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.
It has been reported that the good correlation in sensitivity and resolution between EUV exposure and EB exposure because of the similar mechanism of the photochemical-reaction in photoresists during exposure. However, in the early stages of EUV resist development, there are problems on the points of the cost and time-consuming to evaluate all EUV resist materials by EB exposure. Therefore, we investigated the possibility of using KrF exposure as the initial screening of EUV resists. If the correlation between KrF exposure, EB exposure and EUV exposure can be found, it will be possible to evaluate photoresists in a step-by-step manner, such as screening with KrF exposure first, followed by EB exposure, and finally EUV exposure in the initial evaluation stage. In this paper, we report on our investigations in the case of novolac resists, PHS chemically amplified resists, acrylic chemically amplified resists, and EUV polymer resists.
Irradiation effects of poly(methyl methacrylate) (PMMA) induced by femtosecond-pulsed extreme ultraviolet (EUV) were investigated using Soft X-ray free electron laser (SXFEL) for realization of next generation extreme ultraviolet free electron laser (EUV-FEL) lithography. The sensitivity of PMMA upon exposure to femtosecond-pulsed SXFEL was much higher than that measured for conventional nanosecond-pulsed EUV source. The sensitivity enhancement upon exposure to femtosecond-pulsed SXFEL is similar to the result obtained using laser-induced-plasma based Soft X-ray laser (SXRL) (picosecond-pulsed EUV). This result speculates the reactions induced by femtosecond-pulsed SXFEL and picosecond-pulsed XRL were almost same, but it was different from those induced by nanosecond-pulsed EUV.
Some hybrid inorganic-organic resist materials known as metal-oxo clusters were synthesized and lithographic characteristics were investigated. In particular, the dissolution behaviors of metal oxo clusters were investigated by development analyzer. Our results indicated that the solubility of metal oxo clusters thin films decreased by the exposure to KrF, ArF and electron beam (EB). We clarified the sensitivity in Ti-based oxo clusters was higher than that of Zr-based oxo clusters in both KrF and ArF exposure. The dissolution rate in two kinds of metal oxo cluters was almost same in both KrF and ArF exposure. Furthermore, the dissolution contrast of Ti-based oxo clusters was higher compared to Zr-based oxo clusters. Metal oxo clusters resists have the potential as future negative tone photoresist and EB resist materials.
Extreme ultraviolet (EUV) lithography utilizes photons with 92 eV energy to ionize resists, generate secondary electrons, and enable electron driven reactions that produce acid in chemically amplified photoresists. Efficiently using the available photons is of key importance. To increase photon absorption, sensitizer molecules, containing highly absorbing elements, can be added to photoresist formulations. These sensitizers have gained growing attention in recent years, showing significant sensitivity improvement. Aside from an increasing absorption, adding metal salts into the resist formulation can induce other mechanisms, like higher secondary electron generation or acid yield, or modification of the dissolution rate that also can affect patterning performance. In this work, we used different sensitizers in chemically amplified resists. We measured experimentally the absorption of EUV light, the acid yield, the photoelectron emission, the dissolution rate, and the patterning performance of the resists. Addition of a sensitizer raised the acid yield even though a decrease in film absorbance occurred, suggesting an apparent increase in chemically resonant secondary electrons. While patterning results confirm a significant sensitivity improvement, it was at the cost of roughness degradation at higher sensitizer loading. This is hypothesized by the chemical distribution of the sensitizer in the resist combined with a modification of the dissolution contrast, as observed by dissolution rate monitor measurements.
The performance of chemically amplified resist is approaching its physical limit with the reduction of feature sizes due to the acid diffusion needed for the solubility change of resist polymer. The line edge roughness (LER) of chemically amplified resists rapidly increases in the sub-10-nm-half-pitch region when the half-pitch is decreased. Also, the stochastic defect (pinching and bridges) generation is a significant concern for the high resolution patterning with high throughput. To solve these problems, the increase of the density of resist films is an important strategy. Metal oxide nanoparticle resists have attracted much attention as the next generation resist used for the high-volume production of semiconductor devices because of their high density property. However, the sensitization mechanism of the metal oxide nanoparticle resists is unknown. Understanding the sensitization mechanism is important for the efficient development of resist materials. In the previous study[1], the numbers of electron-hole pairs required for the solubility change of the resist films were estimated for a zirconia nanoparticle and a ligand shell, respectively. In this study, the pattern formation mechanism of zirconia nanoparticle resist was investigated. The elementary reactions possibly induced in the zirconia nanoparticle resist were investigated using a pulse radiolysis method. The pulse radiolysis is a powerful method to directly observe the kinetics of short-lived intermediates produced by an ionizing radiation. The pattern formation mechanism was assumed by integrating the elementary reactions. The resist patterns fabricated using an EUV exposure tool were analyzed on the basis of the assumed pattern formation mechanism. In the material design of metal oxide nanoparticle resists, it is important to efficiently use the electron-hole pairs generated in nanoparticles for the chemical change of ligand molecules.
Acknowledgement
This work was partially supported by Ministry of Economy, Trade and Industry (METI) and the New Energy and Industrial Technology Development Organization (NEDO).
Reference
[1] T. Kozawa, J. J. Santillan, and T. Itani, “Electron–hole pairs generated in ZrO2 nanoparticle resist upon exposure to extreme ultraviolet radiation”, Jpn. J. Appl. Phys. 57, 026501 (2018).
EUV lithography utilizes photons with 91.6 eV energy to ionize resists, generate secondary electrons, and enable electron driven reactions that produce acid in chemically amplified photoresist. Efficiently using the available photons is of key importance. Unlike DUV lithography, where photons are selectively utilized by photoactive compounds, photons at 13.5nm wavelength ionize almost all materials. Nevertheless, specific elements have a significantly higher atomic photon-absorption cross section at 91.6 eV. To increase photon absorption, sensitizer molecules, containing highly absorbing elements, can be added to photoresist formulations. These sensitizers have gained growing attention in recent years, showing significant sensitivity improvement. But there are few experimental evidences that the sensitivity improvement is due to the higher absorption only, as adding metals salts into the resist formulation can induce other mechanisms, like modification of the dissolution rate, potentially affecting patterning performance. In this work, we used different sensitizers in chemically amplified resist. We measured experimentally the absorption of EUV light, the acid yield, the dissolution rate and the patterning performance of the resists. Surprisingly, the absorption of EUV resist was decreased with addition of metal salt sensitizers. Nevertheless, the resist with sensitizer showed a higher acid yield. Sensitizer helps achieving higher PAG conversion to acid, notably due to an increase of the secondary electron generation. Patterning data confirm a significant sensitivity improvement, but at the cost of roughness degradation at high sensitizer loading. This can be explained by the chemical distribution of the sensitizer in the resist combined with a modification of the dissolution contrast, as observed by Dissolution Rate Monitor.
The performance of chemically amplified resist is approaching its physical limit with the reduction of feature sizes due to the acid diffusion needed for the solubility change of resist polymer. The line edge roughness (LER) of chemically amplified resists rapidly increases in the sub-10-nm-half-pitch region when the half-pitch is decreased. Also, the stochastic defect (pinching and bridges) generation is a significant concern for the high resolution patterning with high throughput. To solve these problems, the increase of the density of resist films is an important strategy. Metal oxide nanoparticle resists have attracted much attention as the next generation resist used for the high-volume production of semiconductor devices because of their high density property. However, the sensitization mechanism of the metal oxide nanoparticle resists is unknown. Understanding the sensitization mechanism is important for the efficient development of resist materials. In this study, the sensitization mechanism of ZrO2 nanoparticle resist was investigated. The numbers of electron-hole pairs required for the solubility change of the resist films were estimated for a ZrO2 nanoparticle and a ligand shell, respectively. The radiation chemistry of ligands was investigated using a pulse radiolysis method. The pulse radiolysis is a powerful method to directly observe the kinetics of short-lived intermediate produced by an ionizing radiation. In the material design of metal oxide nanoparticle resists, it is important to efficiently use the electron-hole pairs generated in nanoparticles for the chemical change of ligand molecules.
Acknowledgement
This work was partially supported by Ministry of Economy, Trade and Industry (METI) and the New Energy and Industrial Technology Development Organization (NEDO).
Using an electron beam, thin polymeric films loaded with metal nanoparticles of silver were prepared by a one-step irradiation-induced reduction of the metal ions embedded in the polymer. The metal nanoparticles were observed by either optical absorption or microscopy. The mechanism of the reduction of metal ions and of the polymer crosslinking were deduced from the average absorbance measurements. In view of realizing specific patterns of high resolution using the electron beam, electron beam produces 200 nm wide lines that can be separated by unexposed spaces of adjustable width, where precursors were dissolved. The resolution of the electron beam has been exploited to demonstrate the achievement of nanopatterning on polymer films using a direct-writing process. This method supplies interesting applications such as masks, replicas, or imprint molds of improved density and contrast.
Directed self-assembly (DSA) was investigated on self-assembled monolayers (SAMs) of 6-(4-nitrophenoxy) hexane-1-thiol (NPHT), which were chemically modified by electron beam (EB) irradiation. By irradiating a responsive interfacial surface, the orientation and selective patterning of block copolymer domains could be achieved. We demonstrated that spatially-selective lamellar orientation of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) could be induced via modification of an underlying SAM; for instance the conversion of an NO2 group to an NH2 group, induced by EB. The lamellar orientation of PS-b-PMMA was controlled by the change in the polarity of different regions of the SAM using EB lithography. The reductive treatment of SAM substrates plays a crucial role in the orientation of block copolymer. This method might greatly simplify block copolymer DSA processes as compared to the conventional multi-step chemo-epitaxy DSA process. By examining the lamellae orientation by EB, we found that the vertical orientation persists only for appropriate an irradiation dose and annealing temperature.
Ionizing radiations such as extreme ultraviolet (EUV) and electron beam (EB) are the most promising exposure source for next-generation lithographic technology. In the realization of high resolution lithography, it is necessary for resist materials to improve the trade-off relationship among sensitivity, resolution, and line width roughness (LWR). In order to overcome them, it is essential to understand basic chemistry of resist matrices in resist processes. In particular, the dissolution process of resist materials is a key process. Therefore, it is essential for next-generation resist design for ionizing radiation to clarify the dissolution behavior of the resist film into developer. However, the details in dissolution process of EUV and EB resist films have not been investigated thus far. In this study, main chain scission and dissolution behavior of poly(methyl methacrylate) (PMMA) as main chain scission type resist was investigated using quartz crystal microbalance (QCM) method and gel permeation chromatography (GPC) in order to understand the relationship between the degree of PMMA degradation and dissolution behavior. The relationship between the molecular weight after irradiation and the swelling behavior was clarified.
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.
EUV lithography is the most favorable process for high volume manufacturing of semiconductor devices beyond 1X nm half-pitch at present. Many efforts have revealed effective proton sources in acid generation in EUV resists, and the effective proton generation and the control of the generated acid diffusion are required to improve the breakthrough of the resolution - line width roughness - sensitivity(RLS) trade-off. To clarify the lithographic performance of these derivatives, we synthesized the acrylic ter/tetrapolymers containing novel lactone derivatives - LCHO and LAATB - as model photopolymers and exposed the resist samples based on these polymers to EUV and EB radiation. On the basis of the lithographic performances of these photoresists, we evaluated the characteristics of lactone derivatives upon exposure to EUV radiation. We discuss the relationship between the chemical structures of these derivatives and lithographic performance.
It is challenging to implement extreme ultraviolet (EUV) lithography for mass production because the demands for the EUV resist materials are very strict. Under such circumstances, it is important in EUV resist design to clarify the dissolution behavior of the resist film into alkaline developer. In particular, the dissolution in exposed area of resist films is one of the most critical processes. However, the details in dissolution process of EUV resist have not been investigated thus far. In this study, the dissolution of poly(4-hydroxystyrene) (PHS) polymer and PHS partially-protected with t-butoxycarbonyl group (t-BOC-PHS) with and without additives such as acid generator and amines was studied by using the quartz crystal microbalance (QCM) method. The dissolution behavior of thin films was investigated by varying the exposure dose and the acid generator concentration from the standpoint of a systematic understanding of the effects of each resist component on dissolution kinetics. The dissolution speed became slower with increase of TPS-tf concentration in PHS and t-BOC-PHS. It is important for the EUV resist design to take into account the concentration of undecomposed PAG.
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.
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 better understanding of electron beam resist processes, it is important to characterize the resist materials on the basis
of their reaction mechanisms. In this study, the basic parameters which characterize the chemical reactions for latent
image formation upon exposure to electron beam were evaluated. The electron beam resist used was a chemically
amplified resist, the backbone polymer of which is poly(4-hydroxystyrene). 49% of the hydroxyl groups were protected
with t-butoxycarbonyl groups. The stopping power was 0.529 eV nm-1. The G-value of acid generation was 2.5. The
effective reaction radius for deprotection was approximately 0.02 nm. The diffusion constant of acids was 1.3 nm2 s-1.
The diffusion constant of quenchers was significantly lower than that of acids. The product of LER and chemical
gradient (dm/dx) was approximately 0.06.
Novel resist materials are required for lithographic processing with ionization radiation such as extreme ultraviolet (EUV) and electron beam (EB) exposure tool. In this study, we developed positive-tone chemically amplified molecular resists based on noria derivatives and calixarene derivatives and evaluated the lithographic performance using EUV and EB. We make clear that a small change in modification of noria resists can cause a significant change of sensitivity. Especially, it is useful for the improvement of resist sensitivities to use protecting groups such as 2-acetyloxy-2-methyladamantyl ester (AD) groups and ethoxy groups. Also, novel calixarene derivative such as pillar[5]arene protected by AD showed a semi-isolated pattern with the line width of 40 nm (pitch: 100nm). Noria derivatives and calixarene derivative resists were promising candidates because of high sensitivity, high resolution and etch durability similar to conventional resist such as ZEP 520A and UVIII.
EUV lithography is the most favorable process for high volume manufacturing of semiconductor devices beyond 1X nm half-pitch. Many efforts have revealed effective proton sources in acid generation in EUV resists, and the effective proton generation and the control of the generated acid diffusion are required to improve the breakthrough of the resolution - line width roughness - sensitivity(RLS) trade-off. To clarify the lithographic performance of these derivatives, we synthesized the acrylic terpolymers containing novel hydrophilic derivatives as model photopolymers and exposed the resist samples based on these polymers to EUV and EB radiation. On the basis of the lithographic performances of these resist samples, we evaluated the characteristics of hydrophilic derivatives upon exposure to EUV radiation. We discuss the relationship between the chemical structures of these derivatives and lithographic performance.
EUV lithography is the most favorable process for high volume manufacturing of semiconductor devices below 1X nm
half-pitch. Many efforts have revealed that the effective proton generation and the control of the generated acid diffusion
are required to improve the breakthrough of the RLS trade-off. For the development of EUV resists, the novel protecting
derivatives were designed. To clarify the lithographic performance of these derivatives, we synthesized the acrylic
polymers containing these derivatives as model photopolymers and exposed the resist samples based on these polymers
to EUV/EB radiation. On the basis of the lithographic performances of these resist sample, we evaluated the
characteristics of novel protecting derivatives upon exposure to EUV/EB radiation. We discuss the relationship between
the chemical structures of these derivatives and lithographic performance.
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.
The requirements for the next generation resist materials are so challenging that it is indispensable for feasibility of EUV lithography to grasp basic chemistry of resist matrices in all stage of resist processes. Under such circumstances, it is very important to know dissolution characteristics of the resist film into alkaline developer though the dissolution of exposed area of resist films in alkaline developer to form a pattern is a complex reactive process. In this study, the influence of EUV and KrF exposure on the dissolution behavior of polymer bound PAG and polymer blended PAG was studied in detail using quartz crystal microbalance (QCM) methods. The difference in swelling formation between KrF and EUV exposure was observed. It is likely that difference of reaction mechanism induces the difference of these swelling. Also, it is observed that the swelling of polymer-bound PAG is less than that of polymer blended PAG in both KrF and EUV exposure. This result indicates that polymer-bound PAG suppresses swelling very well and showed an excellent performance. Actually, the developed polymer bound-PAG resist showed an excellent performance (half pitch 50 nm line and space pattern). Thus, polymer bound PAG is one of the promising candidate for 16 nm EUV resist.
The purpose of this study is development of a trapping system for nano-particles by periodically localized light and of a
detecting system for the trapped state by an ellipsometoric method. Nano-particles are of interest for some different
attractive properties with a bulk body in terms of their reactivity. Those attractive properties are applicable to production
of an optical element and a device. For production of nano-particles, it is necessary to manipulate nano-particles and to
measure the trapped state without contact in micro region. In this study, periodically localized light which is generated
by the nano-periodic structure allows us to trap nano-particles. Evaluation of trapping can be accomplished by using a
rotating-analyzer ellipsometer for comparing the ellipsometrical parameter before and after trapping. In confirmation of
affectivity ellipsometrical method, we obtained that the trapped state associated with varying a shape of the nanoperiodic
structure depends on polarization properties. The trapping light intensity also was found to depend on trapping
volume of the nano-particles. From experimental results, the nano-particles can be trapped by the periodically localized
light. And the trapping volume was found to increase with increasing in trapping light intensity. Hence, this system
achieved trapping and deducing nano-particles.
The trade-off among resolution, sensitivity, and line edge roughness (LER) is the most serious problem in actualization
of extreme ultraviolet (EUV). As feature sizes are reduced, it becomes very strict to simultaneously meet these
requirements. Also, reaction in resist materials induced by EUV photon is more complicate. In chemically amplified
EUV resists, not acid generator but polymers mainly adsorbed EUV photons. The secondary electrons are generated from
polymer upon exposure to ionizing radiation such as EUV radiation and electron beam. Therefore, the increase in
secondary electrons generated by EUV photons adsorbed in resist film is very important factor in the resist design.
Therefore, it is essential to know the ionization mechanisms of backbone polymers and understand the reaction
mechanism in details in order to accomplish high sensitivity and ultra-fine pattern in EUV lithography. We investigated
the photoelectron spectra of typical backbone polymers for chemically amplified EUV resists using ultraviolet
photoelectron spectroscopy (UPS). Also, the structure degradations in polystyrene (PS) derivatives thin films induced by
EUV radiation were analyzed by X-ray photoelectron spectroscopy (XPS) and UPS.
The yields of acid have been measured in the electron-beam irradiation of triphenylsulfonium triflate (TPS-Tf) and
pinanediol monosulfonates, which consist of tosylate (PiTs), 4-fluorobenzenesulfonate (Pi1F), or 4-trifluoromethylbenzenesulfonate
(Pi3F), as an acid amplifier blended in 4-hydroxystyrene matrixes. The acid yields efficiency
decreases when PiTs is present, while its efficiency increases in the presence of Pi3F. Reactions of the electrons with
TPS-Tf and pinanediol monosulfonates have been studied using pulse radiolysis in liquid tetrahydrofuran (THF) to
evaluate the kinetic contributions to acid production. The THF-solvated electrons react with PiTs, Pi1F, and Pi3F to
produce the corresponding radical anions; the rate constants are estimated to be 4.1, 5.1, and 9.2 × 1010 M-1 s-1,
respectively. Electron transfer from PiTs•-, Pi1F•-, and Pi3F•- radical anions to TPS-Tf occurs with the rate constants of
5.7×1010, 1.2×1011, and 6.3 × 1010 M-1 s-1, respectively. The long-lived Pi3F•- efficiently undergoes the electron transfer
to TPS-Tf to form the TPS-Tf•-, which subsequently decompose to generate TfOH. On the other hand, the decay
channels of PiTs•- and Pi1F•-, which possess a relatively short lifetime, are presumably dependent on its reactions with
solvated protons (charge recombination) rather than the electron transfer to TPS-Tf. The novel acid production pathway
via the electron transfer from pinanediol monosulfonate radical anions to TPS-Tf is presented.
Extreme ultraviolet (EUV) lithography is the most favorable process for high volume manufacturing of semiconductor
devices at 22nm half-pitch and below. Many efforts have revealed that the phenolic hydroxyl groups of polymers are
also an effective proton source in acid generation in EUV resists, and the effective proton generation and the control of
the generated acid diffusion are required to improve the breakthrough of the resolution - line width roughness -
sensitivity (RLS) trade-off. To clarify the lithographic performance of these derivatives, we synthesized the acrylic
terpolymers containing phenolic and alcoholic hydroxyl derivatives as model photopolymers and exposed the resist
samples based on these polymers to EUV and electron beam (EB) radiation. On the basis of the lithographic performances of these resist samples, we evaluated the characteristics of phenolic and alcoholic derivatives upon exposure to EUV radiation. We discuss the relationship between the chemical structures of these derivatives and lithographic performance.
We developed negative-tone chemically amplified molecular resists based on a fullerene derivative and evaluated the
lithographic performance using 75 keV electron beam (EB) exposure tool to explore the potential of fullerene derivatives
as a negative-type EB resist with high resolution and high etching durability. The etching rate of fullerene derivatives is
lower than that of conventional resist materials such as PHS, ZEP530 and UVIII. Although a dose of 800 μC/cm2 is
required, 60 nm line resolution and aspect ratio five was obtained in best of four kinds of fullerene derivative films. Also,
the effect of acid generators to a fullerene derivative resists were investigated. Fullerene derivative resists are a
promising candidate for nanolithography because it is essential for next generation lithography to have high aspect ratio related collapse of high resolution pattern and high etching durability in ultra-thin films.
Polymer structure effects on the dissolution kinetics and deprotection reaction were investigated to understand inherent
extreme ultraviolet (EUV) resist characteristics because it is important for EUV lithography to select appropriate
protecting group and protecting ratio. The difference of activation energy caused by protecting groups and protecting
ratio was observed. For small protecting group such as tert-butoxy carbonyl group and ethoxy ethyl group, dependence
of activation energy on protecting ratio was small. On the other hands, for bulky protecting group such as naphtoxy
group protecting ratio significantly affect the activation energy probably due to the effect of steric hindrance. Also, the
deterioration of resist sensitivity was observed with increase of protecting ratio while the dissolution slope increase with
increase of protecting ratio. A slight difference in Rmax was observed due to the difference of resulting products because
it is not chemically identical to polyhydroxystyrene (PHS) because of side reaction occurred during post exposure bake
(PEB). Also, Rmin decreased with increase of protecting ratio. Thus, the dissolution rates and sensitivity were more
affected by changing the protection ratio of polymer than the type of protecting group.
We developed a chemically amplified molecular resist based on a fullerene derivative and evaluated the lithographic
performance using 75 keV electron beam (EB) exposure tool to explore the potential of fullerene derivatives as a
positive-type EB resist with high resolution and high sensitivity properties. The etching rate of fullerene derivative is
almost similar to that of ZEP and UVIII. Also, the fullerene derivative resist containing 6 wt% acid generator shows a
sensitivity of 33 &mgr;C/cm2 when it was exposed to 75 keV electron beam and postbaked at 170 °C. Although it required a
dose of 800 &mgr;C/cm2, a fullerene derivative film yielded line resolution of better than 30 nm. Moreover, the effect of the
types of acid generators to the resist performance of fullerene derivatives was investigated. It is very important for a
fullerene derivative resist to select appropriate acid generator and process conditions. Fullerene derivative resists are a
promising candidate for nanolithography.
For chemically amplified resists which generally consists of a polymer and an acid generator, the homogeneity of resist
materials is a serious issue. The incorporation of acid generators into polymers via covalent bonds has attracted much
attention because it removes the compatibility problem of acid generators with polymers. In this study, we designed a
single-component chemically amplified resist, taking advantage of the difference of reaction mechanisms between
electron beam and photoresists. The designed resist has a hydroxyl group as a proton source and halogen atoms as an
anion source for acid generation. The developed resist showed an excellent performance.
KEYWORDS: Line edge roughness, Diffusion, Polymers, Ionization, Chemically amplified resists, Line width roughness, Electron beams, Lithography, Optical lithography, Monte Carlo methods
Nanoscale resist topography such as line edge roughness (LER) or line width roughness (LWR) is the most serious concern in sub-100 nm fabrication. Although many factors have been reported to affect LER, the generation mechanism of LER is still unclear. It is well known that the slope of image contrast correlates to the degree of roughness. However, significant LER is sill observed in chemically amplified resists for electron beam (EB) lithography, which can produce a steeper slope of image contrast than photolithography. To make clear a cause of LER, the distribution of protons and counter anions generated in chemically amplified EB resists was investigated. It was found that counter anion distribution is significantly different from proton distribution. Counter anions are inhomogeneously distributed outside a relatively smooth edge of proton distribution. This is caused by the fact that acid generators can react with low energy (~ 0 eV) electrons. The inhomodeneous distribution of counter anions outside proton distribution is considered to contribute to LER formation in chemically amplified resists for EB lithography.
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.
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