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.
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.
We have designed and synthesized molecular resist material, which has just only two part protecting groups in
one molecule (Prot-Mad-2). The resist can resolve below 30 nm hp pattern. We analyzed decomposition reaction using
Prot-Mad-2 at the un-exposed and exposed area quantitatively by taking advantage of its property of high purity and
simple structure. From the HPLC results, it was found that main decomposition reaction was deprotection of Prot-Mad-2.
The ratio of one part de-protected material (Deprot-1-prot-Mad-1) and fully de-protected material (Deprot-2) changed
with exposure dose. It was found that exposure dose of surface roughness maximum coincided with the exposure dose
where materials of two-part protection, one part de-protection and fully de-protection existed equally in the resist film.
Furthermore, dissolution rates of Prot-Mad-2, Deprot-1-prot-Mad-1 and Deprot-2 were totally different. It is considered
that surface roughness was generated by different dissolution rates in the presence of Prot-Mad-2, Deprot-1-prot-Mad-1
and Deprot-2. Our result suggests that reducing a variety of dissolution rates at exposed and un-exposed boundary is a
key to improve line edge roughness (LER).
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.
In order to enable design of a negative-tone polyphenol resist using polarity-change reaction, five resist
compounds (3M6C-MBSA-BLs) with different number of functional group of &ggr;-hydroxycarboxyl acid were prepared
and evaluated by EB lithography. The resist using mono-protected compound (3M6C-MBSA-BL1a) showed 40-nm hp
resolution at an improved dose of 52 &mgr;C/cm2 probably due to removal of a non-protected polyphenol while the
sensitivity of the resist using a compound of protected ratio of 1.1 on average with distribution of different protected
ratio was 72 &mgr;C/cm2. For evaluation of the di-protected compound based resist, a di-protected polyphenol was
synthesized by a newly developed synthetic route of 3-steps reaction, which is well-suited for mass production. The
resist using di-protected compound (3M6C-MBSA-BL2b) also showed 40-nm hp resolution at a dose of 40 &mgr;C/cm2,
which was faster than that of mono-protected resist. Fundamental EUV lithographic evaluation of the resist using
3M6C-MBSA-BL2b by an EUV open frame exposure tool (EUVES-7000) gave its estimated optimum sensitivity of 7
mJ/cm2 and a proof of fine development behavior without any swelling.
We have designed and synthesized cholate derivatives (1,4-Bis(methyloxymethylcholate)cyclohexane: C2ChDM and 1,2-Bis(oxymethylcholate)ethane: C2E) to investigate the properties as a chemically amplified (CA) positive-tone Electron-beam (EB) resist material. C2ChDM and C2E which were easily obtained by one-step esterification from cholic acid and dichloride showed glass transition temperatures (Tgs), 85 and 84oC, respectively. These compounds were dissolved in propylene glycol monomethyl ether acetate (PGMEA) and formed amorphous thin films onto silicon wafers by using a spin-coat method. The etch rates of C2ChDM and C2E, which were measured under CF4/CHF3/Ar mixed gas process, were almost the same as poly (p-hydroxystyrene) (PHS). The model resist samples were formulated with C2ChDM and C2E as base matrix and photo-acid generator (PAG) originated from sulfonium-salt (resist-A and B, respectively). These resists showed good sensitivities with EB exposure. Furthermore, the FT-IR spectra of resist-A and B films unexposed and exposed by the EB lithography tool were measured. From the spectral changes of resist-A and B films, we confirmed that a cleavage reaction of ester bond occurred by EB irradiation and bake treatment, and these resists worked as common CA positive-tone resist. The evaluation results with the resist-A and B by using EB exposure tool indicated the resolution of 120 nm lines and spaces pattern.
We designed a novel chemically-amplified negative-tone molecular-resist compound of 3M6C-MBSA-BL, which is a γ-hydroxycarboxylated polyphenol (4,4'-methylenebis[2-[di(2-methyl-4-hydroxy-5-cyclohexylphenyl)] methyl]phenol (3M6C-MBSA)) for EB and EUV lithographies to be used in hp 45 and beyond technology nodes. After selection of photo acid generators (PAGs) and optimization of the concentration of PAG in the resist, we could demonstrate 40-nm line and space patterns resolution by EB exposure. Also dry-etching durability and 1-month shelf life at -20oC were confirmed. Small line-edge roughness (LER) values of 4.5 nm (inspection length: L = 620 nm) and 6.2 nm (L = 1800 nm) were achieved using the 3M6C-MBSA-BL resist.
We have investigated the possibility of amorphous low molecular weight polyphenols as a chemically amplified positive-tone electron-beam (EB) resist. Low molecular weight polyphenol, 4'4-methylenebis{2-[di(2-methyl-4-hydroxy-5-cyclohexylphenyl)]methyl} phenol (3M6C-MBSA) as a base matrix, was protected by 1-ethoxyethyl (EE) groups to control the dissolution rate in 0.26 N tetramethylammonium hydroxide aq. developer. The film distribution in the depth direction for resist components with a Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and the Fourier amplitude spectra of line-edge roughness (LER) have been investigated to understand the relationship between them for the resists formulated with 3M6C-MBSA and two types of photo acid generator (PAG), triphenylsulfonium perfluoro-1-butanesulfonate (TPS-PFBS) and triphenylsulfonium n-octanesulfonate (TPS-nOS). From these results, it was found that the resist film consisting of TPS-nOS showed more homogeneous in the depth film distribution than that with TPS-PFBS, and the resist with TPS-nOS also indicated the suppressed LER value of 5.1 nm in the wide frequency range. Therefore, the homogeneity of the resist film may affect the pattern LER.
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