Epoxy-containing ArF resists with narrow molecular weight distribution

Abstract

Terpolymers consisting of ␥-butyrolactone-2-yl methacrylate, 2-methyl-2-adamantyl methacrylate, and 1-methyl-1-͑6-methyl-7-oxabicyclo͓4,1,0͔hept-3-yl͒ethyl methacrylate were prepared by the reversible addition-fragmentation chain transfer polymerization technique. The molecular weight distribution of the polymers was 1.29-1.39. Although the polymers have epoxy units and cross-linking of the polymer occurred during prebake treatment, they worked as a highly sensitive positive-tone resist. The cross-linking efficiency of the resist was dependent on the type of amines used as a quencher. The line edge roughness values were dependent on the prebake temperature.

Synthesis of ArF photoresist polymer composed of three methacrylate monomers via reversible addition-fragmentation chain transfer (RAFT) polymerization

“…First, the proton peaks attributed to naphthalene (7.38-8.30 ppm) in 1 H NMR spectrum (Figure 2(a)) and pink color of the polymers suggests the existence of thiocarbonylthionaphalate moiety in the polymer. 28 Figure 3), indicating that the radical concentration are almost constant during the polymerization. [10][11][12][13][14]20 Third, the molecular weight of the polymerization with CPDN (entries 5, 7, and 9) increases with the conversions of monomers ( Figure 4(a)).…”

“…[11][12][13]15 2-Cyanoprop-2-yl-1-dithionaphthalate (CPDN) was synthesized and used as the RAFT chain transfer agent (CTA) in this research, because it is an effective CTA for the polymerization of methacrylate monomers. 28,[31][32][33] The influence of different monomer reactivities and different polymerization methods on the composition variation was postulated by studying conversion and composition changes with respect to polymerization time. In addition, the effect of different polymer homogeneities on lithographic performance was studied.…”

“…15,[21][22][23][24] Several research groups have studied the synthesis of ArF PR polymers using these LRP methods. [25][26][27][28][29][30] For example, various ArF PR polymers were prepared using ATRP or RAFT polymerization techniques, and the effects of their physical and chemical properties such as their molecular weights, PDI values, compositions, and structures, were studied with respect to lithographic performance. [25][26][27][28][29][30] However, the composition homogeneity of polymers has rarely been counted as the important factor for lithographic performance of PR polymers.…”

“…[25][26][27][28][29][30] For example, various ArF PR polymers were prepared using ATRP or RAFT polymerization techniques, and the effects of their physical and chemical properties such as their molecular weights, PDI values, compositions, and structures, were studied with respect to lithographic performance. [25][26][27][28][29][30] However, the composition homogeneity of polymers has rarely been counted as the important factor for lithographic performance of PR polymers. 3,4 In this study, a series of ArF PR polymers composed of three methacrylate monomers, such as 2-ethyl-2-adamantyl methacrylate (EAdMA), α-gamma-butyrolactone methacrylate (GBLMA), and 3-hydroxy-1-adamantyl methacrylate (HAdMA), were prepared via both FRP and RAFT polymerization under various conditions.…”

Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

“…The reduction in the minimum feature size in microelectronic devices requires the design of functional polymers with well‐defined molecular properties. Line edge roughness (LER) and line width roughness (LWR), which are parameters used to characterize pattern resolution, are influenced by physical/chemical properties such as molecular weight, dispersity ( or Đ), composition, and microstructure . Controlled radical polymerization (CRP) has emerged as a viable route toward making polymers with controlled microstructure and narrow molecular weight distributions, which were usually attained by ionic or other “living” polymerizations.…”