In a chemically amplified (CA) resist process, photochemically generated acid can diffuse in the resist matrix,
inducing the de-protection reactions. The concentration of acid in resist matrix should be constant during the
post-exposure-bake (PEB) treatment. In the practical resist processes, bottom anti-reflective coating (BARC) is
essentially important to provide reflectivity control for resist patterning. In some cases, however, the
photochemically generated acid in resist layer can diffuse into BARC layer, which causes the footing for resist
patterns. In this work, we have studied the diffusion of acid from CA resist layer to Si-hardmask (Si-HM) layer.
The Si-HM is essential for the multi-layer patterning process. The acid concentration in the resist layer was
estimated based on the de-protection reaction kinetics for the CA resist using rapid scan FT-IR spectroscopy. It
was found that the acid in resist layer diffused into the Si-HM layer. The diffusion efficiency of the acid was
dependent on the crosslinking density of the Si-HM and the chemical structure of the resist.
Non-conventional chemically amplified (CA) negative resist for EUV lithography was studied. We have
designed negative-tone EUV resist based on thiol-yne stepwise radical reactions. OH groups of
poly(4-hydroxystyrene) (PHS) were modified with functional units bearing C-C triple bond structure. Resist was
formulated as a mixture of modified-PHS, multifunctional thiol compound, and photoradical generator. The
present resist was developable with standard 2.38 wt% TMAH aq. solution. Photo-sensitivity of the resist was
obtained on irradiation at 254 nm and 13.5 nm. The resist was highly sensitive to EUV exposure. The sensitivity
and the contrast were affected by the structure of modified-PHS and process conditions.
In chemically amplified (CA) resist systems, photo-chemically generated acid can diffuse in resist matrix and the
acid induces the de-protection reaction of resists. To control the rate of the de-protection reaction, small amounts
of amines must be added as a quencher. The concentration of amines in resist matrix should be constant during
the post-exposure-bake (PEB) treatment. In the practical resist processes, organic bottom anti-reflective coating
(BARC) is essentially important to provide reflectivity control for resist patterning. In this study, we have
studied the diffusion characteristics of amines from resist layer to BARC layer by bake treatment. The amine
concentration in resist layer was estimated using the rate of de-protection reaction of conventional CA resist. It
was found that the diffusion rate of amines from resist layer to BARC layer was negligibly low.
Non-conventional chemically amplified (CA) resist was designed. Photo-induced thiol/ene radical reaction
was used to insolubilize the resist based on multifunctional thiol and poly(4-hydroxystyrene) (PHS) derivatives.
Hydroxy groups of PHS were modified with allyl or propargyl moiety. Dissolution property of the
modified-PHS in TMAHaq solution was affected by the modification degree. Resist was prepared by mixing
the modified-PHS, multifunctional thiol compound, and photoradical generator. Photosensitivity of the resist
was studied at 254 and 13.5 nm. The sensitivity was strongly affected by the modification degree of PHS,
molecular weight of PHS, molecular weight distribution of PHS, amounts of thiol compound and photoradical generator added. It was found that the present resist system was highly sensitive to EUV exposure.
Non-chemically amplified (CA) negative resist for EUV lithography was studied. Photo-induced thiol/ene
radical reaction was used to insolubilize the resist based on poly(4-hydroxystyrene) (PHS) derivatives.
Hydroxy groups of PHS were modified with allyl, norbornen, or methacrylate moiety. Dissolution property of
the modified-PHS in TMAHaq solution was studied. The degree of the modification of PHS strongly affected
the solubility in TMAHaq. Resist was a mixture of modified-PHS, multifunctional thiol compound, and
photo-radical generator. Photo-sensitivity of the resist was studied at 254 nm and 13.5 nm. The sensitivity
was affected the concentration of thiol compound added. It was found that the present resist system was highly
sensitive (5~6 mJ/cm2) to EUV exposure.
In chemically amplified (CA) resist process, photo-chemically generated acid is needed to diffuse in resist matrix
to induce the de-blocking reaction. The concentration of acid in resist matrix should be constant during the
post-exposure-bake (PEB) treatment. Organic bottom anti-reflective coating (BARC) is essentially important to
provide reflectivity control for resist patterning. In some cases, the photochemically generated acid and amine
added as a quencher can diffuse from resist layer to BARC layer, which causes the footing or undercut of resist
patterns. In this study, we have devised novel concept to qualitatively observe the diffusion of acids and amines
from resist layer to BARC layer and vice versa. The rate of de-blocking reaction of CA resist was used to
estimate the amount of acid in resist layer. It was found that the acid in resist layer can diffuse into BARC layer
and the acid in BARC layer can also diffuse into resist layer during PEB treatment. Diffusion efficiency of the
acid at resist / BARC interface was dependent on the chemical structure of resist and crosslinking density of
BARC materials. Diffusion of amines from resist layer to BARC layer was negligible.
Two types of dimethacrylate which have hemiacetal ester moiety in a molecule were synthesized from difunctional
vinyl ethers and methacrylic acid. UV curing of the monomers and photo-induced degradation of the UV cured resins
were investigated. On UV irradiation at 365 nm under N2 atmosphere, these dimethacrylates containing
2,2-dimethoxy-2-phenylacetophenone and triphenylsulfonium triflate became insoluble in methanol. The UV cured
resins degraded if acids were generated in the system. Present resins were applied to make a plastic replica of mold
for imprint lithography and the plastic replica was prepared in good form. The effect of imprint conditions on volume
shrinkage of methacrylates was investigated. Dimethacrylate that has adamantyl unit showed a low-shrinkage
property.
Two types of EUV resists based on poly(4-hyrdoxystyrene) (PHS) were designed, i.e., PHS-bound sensitizer (PHS-FISS)
and PHS/sensitizer blend (PHS/FITS). Imino sulfonate compounds were used as a photosensitizer. A PHS-bound
sensitizer resist was prepared by the conventional radical copolymerization of 4-(tertbutyldimethylsilyl)oxystyrene
(MSOST) and 9-fluorenilideneimino p-styrenesulfonate (FISS) and subsequent de-silylation of the copolymer. PHS
with low molecular weight distribution was obtained by the anionic polymerization of MSOST and followed by
de-silylation of the polymer. It was found that both types of resist were negative type and highly sensitive ( 10-20
mJ/cm2 ) on exposure at 254 nm and 13.5 nm. In the case of blended resist, the sensitivity was dependent on the
amounts of sensitizer added and molecular weight of PHS. Outgassing from the present resists on EUV exposure was
lower than that observed for MET-2D resist.
Polymers with methyl acetal ester moiety in the side chain as acid labile protecting group were synthesized and their thermal property, plasma stability and chemical amplification (CA) positive-tone resist characteristics were investigated. 2-Admantyloxymethyl (AdOM) groups in the copolymer indicated lower glass transition temperatures and higher thermal decomposition temperatures than those of 2-methyl-2-admantyl (MAd) groups in the copolymer. AdOM polymer film showed smooth surface roughness after Ar plasma exposure compared with MAd polymer film due to the high thermal stability. The activation energies (Ea) of these deprotection reactions were calculated from Arrhenius plots of these deprotection reaction rate constants. In the low post exposure bake (PEB) temperature region, the Ea of these resists decreased in the order MAd > AdOM. The low Ea methyl acetal resists displayed good thermal flow resist characteristics for contact holes printing. In addition, the low Ea methyl acetal resist achieved a wide exposure latitude of 8.1 % and depth of focus of 400 nm for printing 80 nm 1:1 dense line pattern using NSR-306C (NA 0.78, 2/3 annular). Furthermore, the 65 nm 1:1 dense lines using ASML XT1400 (NA 0.93, C-Quad) for low Ea methyl acetal resist pattern showed no tapered and no footing profiles and small roughness on the lines pattern sidewall was observed.
An in-situ quartz crystal microbalance (QCM) method was applied to quantitatively measure the outgassing from 157-nm resists, i.e., fluorinated cyclopolymer (FCP) and its derivatives blocked with alkoxymethyl ether units, in real time. The frequency change of quartz crystal coated with resist films was monitored during exposure and the mass desorbed from the resist films was calculated as amounts of outgassing. The sensitivity of the present QCM system was about 1 ng. The outgassing rate from FCP was much lower than FCP blocked with alkoxymethyl ether moiety, suggesting that the outgassing was mainly caused from the blocking units. Acidic components in outgassing were quantitatively measured by in-situ QCM technique using the quartz crystal coated with poly(4-vinylpyridine) (PVP) or a copolymer (DMEST) of 2-(dimethylamino)ethyl methacrylate and styrene. The acidic materials adsorbed on quart crystal were monitored during exposure and the mass adsorbed was calculated. The amount of acidic compounds in outgassing was dependent on fluorine content of the resist polymers.
An in-situ quartz crystal microbalance (QCM) method was applied to quantitatively measure the outgassing from F2 resist materials in real time. The frequency change of quartz crystal coated with resist films was monitored during exposure and the mass desorbed from the resist films was calculated as amounts of outgassing. The sensitivity of the present QCM systems was about 1 ng. The outgassing rate during exposure was strongly dependent on the structure of polymer backbone and blocking unit of resists. VUV light-induced degradation of resist films was investigated using reflection absorption FT-IR spectroscopy and it was confirmed that the outgassing was mainly generated from the photodegradation of acid labile protecting groups in resist films. Outgassing from photoacid generators incorporated in fluorinated cyclopolymers and poly(methacrylonitrile) films was also studied. Outgassing rate for diphenyliodonium triflate and diphenyliodonium nonaflate was slightly higher than those for triphenylsulfonium triflate and triphenylsulfonium nonaflate.
This paper describes a novel laser-based method for preparing microchannels in a bilayer system consisting of a UV sensitive polymer, acetophenone O-acryloyloxime (AAPO), layered with bovine serum albumin (BSA); BSA acts as a common blocking agent to prevent biomolecular attachment to the unexposed regions. The focus of the paper is on the use of a computer-controlled laser ablation system comprising a research-grade inverted optical microscope, a pulsed nitrogen laser emitting at 337 nm and a programmable X-Y-Z stage. By using a 100x oil immersion objective, channels of 1micrometers width and ca. 1 mm depth can be etched into the BSA-coated polymer. The precise width of the channel can be controlled by simply adjusting both the laser power and focusing. The addition of myosin to the base of these channels provides tracks on which actin filaments can move. By adjusting the width of the tracks, it is possible to regulate the direction of motion of the actin filaments.
With the objective to make smaller device structures at a given illumination wavelength the semiconductor industry is more and more trying to implement Phase-Shifting Masks (PSMs) as resolution enhancement technique for DUV lithography. However, with positive photoresists there is a phase edge problem. Using negative resists is the easiest approach to solve the phase edge problem. This is one of the reasons why negative resists are becoming more and more attractive for leading edge lithography. Therefore, we are developing a novel negative resist with 248/193 nm crossover capability. Most experiments were done in imitation of the CARLR bilayer resist process. The goal was to use established resist techniques and polymer materials, and just to change the generators and additives to get tone reversal. Using a photoacid generator (PAG) as additive leads to positive tone. In contrary with a photobase generator (PBG) and thermoacid generator (TAG) combination in a negative tone behavior is observed. Comprehensively, this blending concept allows the use of similar working polymers in both, positive and negative resists. The generator efficiencies were studied as well as the diffusion behavior of resist components during resist processing. Especially, process factors like baking conditions were investigated with the objective to control diffusion and limit resist outgassing in a high activation energy resist platform. Furthermore, in adaptation of the CARLR process, a separate liquid silylation step was integrated and investigated for various process conditions. In our paper we will discuss the characteristics and the lithographic capabilities of the novel methacrylate based negative resists. First promising results are based on DUV (248/193 nm) and ebeam exposures. Recent results with our positive version indicate the same outstanding possibilities. We expect a similar performance for the negative pendant in the near future.
We investigated characteristics of resists consisting of well- known resist polymers by the F2 excimer laser exposure. Negative-resist behavior due to crosslinking or decarboxylation was observed for poly(p-hydroxystyrene) based resists, polysilsesquioxane based resists and polynorbornenecarboxylate based resists. On the other hand, polymethacrylate based resists indicated a clear positive- resist behavior with high contrast without crosslinking. Therefore we studied further details of the characteristics of resists consisting of photodecomposable polymers such as methacrylate polymers and found methacrylate polymers bearing alicyclic groups to be resist with high dissolution contrast and little outgassing. The 200 nm L/S pattern with vertical profile at 1000 angstrom thickness was obtained by F2 excimer laser contact exposure in spite of poor transmittance of 30% per 1000 angstrom thickness. It was showed that the resolution by a 157 nm scanner with the lens of NA0.7/(sigma) 0.7 was 70 nm L/S and 40 nm iso-line at 1000 angstrom thickness by PROLITH/3D lithography simulator using experimental parameters.
The surface modification resist process, which gives negative-tone image owing to the polysiloxane formation on the expected resist surface using a chemical vapor deposition, was studied for ArF lithography. We have designed the resist polymer for improving the resolution, the pattern profile and the sensitivity. We developed the polymer having a photoacid generating unit and a polarity change unit for improving the resolution. Though there was a problem of the pattern degradation by heating in the dry development using a TCP etcher, 0.13 micrometers pattern was achieved with steep wall profile by introducing the thermally stable alicyclic unit to this polymer system. Moreover, we investigated the polymer having a photoacid generating unit and a hydrophilic unit for improving sensitivity. It was found that the introduction of an adequate amount of the hydrophilic unit was effective for improving the sensitivity.
With increase in density of semiconductor devices, 193 nm lithography is promising to attain smaller feature size patterns. Surface imaging process is useful for this lithography in terms of large depth of focus and prevention from substrate reflection. As the surface imaging process, so far we developed positive surface modification resist process using CVD for various device patterns' fabrication. To solve the issues of selective polysiloxane layer formation and sensitivity, we have improved this positive surface modification resist process using a new polymer, poly(cyclohexyl p-styrenesulfonate-co-methyl methacrylate), and a new photobase generator, O-phenylacetyl acetonaphthone oxime. 0.15 micrometers pattern was successfully fabricated using the new process with improved sensitivity of 80 mJ/cm2.
Improved tunneling spectroscopy was carried out on high-Tc BSCCO(2212) single crystal, and it provided us a reflection spectrum of the quasi-particle that mediates the strong Cooper pairing. The point contact junction enabled us to observe significant fine structure spectrum beyond the gap edge up to 0.2 eV. The spectrum peaks both in positive and negative bias ranges were found to be in a good one-to-one correspondence to the phonon density-of-states peaks at energy level $HBAR(omega) i reported by the neutron scattering experiment. The significant peaks at higher energies could be also assigned by n(epsilon) O + $HBAR(omega) i (n equals 0.1.2) where (epsilon) O is the breathing mode energy. Numerical computation in terms of the Eliashberg gap equation was carried out and the electron-phonon coupling intensity function (alpha) 2F((omega) ) was elucidated. Most of the peak modes were attributed to the optical phonons due to oxygen oscillations in and around the (CuO2)n plane, wherein the superconducting electronic state takes place. Consequently it turns out that the breathing mode has an essential role in the high-Tc superconductivity in the perovskite type-oxides.
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