Chemically amplified resists (CARs) have been widely used for lithography of semiconductors. To suppress stochastic defects, the increase in the number of absorbed photons is essential and the increase in acid generator concentration is needed to capture all the generated electrons. Therefore, the effect of the acid generators on the dissolution of the resist increased. In this study, radiation-induced decomposition of acid generator and dissolution of poly(4-vinylphenol) (PHS) containing 30 wt% of acid generators was investigated using pulse radiolysis, γ radiolysis, quartz crystal microbalance (QCM) methods. TPS-TF was used as the reference structure, and three acid generators with different anionic and cationic structures were prepared, respectively. The structure of the cation was found to affect the decomposition product ratio of the final product. Both cation and anion structures were found to affect the dissolution behavior of the PHS films.
Tetramethylammonium hydroxide (TMAH) aqueous solutions has been used as a developer for chemically amplified resists (CARs), dissolving polymer with polar groups generated by exposure. Although the dissolution kinetics of CARs has been widely studied, it is necessary to understand molecular-level information such as interaction between polymer chains, to consider the dissolution of thin and minute resist films that are used nowadays. In this study, we used dynamic light scattering (DLS) to study the state of PHS chains in TMAH aqueous solution. The effect of the concentration of each ionic species on dispersion of PHS chains was investigated using solutions whose base concentrations were changed by two methods: dilution with pure water and neutralization with acid. PHS chains were well dispersed as the base concentration and ionic strength of the solution increased, while they aggregated as these two factors decreased. We also studied the dissolution behavior of PHS films under nearly identical conditions using quartz crystal microbalance (QCM). The dissolution of the films was also affected by the two factors described above. In addition to this, with the decrease in the above two factors, we observed formation of large swollen layer as we have reported in the past. We assumed these effects on dissolution of films were mainly due to the acid-base equilibrium at the solid-liquid interface.
Photoresists have been widely used as patterning materials for electric devices such as displays and semiconductor. Understanding pattern formation mechanism is essential for the efficient development of resist materials. In this study, we investigated the dissolution kinetics of poly(4-hydroxystyrene) (PHS) with weight-average molecular weights (Mw) of 9000-30000 and molecular weight distribution (Mw/Mn) of 1.07-1.20. The dissolution kinetics of PHS films was observed in tetramethylammonium hydroxide (TMAH) aqueous developers using a quartz crystal microbalance (QCM) method. The TMAH concentration was changed from 0 to 2.38 wt%. The obtained data were analyzed using polynomial regression to clarify the effects of Mw and Mw/Mn on the dissolution kinetics of PHS films. From the results of analysis, both dissolving and swelling behavior largely depended on Mw/Mn. Mw had a little effect on the dissolving, and however, had a large effect on the swelling in dilute TMAH aqueous solution.
In the development of highly resolving and highly sensitive resist materials, stochastic phenomena (LER and stochastic defect generation) are a critical issue. In this study, the dependence of the transient swelling layer formation of resist backbone polymer on its molecular weight and dispersion was investigated for the development of highly resolving resist materials. The dissolution kinetics was measured for different molecular weights and dispersions using quartz crystal microbalance (QCM) method. The relationship between transient swelling layer and stochastic defect formation is discussed.
We investigated the dissolution kinetics of poly(4-hydroxystyrene) (PHS) in an alkali developer with tetramethylammoniumhydroxide (TMAH). Experiments using PHS with different molecular weights and molecular weight dispersions and developer with different concentrations of TMAH led to the clarification of the dissolution behavior. Not only a change in the dissolution time but also a change in the dissolution behavior was observed upon changing the concentration of the developer. The dissolution behavior depends on an index calculated from values indicating the effects of swelling and dissolving. The dissolution occurred through the swelling of the polymer bulk and the subsequent diffusion of polymer chains into the solution bulk. The development using the alkali aqueous solution system was complex. The swelling rate should not be much larger than the dissolving rate for the development of high-resolution resists because a high swelling rate causes the generation of defects during the fabrication of fine structures.
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.
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.
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.
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.
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.
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.
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