Yoshitaka Komuro

Studies of the Photo Acid Generator Material Design for Chemically Amplified Photoresists

In current optical lithography, resolution is required to reach for 45 nm half-pitch and a chemically amplified resist (CAR) is used for a wide variety of applications. For ArF lithography beyond the 45 nm half-pitch, it is important to control pattern quality. The molecular design of a photo acid generator (PAG) is very important in the study to control not only acid strength but also acid diffusion length. Various novel PAGs that have different characteristics were synthesized for resist performance improvement. Acid molecular size was determined by molecular orbital (MO) calculation, and the acid diffusion coefficients (D) of these PAGs were evaluated by a bilayer method. As a result, it was found that acid diffusion coefficient (D) could not be controlled simply by adjusting anion molecular size. It may be presumed that the molecular interaction between acid generated by the exposure and polymer matrix areas is one of the most important key factors for controlling acid diffusion.

Electron and Hole Transfer in Anion-Bound Chemically Amplified Resists Used in Extreme Ultraviolet Lithography

The uniformity of acid generator distribution and the length of acid diffusion are serious problems in the development of resist materials used for the 16 nm node and below. Anion-bound polymers in which the anion part of onium salts is polymerized have attracted much attention for solving these problems. In this study, the reaction mechanism of an anion-bound polymer in cyclohexanone was clarified using pulse radiolysis. The design of an efficient electron and hole transfer system is essential to the enhancement of resist performance.

Modeling and simulation of acid generation in anion-bound chemically amplified resists used for extreme ultraviolet lithography

Extreme ultraviolet (EUV) lithography is the most promising candidate technique for the high-volume production of semiconductor devices with half-pitches of sub-10 nm. An anion-bound polymer, in which the anion part of onium salts is polymerized, has attracted much attention from the viewpoint of the control of acid diffusion. In this study, we modeled the acid generation processes in the anion-bound chemically amplified resists upon exposure to EUV radiation and developed a Monte Carlo simulation code. Using the developed simulation code, the dependence of the quantum efficiency of acid generation on the concentration of acid generator units was calculated. The calculated quantum efficiencies well agreed with the experimental values with a fitting error of less than 10%. The thermalization distance was considered to be approximately 3 nm. The blur of proton distribution intrinsic to the reaction mechanisms of anion-bound chemically amplified resists was roughly estimated to be 4.5–6.5 nm.

Patterning performance of chemically amplified resist in EUV lithography

Extreme Ultra Violet (EUV) lithography is one of the most promising candidate technologies for the high-volume manufacturing (HVM) of semiconductor devices at the sub-14 nm half pitch lines and spaces (LS) pattern for 7 nm node and beyond. EUV resists is strongly required high resolution (R) with high sensitivity (S) and low line edge/ width roughness (L) for HVM application. Experimental results on chemically amplified (CA) resist will be shown to study the influence of proton source, photo acid generator (PAG) cation and the other materials on lithographic performance, and then resist formulation designed for improving RLS trade-off will be discussed.

Development of EUV chemically amplified resist which has novel protecting group

Extreme Ultra Violet (EUV) Lithography is being thought to be one of the most promising candidate technologies to replace current optical lithography for the high-volume manufacturing of semiconductor devices at the 10 nm node and below. Through-put still seems to be under the target, so EUV resist materials are strongly required high resolution (R) with high sensitivity (S) and low line edge/width roughness (L). However, the chemically amplified resists should overcome RLS-trade-off. We focused on the development of EUV resist by the combination of the low activation energy protecting group (PG) and high quantum yield PAG for overcoming RLS trade-off.

Fundamental Studies on the Acid Generator to Improve the Resolution, Line Width Roughness, and Sensitivity Tradeoff under Ionizing Radiation

The effects of acid generation efficiency and other properties on the resolution, line width roughness (LWR), and sensitivity (RLS) tradeoff for extreme ultraviolet (EUV) photoresists were evaluated under electron beam (EB) exposure. The acid generators (AGs) introducing a trifluoromethyl group as an electron-withdrawing group on the sulfur atom had a much higher reduction potential than current AGs. We determined acid generation efficiency by the 13C-NMR method and standard titration. The dissolution inhibitory effect on the alkaline developer and the thermal property of the resist film using each AG were also evaluated. The RLS performance of resists containing AGs with a higher acid generation efficiency than conventional AGs was characterized using the relative Z-factor under EB exposure.

Block co-polymer approach for CD uniformity and placement error improvement in DSA hole grapho-epitaxy process

Directed Self-Assembly (DSA) of Block Co-Polymer (BCP) with conventional lithography is being thought as one of the potential patterning solution for future generation devices manufacturing. Many studies have been reported to fabricate the aligned patterns both on grapho and chemoepitaxy for semiconductor application1, 2. The hole shrink and multiplication by graphoepitaxy are one of the DSA implementation candidates in terms of relatively realistic process and versatility of chip design. The critical challenges on hole shrink and multiplication by using conventional Poly (styrene-b-methyl methacrylate) (PS-b-PMMA) BCP have been reported such as CD uniformity, placement error3 and defectivity. It is needed to overcome these challenging issues by improving not only whole process but materials. From the material aspect, the surface treatment material for guide structure, and process friendly BCP material are key development items on graphoepitaxy. In this paper, it will be shown in BCP approach about conventional PS-b-PMMA with additives and new casting solvent as PS-b-PMMA extension for CD uniformity and placement error improvement and then it’ll be discussed on what is the key factor and solution from BCP material approach.

Excluded volume effects caused by high concentration addition of acid generators in chemically amplified resists used for extreme ultraviolet lithography

The resolution of lithography used for the high-volume production of semiconductor devices has been improved to meet the market demands for highly integrated circuits. With the reduction in feature size, the molecular size becomes non-negligible in the resist material design. In this study, the excluded volume effects caused by adding high-concentration acid generators were investigated for triphenylsulfonium nonaflate. The resist film density was measured by X-ray diffractometry. The dependences of absorption coefficient and protected unit concentration on acid generator weight ratio were calculated from the measured film density. Using these values, the effects on the decomposition yield of acid generators, the protected unit fluctuation, and the line edge roughness (LER) were evaluated by simulation on the basis of sensitization and reaction mechanisms of chemically amplified extreme ultraviolet resists. The positive effects of the increase in acid generator weight ratio on LER were predominant below the acid generator weight ratio of 0.3, while the negative effects became equivalent to the positive effects above the acid generator weight ratio of 0.3 owing to the excluded volume effects.

Acid generation mechanism in anion-bound chemically amplified resists used for extreme ultraviolet lithography

Extreme ultraviolet (EUV) lithography is the most promising candidate for the high-volume production of semiconductor devices with half-pitches of sub 10nm. An anion-bound polymer(ABP), in which at the anion part of onium salts is polymerized, has attracted much attention from the viewpoint of the control of acid diffusion. In this study, the acid generation mechanism in ABP films was investigated using γ and EUV radiolysis. On the basis of experimental results, the acid generation mechanism in anion-bound chemically amplified resists was proposed. The protons of acids are considered to be mainly generated through the reaction of phenyl radicals with diphenylsulfide radical cations that are produced through the hole transfer to the decomposition products of onium salts.

Electron and hole transfer in anion-bound chemically amplified resists used in extreme ultraviolet lithography

The uniformity of acid generator distribution and the length of acid diffusion are serious problems in the development of resist materials used for the 16nm node and below. Anion-bound polymers in which the anion part of onium salts is polymerized have attracted much attention for solving these problems. In this study, the reaction mechanism of an anion-bound polymer in cyclohexanone was clarified using pulse radiolysis. The design of an efficient electron and hole transfer system is essential to the enhancement of resist performance.