In the realization of further miniaturization at scales of 10nm and below in semiconductor devices, it is essential to get the new resist design such as hybrid inorganic-organic resist materials for ionizing radiation to clarify the effect of metal resist structure on resist performances. In this study, some hybrid inorganic-organic resist materials known as metal-oxo clusters were synthesized and their lithographic characteristics were investigated to clarify the difference in sensitivity and resolution among Ti-based, Zr-based and Hf-based oxo clusters by using EUV and EB exposure. Our results indicated that the sensitivity in Hf-based oxo clusters was higher than those of Ti-based and Zr-based oxo clusters in both EB and EUV exposure. Also, we clarified that it is very important for the new resist design such as hybrid inorganic-organic resist to increase photo-absorption cross section and density of elements. In particular, the size and homogeneity of particle and film quality is very important for resist performance of hybrid inorganic-organic resist materials. In addition, it is clarified that etch durability increased by annealing metal oxo clusters.
Electron beam (EB) lithography is indispensable for the fabrication of photomasks including extreme ultraviolet masks. With the miniaturization of electronic devices, the requirement for photomasks becomes severe. When the feature size was decreased, the resist patterns collapse due to the surface tension of liquid. The decrease of resist film thickness is required for the high-resolution patterning in order to avoid pattern collapse. However, the quality of resist patterns is known to be degraded.
In this study, the resist film thickness dependence of the pattern formation of a chemically amplified electron beam resist on chromium nitride substrate was investigated.
The transistors have been miniaturized to increase their integration. With the miniaturization, the thickness of resist has been decreased to prevent them from collapsing. In this study, the resist thickness dependence of the pattern formation of a chemically amplified electron beam resist was investigated. The line width roughness (LWR) of resist patterns increased with the decrease of initial resist film thickness. It was found that the dissolution kinetics depended on the initial resist film thickness. The escape of low-energy electrons to the substrates is considered to have resulted in the difference in the dissolution kinetics and LWR
Introduction of EUV lithography using soft X-ray at wavelength of 13.5 nm has been started because of demand for miniaturization at low cost in mass production of semiconductor devices. Chemically amplified resist (CAR) has been utilized for many years and is also one of the promising materials for EUV resist. However, resist performances (resolution, line edge roughness, and sensitivity) show trade-off relationship and the searching for the solution has been still a serious problem. In the previous work, our group has shown that addition of Di-p-tolyl sulfone (DTS) into CAR increases acid generation efficiency (acid-generating promoter (AGP)). DTS acts as deprotonation promoter and recombination inhibitor between ionized polymer and electron. The resist performance upon exposure to electron beams (EB) was improved. In this study, we investigate the sensitivity of CAR to 13.5 nm EUV light upon adding new diphenyl sulfone derivatives. EB lithographic effects by adding some diphenyl sulfone derivatives were also studied. And the detail roles of AGP are also discussed.
The photo-mask in lithographic process of semiconductor device has an important role to transfer the downsized target image to the wafer. Due to the development of information society, demand for semiconductor devices has been growing. In order to increase photo-mask manufacturing throughput, the current density of electron beam (EB) has been getting higher. EB exposure increases the resist temperature on mask substrate inhomogeneous depending on its current density, shot size, writing order and etc. It is known that the resist sensitivity increases with irradiated resist temperature (heating effect). So, inhomogeneous temperature increase of resist on mask substrate disturbs precise pattern formation. However, the physical or chemical mechanism of heating effect has been still unknown. Here, we examined temperature dependence of acid generation process in chemically amplified resists (CARs). Poly(4- hydroxystyrene) (PHS) and poly(4-[(tert-butoxycarbonyl)oxy]styrene-co-4-hydroxystyrene) (PTBSHS) were used as CAR resin. Monte Carlo simulation moving thermalized electron under the electric field between polymer radical cations were performed with changing the temperature. From the simulation, it was revealed that the energy increase of thermalized electron contributes to the acid yield by 0.038 %/K. Quantification of the acid yields in resist films upon exposed to EB were performed with changing the temperature by titration method using Coumarin 6 (C6) as an acid sensitive dye. The acid yield increased by 0.14 %/K in PHS film and 0.21 %/K in PTBSHS film, respectively. Both values were higher than the simulation value (0.038 %/K). Pulse radiolysis experiment was also performed to observe deprotonation of polymer radical cations at 298 and 343 K. The decay of dimer radical cation of PTBSHS became 1.6 times faster at 343 K than that at 298 K. From the results, it is suggested that the heating effect mainly caused by the temperature dependence of deprotonation rate from the radical cations of PTBSHS.
To realize extreme ultraviolet (EUV) lithography for mass production of semiconductor devices, enhancements of performance of chemically amplified resist have been still important issue. In EUV resist, radiation chemical reactions occur after irradiations of the EUV light. Dynamics of chemical intermediates of EUV resist after exposure to the ionizing radiations is important for understanding new resist design. Fluorinated resists have been developed for ArF, F2, and EUV lithography. Fluorinated polymers are effective to enhance the sensitivity of the EUV resist because F atom has higher absorptivity of EUV photons. However, the fluorination effect on the radiation chemical reactions in the resist has not been clarified in detail. In this study, we investigated the dynamics of radical ions of fluorinated polymers (FPs) by pulse radiolysis method and quantum chemical calculations to clarify the reaction mechanism for EUV lithography.
Poly(4-hydroxystyrene) (PHS), a backbone polymer in resist constituents is also a promising material for
extreme ultraviolet (EUV) and electron beam (EB) lithography. Efficient deprotonation occurs from
radical cations of irradiated PHS. A hydroxystyrene unit is incorporated in the chemically amplified resist
structure as a proton source, in which reaction mechanism has not been well established. In this study,
deprotonation mechanism of an ionized PHS was characterized by using pulse radiolysis techniques. The
influence of several additives such as sulfoxides and amides with high acidity on the kinetics of the
deprotonation was investigated to clarify the fundamentals of the enhancement of deprotonation
efficiency from the PHS radical cation. Influence of the additives on the acid yield in thin film was also
investigated.
Chemically amplified resists have been widely used in the mass production line. An acid generation mechanism induced
by ionizing radiation with extreme ultraviolet (EUV) and electron beam is an important issue for improvement of the
resist performance such as sensitivity, roughness, and resolution below 16 nm. However, the details of deprotonation
kinetics from the ionized resist solid film immediately after the ionization have been still unclear. In this study, pulse
radiolysis of highly concentrated poly(4-hydroxystylene) (PHS) solutions was performed. The viscosity dependence on
the deprotonation dynamics of the ionized concentrated solutions was investigated to clarify the proton generation of
ionized PHS in a medium with low mobility. The deprotonation from the PHS radical cation becomes slower with
increasing PHS concentration. It is suggested that the deprotonation reaction is slower in a less mobile medium because
of decrease of the molecular motions.
For chemically amplified EUV resists, secondary electrons derived from ionization events play a critical role
in the sensitization of acid generators. In this study, we show the dependence of acid generation efficiency on
dose rate (fluence per pulse duration) by using 61 nm free-electron laser (FEL) light irradiation. The
wavelength of 61 nm (20.3 eV) is applied because single incident photon induces only single ionization event,
in contrast to the 13.4 nm EUV photon that induces 4.2 ionization events on average. The acid yield
efficiency has enhances with decreasing the dose rate. It is suggested that high density ionization enhances the
multiple spur effect.
The influence of degree of copolymerization of poly(styrene-ran-methyl methacrylate) [P(S-MMA)] on the
deprotonation mechanism for EUV chemically amplified resists were investigated by pulse radiolysis, quantity of the
acid yield, and density functional theory methods. The degradation of MMA unit occurs immediately before the hole
transfer to the styrene unit in P(S-MMA) in the low PS mole fraction (< 50 %). The hole transfer from MMA unit to
styrene units occurred in the high PS mole fraction (> 70 %). It is assumed that the formation of styrene multimer (n > 3)
causes the hole transfer.
In chemically amplified resists for extreme ultraviolet (EUV) and electron beam (EB) lithographies, the reaction
mechanism of acid generation is different from that for photolithography. However, details of acid generation are still
unclear. In particularly, details of the deprotonation dynamics of radical cations in solid resist films have not been
investigated. The dynamics of radical cations of resist polymer is important for understanding proton generation.
Poly(4-hydroxystyrene) (PHS) is a typical polymer for EUV and EB lithographies. We observed the dynamics of PHS radical cation in PHS film by using pulse radiolysis.
We have performed the three dimensional (3D) numerical analysis for a gap plasmon waveguide with two stubs in a
silver film by using the 3D finite-difference time-domain (FDTD) method. The simulated transmittance shows that such
the 3D structure works as a wavelength selective device with submicron size as already predicted in the 2D simulations.
We have also fabricated such a structure on a glass substrate by using the focused ion beam method. The width of the
gap is around 150 nm. The observed transmittance spectra of the structure have clearly indicated the wavelength
dependence and agree well with those obtained by a numerical simulation. Our results show that the structure proposed
by us is promising for a compact wavelength selective device.
We have analyzed the characteristics of three types of gap plasmon waveguides having wavelength
selective functions: one is structured by a Fabry-Perot resonator with reflectors, one is structured by a
slot resonator and the other is the waveguide with a single or two stubs. We have presented the
numerical results of the transmittance spectra for these structures calculated by using the finite-difference
time-domain method. The numerical results have clearly indicated that all structures of a sub-micron
size work properly as wavelength selective devices. The advantage of a stub type of waveguide
is on easiness in fabricating, while that for a Fabry-Perot type of waveguide is to lead to making the size
decrease considerably and relatively high Q-factor.
Poly(4-hydroxystyrene) (PHS) has been used in KrF excimer laser (248 nm) lithography as a backbone polymer, and is also a promising material for EUV or electron beam lithography. Analysis of the intermediate species is important for the control of reactions in resist materials. Since the size of integrated circuits fabricated for mass production will decrease below 30 nm and the size error must also be decreased to the molecular level, the elucidation of proton dynamics at the molecular level is also important for reducing the deviation of the resist pattern size. In this study, the dynamics of PHS radical cations were studied, because PHS radical cation is main source of proton. The transient absorption of PHS was observed in the near-infrared region (NIR) in p-dioxane solutions by pulse radiolysis. The intramolecular PHS dimer radical cation (M2+.) were observed, whereas p-cresol shows no distinct CR band. Although the radical cations of phenol derivatives are known to be easily deprotonated, it was found that M2+. formation prevents deprotonation by its charge resonance stabilization.
In chemically amplified resists, amines (base compounds) play important roles such as the control of acid diffusion, the sharpening of image slope and the improvement of environmental resistivity of resist materials. However, the details in the reactions between amines and protons in solid films are still unknown. In this research, we have investigated the neutralization of acids by amines in poly(4-hydroxystyrene) (PHS). Proton dynamics in the presence of amines in PHS films is discussed.
It is a well-known strategy for the improvement of resist performance to halogenate resist materials especially in electron beam and X-ray resists. However, the halogenation of polymers requires special caution for chemically amplified resists, because it may interfere with acid generation. In this work, the acid generation in poly[4-hydroxystyrene-co-4-(1,1,1,3,3,3-hexafluoro-2-hydroxypropyl)-styrene] films was investigated. Acid yields decrease as the ratio of hexafluoroalcohol units increases. This study showed that the reactivity of the polymers with low energy electrons (~0eV) correlates to the decrease of acid yields.
With the shrinkage of pattern sizes, the elucidation of reaction mechanisms at molecular level has become essential to resist design. Especially, proton dynamics is the most important issue for sensitivity and resolution of chemically amplified resists. Also, nanoscale topography of patterned resist surface such as line edge roughness may be explained by precise proton dynamics. In chemically amplified resists for post-optical lithographies such as EUV and electron beam lithography, it has been reported that protons come not from acid generators but from base polymers. Determining proton sources is a key to understanding reaction mechanisms at molecular level. In this article, we investigated deprotonation mechanism of poly(4-hydroxystyrene) and poly(4-methoxystyrene) on the exposure to ionizing radiation.
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