Novolak/DNQ based, chemically amplified photoresist

Patent metadata

Field	Value
Publication number	US-12276909-B2
Application number	US-201917056773-A
Country	US
Kind code	B2
Filing date	May 22, 2019
Priority date	May 24, 2018
Publication date	Apr 15, 2025
Grant date	Apr 15, 2025

Abstract

The present invention relates to resist compositions comprising a polymer component, a photoacid generator component (PAG), a photoactive diazonaphthoquinone component (PAC), a base component, a solvent component, and optionally, a heterocyclic thiol component. The polymer component is a Novolak derivative, comprising Novolak repeat units with free phenolic hydroxy moieties, and Novolak repeat units comprising phenolic hydroxy moieties protected with an acid cleavable acetal moiety. The acetal moiety is elected from a mono functional alkyl acetal moiety protecting a repeat unit comprising a Novolak phenolic hydroxy moiety, an acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety; a di-functional acetal comprising moiety, linking and protecting two repeat units comprising Novolak phenolic hydroxy moieties, forming a linking point in said polymer component between two different polymer chains in said polymer component, and a mixture of any of these three types of acid cleavable acetal moieties. The PAC component is selected from said acetal, comprising a moiety functionalized with a PAC moiety, protecting a repeat unit comprising a Novolak phenolic hydroxy moiety, a free PAC component, and a mixture of these two types of PAC components. The present invention also relates to the methods of using the present compositions in either in thick or thin film photoresist device manufacturing methodologies.

First claim

We claim:

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(CH 3 ) 2 —, —(C═O)— or —SO 2 —, 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(CH 3 )—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH 3 )—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene) x -O—CH(CH 3 )—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;

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 , 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(CH 3 ) 2 —, —(C═O)— or —SO 2 —, 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(CH 3 )—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH 3 )—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene) x -O—CH(CH 3 )—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;

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 , 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(CH 3 ) 2 —, —(C═O)— or —SO 2 —, 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(CH 3 ) 2 —, —(C═O)— or —SO 2 —;
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 , 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(CH 3 )—O—),
an alkyleneoxyalkyleneacetal moiety (-alkylene-O-alkylene-O—CH(CH 3 )—O—), and
an alkylene(oligooxyalkylene)acetal, (-alkylene(-O-alkylene) x -O—CH(CH 3 )—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;

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 , 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(CH 3 ) 2 —, —(C═O)— or —SO 2 —, and na, nc, ng, nk and np independently, are 0 to 3; nb, n

Assignees

• Merck Patent Gmbh

Inventors

• Toukhy Medhat A
• Liu Weihong
• Kudo Takanori
• Chen Hung-Yang
• Yin Jian

Classifications

• G03F7/30

  Imagewise removal using liquid means · CPC title

• G03F7/38

  Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} · CPC title

• G03F7/0236 Primary

  Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins · CPC title

• G03F7/0226

  characterised by the non-macromolecular additives · CPC title

• C09D163/04

  Epoxynovolacs · CPC title