linking point in said polymer component between two different polymer chains in said polymer component, and further;
Ra, Rg, Rk and Rp are independently a C-1 to C-4 alkyl; Rb, Rh, Rl and Rq are independently a —X-Phenol, wherein X is —O—, —C(CH3)2—, —(C═O)— or —SO2—, and na, ng, nk and np independently, are 0 to 3; nb, nh, nl and nq, independently are 0 or 1, and the sum of na and nb, the sum of nh and ng, the sum of nl and nk, and the sum of np and nq respectively, do not exceed 3;
Ri, Rm, and Rr are independently selected from a C-1 to C-4 alkyl,
Xa is an alkylene, an -alkyleneoxyalkylene- moiety, or an -alkylene(-O-alkylene)x′- moiety wherein x′ is 2 to 6; and further wherein;
PACb is a PAC component in the repeat unit having structure (VI) attached through a linking group Xd, wherein Xd is selected from the group consisting of,
a direct valence bond,
an alkylene moiety,
an alkyleneoxy moiety, wherein the alkylene end is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the oxy end of the alkyleneoxy moiety is attached to the PACb moiety, and
a moiety comprising an acetal selected from the group consisting of the following;
an alkyleneacetal moiety (-alkylene-O—CH(CH3)—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH3)—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene)x-O—CH(CH3)—O—),
wherein x is 2 to 6, and further wherein, in each of said acetal comprising moiety, the alkylene end of this moiety is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the acetal portion of said moiety comprising an acetal is attached to the PACb moiety;

OG Complex Work Unit Chemistry
Polymer Component E comprising repeat units of structures (I), (III), (V) and (VI), where structure (VI) is an acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety;
wherein the repeat units having structures (III) and (V) are attached together through the positions designated by custom character, forming a di-functional acetal comprising moiety, forming a linking point in said polymer component between two different polymer chains in said polymer component,
Ra, Rg, Rn and Rp are independently a C-1 to C-4 alkyl; Rb, Rh, Ro and Rq are independently a —X-Phenol, wherein X is —O—, —C(CH3)2—, —(C═O)— or —SO2—, and na, ng, nn and np independently, are 0 to 3; nb, nh, no and nq, independently are 0 or 1, and the sum of na and nb, the sum of ng and nh, the sum of nn and no, and the sum of np and nq respectively, do not exceed 3;
Ri, Rr and Rm2 independently are selected from a C-1 to C-4 alkyl
Xb is —O—, —C(CH3)2—, —(C═O)— or —SO2—;
Xc is an alkylene, an -alkyleneoxyalkylene- moiety, or an -alkylene(-O-alkylene)x′- moiety wherein x′ is 2 to 6; and further wherein repeat unit of structures (III) and (V) are attached together through the positions designated by custom character, forming a di-functional acetal comprising moiety, forming a linking point in said polymer component between two different polymer chains in said polymer component;
PACb is a PAC component in the repeat unit having structure (VI) attached through a linking group Xd, wherein Xd is selected from the group consisting of the following;
a direct valence bond,
an alkylene moiety,
an alkyleneoxy moiety, wherein the alkylene end is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the oxy end of the alkyleneoxy moiety is attached to the PACb moiety, and
a moiety comprising an acetal selected from the group consisting of the following;
an alkyleneacetal moiety (-alkylene-O—CH(CH3)—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH3)—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene)x-O—CH(CH3)—O—),
wherein x is 2 to 6, and further wherein, in each of said acetal comprising moiety,
the alkylene end of this moiety is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the acetal portion of said moiety comprising an acetal is attached to the PACb moiety;

OG Complex Work Unit Chemistry
Polymer Component H comprising the repeat unit of structure (I), Structure (II), Structure (III), Structure (IV) and structure (VI) where structure (VI) is an acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety;
wherein the repeat units having structures (III) and (IV) are attached together through the positions designated by custom character, forming a di-functional acetal comprising moiety, forming a linking point in said polymer component between two different polymer chains in said polymer component, and further;
Re and Rf are independently selected from a C-1 to C-4 alkyl
Ra, Rc, Rg, Rk and Rp are independently a C-1 to C-4 alkyl; Rb, Rd, Rh, RI and Rq are independently a —X-Phenol, wherein X is —O—, —C(CH3)2—, —(C═O)— or —SO2—, and na, nc, ng, nk and np independently, are 0 to 3; nb, nd, nh, nl and nq, independently are 0 or 1, and the sum of na and nb, the sum of nh and ng, the sum of nl and nk, and the sum of np and nq respectively, do not exceed 3;
Ri, Rm, and Rr are independently selected from a C-1 to C-4 alkyl,
Xa is an alkylene, an -alkyleneoxyalkylene- moiety, or an -alkylene(-O-alkylene)x′- moiety wherein x′ is 2 to 6; and further wherein;
PACb is a PAC component in the repeat unit having structure (VI) attached through a linking group Xd, wherein Xd is selected from the group consisting of,
a direct valence bond,
an alkylene moiety,
an alkyleneoxy moiety, wherein the alkylene end is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the oxy end of the alkyleneoxy moiety is attached to the PACb moiety, and
a moiety comprising an acetal selected from the group consisting of the following;
an alkyleneacetal moiety (-alkylene-O—CH(CH3)—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH3)—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene)x-O—CH(CH3)—O—),
wherein x is 2 to 6, and further wherein, in each of said acetal comprising moiety,
the alkylene end of this moiety is attached to the acetal oxygen moiety of the repeat unit of structure (VI), and the acetal portion of said moiety comprising an acetal is attached to the PACb moiety;

OG Complex Work Unit Chemistry
and further wherein, said photoactive diazonaphthoquinone compound (PAC) component, is either said acetal comprising moiety functionalized with a PAC moiety protecting a repeat unit comprising a Novolak phenolic hydroxy moiety of structure (VI) present in said polymer component Polymer Component C Polymer Component D Polymer Component E Polymer Component H as sole PAC component, or is in combination with a free PAC component.