Extreme ultraviolet lithography at a wavelength of 13.5 nm has been prepared for next generation lithography for several
years. Of primary concern in EUV lithography is line edge roughness as well as high sensitivity. In recent years, various
types of resist, such as protected PHS resin resist and molecular resist, have been investigated. In order to reduce LER,
we have studied novel molecular resists which are promising alternative to polymeric photoresists for use as imaging
materials with improved resolution and line edge roughness. The work reported in this paper has focused on the
development of a new class of chemically amplified molecular resists that are composed of a single molecule which
contains all of the different functionalities desired in a chemically amplified resists. For the purpose of improvement of
the resist performance, we have designed the resist material of a protected polyphenol derivative (protected Compound
A). PAG moiety is bonded to Compound A to achieve uniform PAG density and to control the acid diffusion length in a
resist film. We analyzed uniformity of PAG density in a resist film by using gradient shaving preparation and TOF-SIMS
analysis. From the TOF-SIMS spectra, the ions intensities of the PAG moiety are almost constant from the surface to the
bottom of the film. Therefore, we can conclude that PAG is distributed homogeneously. Under e-beam exposure, a
100nm thick film of the PAG bonded molecular resist resolved lines down to 100nm. We also discussed the new design
for molecular resists, their synthesis and lithographic performance.
Our recent research effort has been focused on new top coating-free 193nm immersion resists with regard to leaching of
the resist components and lithographic performance. We have examined methacrylate-based resins that control the
surface properties of ArF resists thin films by surface segregation behavior. For a better understanding of the surface
properties of thin films, we prepared the six resins (Resin 1-6) that have three types fluorine containing monomers, a new
monomer (Monomer A), Monomer B and Monomer C, respectively. We blended the base polymer (Resin 0) with Resin
(1-6), respectively. We evaluated contact angles, surface properties and lithographic performances of the polymer blend
resists. The static and receding contact angles of the resist that contains Resin (1-6) are greater than that of the base
polymer (Resin 0) resist. The chemical composition of the surface of blend polymers was investigated with X-ray
photoelectron spectroscopy (XPS). It was shown that there was significant segregation of the fluorine containing resins
to the surface of the blend films. We analyzed Quantitative Structure-Property Relationships (QSPR) between the surface
properties and the chemical composition of the surface of polymer blend resists. The addition of 10 wt% of the polymer
(Resin 1-6) to the base polymer (Resin 0) did not influence the lithographic performance. Consequently, the surface
properties of resist thin films can be tailored by the appropriate choice of fluorine containing polymer blends.
With no apparent showstopper in sight, the adoption of ArF immersion technology into device mass production is not a matter of 'if' but a matter of 'when'. As the technology matures at an unprecedented speed, many of initial technical difficulties have been cleared away and the use of a protective layer known as top coat, initially regarded as a must, now becomes optional, for example. Our focus of interest has also sifted to more practical and production related issues such as defect reducing and performance enhancement. Two major types of immersion specific defects, bubbles and a large number of microbridges, were observed and reported elsewhere. The bubble defects seem to decrease by improvement of exposure tool. But the other type defect - probably from residual water spots - is still a problem. We suspect that the acid leaching from resist film causes microbridges. When small water spots were remained on resist surface after exposure, acid catalyst in resist film is leaching into the water spots even though at room temperature. After water from the spot is dried up, acid molecules are condensed at resist film surface. As a result, in the bulk of resist film, acid depletion region is generated underneath the water spot. Acid catalyzed deprotection reaction is not completed at this acid shortage region later in the PEB process resulting in microbridge type defect formation. Similar mechanism was suggested by Kanna et al, they suggested the water evaporation on PEB plate. This hypothesis led us to focus on reducing acid leaching to decrease residual water spot-related defect. This paper reports our leaching measurement results and low leaching photoresist materials satisfying the current leaching requirements outlined by tool makers without topcoat layer. On the other hand, Nakano et al reported that the higher receding contact angle reduced defectivity. The higher receding contact angle is also a key item to increase scan speed. The effort to increase the receding contact angle become very important issue for not only defectivity but also scanner throughput. Some of our experimental results along this line of study are also included in the report. The last topic covered is LWR (Line Width Roughness) as an essential leverage for performance improvement, especially for the smaller CD that immersion lithography is aiming to define. Our recent effort to find effect and working concept to reduce LWR with low leaching materials is also described.
Polyperinaphthalenic organic semiconductor (PPNOS) nano-particles are prepared by excimer laser ablation (ELA) of a 3, 4, 9, 10-perylenettracarboxylic dianhydride (PTCDA) target using XeCl excimer laser beams. Heterojunctions of the films consisting of nano-particles of PPNOS with Si wafers are fabricated. Well rectifier property is obtained for the junction of the PPN with a n-Si substrate. Current versus voltage curves of the heterojunction in the dark and under illumination show that the junction is promising as a photovoltaic cell. Furthermore, the films are applied to anode electrodes for ultra thin rechargeable Li ion batteries. In-situ Raman spectroscopy of the films under lithium ion doping and undoping is performed to elucidate the storage mechanism of lithium ion at cis-polyacetylene-type (phenanthrene-edge) of PPN structure.
A mixture of high Mw fractionated novolac resin and 2EAdMA (2-ethyl-2-adamantyle methacrylate)/HST (hydroxy styrene) copolymer brought about high resolution almost comparative to simple 2EAdMA/HST copolymer. Dry etching resistance was higher than 2EAdMA/HST copolymer. A mixture of unfractionated novolac resin and 2EAdMA/HST copolymer showed low resolution. Discrimination curve was measured by DRM on each case. Dissolution contrast of fractionated mixture was almost same as unfractionated one. Dissolution characteristics cannot tell the difference of resolution between fractionated and unfractionated novolac mixture.
Carbonous nano-particles basically consisting of PPN, one of the low dimensional conducting polymers, are prepared on substrates at various temperatures by excimer laser ablation of 3, 4, 9, 10-perylenetetracarboxylic dianydride using a 308nm pulsed excimer laser beam. Particles deposited on the substrates are applied to anode electrodes for ultra thin rechargeable Li ion batteries. Substrate temperature dependence of effective capacitance of lithium ions at first cycle are investigated. In addition, in-situ Raman spectroscopy of the particles under lithium ion doping and undoping is performed to elucidate the storage mechanisms of lithium ion at cis-polyacetylene-type edge of PPN structure. Reversible change of the spectrum in the region related C-H bending of PPN structure in lithium doping and undoping process supports a lithium insertion mechanism proposed by Zheng et al where lithium atoms bind on the hydrogene- terminated edged of hexagonal carbon fragments.
Polyperinaphthlenic organic semiconductor (PPNOS) films with polyperinaphthalene (PPN) structure for anode electrodes for ultra thin rechargeable Li ion batteries are prepared on temperature-controlled substrates by excimer laser ablation (ELA) of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) or mixture target of PTCDA with a few metal powder (PTCDA/M) using a 308 nm (XeCl) pulsed excimer laser beam. It is demonstrated that ELA of PTCDA at a fluence of less than 0.5 Jcm-2pulse-1 enables us to obtain PPNOS on a substrate at 300 degree(s)C. It is found that ELA of PTCDA/Co at a fluence of more than 1.0 Jcm-4pulse-1 leads to produce effectively fragments without anhydride groups of PTCDA. FT-IR and Raman spectroscopies reveal that ELA of PTCDA/Co enables us to obtain better-defined PPN films with electric conductivity of approximately 1x10-1Scm-1 on a substrate at 300 degree(s)C. Electrochemical doping characteristics of lithium ion into the films obtained by ELA are performed to verify the lithium doping mechanism by in situ Raman spectroscopy. Furthermore a trial piece of thin lithium ion rechargeable battery with the films is fabricated to appraise performance of the films as anode thin electrodes for ultra thin rechargeable lithium ion batteries.
Amorphous organic semiconductor thin films are prepared on temperature-controlled substrates by excimer laser ablation
(ELA) of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) or PTCDA/Co mixture target with a 308(XeCl) pulsed excimer laser beam. Drastic increase in conductivity was observed along with decrease in the IR peak intensities related to the side groups of PTCDA monomers for films prepared on substrates above 200°C. Electric conductivity of a film prepared on a substrate at 300°C comes up to 10-1Scm-1. Although carbon radicals are detected to some extent, indicating incomplete polymerization. Raman spectroscopic measurement reveals that this film basically consists of polyperinaphthalene (PPN) structure. This material is named polyperinaphthlenic organic semiconductor (PPNOS). ELA of mixture target of PTCDA and Co enables us to obtain PPNOS at room temperature. Electrochemical doping of PPNOS films with lithium ion suggests the passable performance of this film as anode electrodes of ultra thin rechargeable lithium ion batteries.
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