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).
We have designed and synthesized a molecular resist material, which has no distribution of the protecting
groups and have evaluated its performance as a molecular resist with EB and EUV exposure tool. The molecular resist
attained a resolution of sub-45 nm patterning at an exposure dose of 12 mJ/cm2. It was found that controlling the
distribution of the protecting groups in a molecular resist material has a great impact on improving Line Edge
Roughness (LER). Low LER values of 3.1 nm (inspection length: L = 620 nm) and 3.6 nm (L = 2000 nm) were
achieved with this molecular resist using Extreme UltraViolet (EUV) lithography tool.
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.
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.
We succeed in developing beneficial photoacid generator (PAG) for EUV exposure. In a high annealing type resist system in which poly-hydroxystyrene employed as a base resin, we found that sulfonium salts which employed cyclo(1,3-perfluoropropanedisulfone) imidate employed as a anion of PAG is more sensitive than perfluorobutanesulfonate employed as an anion of PAG under extreme ultraviolet (EUV) exposure. However, the sensitivities were different under EUV and electron beam (EB) exposures. It indicates that the distinctive acid production reaction is occurred under EUV exposure in comparing under EB exposure. As results of the time dependency mass spectroscopy and the Fourier Transform Infrared Spectroscopy (FT-IR), EUV induced reaction of cyclo(1,3-perfluoropropanedisulfone) imidate employed as an anion of PAG occurred more efficiently than that of perfluorobutanesulfonate employed as an anion of PAG.
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 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.
Larry Rhodes, Chun Chang, Cheryl Burns, Dennis Barnes, Brian Bennett, Larry Seger, Xiaoming Wu, Andy Sobek, Mike Mishak, Craig Peterson, Leah Langsdorf, Hideo Hada, Hiroaki Shimizu, Kazuhito Sasaki
Of all candidate 193 nm photoresist binder resins, transition metal catalyzed vinyl addition cyclic olefin (i.e., norbornene) polymers (PCO) hold the promise of high transparency and excellent etch resistance. In order to access lower molecular weight polymers, which are typically used in photoresists, α-olefin chain transfer agents (CTAs) are used in synthesizing vinyl addition poly(norbornenes). For example, HFANB (α,α-bis(trifluoromethyl)bicyclo
[2.2.1]hept-5-ene-2-ethanol) homopolymers (p(HFANB)) with molecular weights (Mn) less than 5000 have been synthesized using such chain transfer agents. However, the optical density (OD) at 193 nm of these materials was found to rise as their molecular weights decreased consistent with a polymer end group effect. Extensive NMR and MS analysis of these polymers revealed that olefinic end groups derived from the chain transfer agent were responsible for the deleterious rise in OD. Chemical modification of these end groups by epoxidation, hydrogenation, hydrosilation, etc. lowers the OD of the polymer by removing the olefinic chromophore, however, it does require a second synthetic step. Thus a new class of non-olefinic chain transfer agents has been developed at Promerus that allow for excellent control of vinyl addition cyclic olefin polymer molecular weight and low optical density without the need of a post-polymerization chemical modification. Low molecular weight homopolymers of HFANB have been synthesized using these chain transfer agents that exhibit ODs ≤ 0.07 absorbance units per micron. This molecular weight control technology has been applied to both positive tone and negative tone vinyl addition cyclic olefin binder resins. Lithographic and etch performance of positive tone photoresists based on these binder resins will be presented.
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.
Extreme ultraviolet (EUV) lithography requires a vacuum environment for exposure. Therefore the understanding of the outgassing hydrocarbon ion species of the photoresist becomes important. Contamination due to the hydrocarbons affects the optics of the EUV tool such as the reflectivity of the mask and the imaging mirror.
We discuss here of the outgassing dependence of resist polymer structure and solvent type under the EUV irradiation. The resist components require photochemical stability and low evaporating species for EUV lithography.
The Methacryl backboned polymer has indicated larger outgassing value rather than PHS backboned polymer, which due to the quaternary carbon induced de-polymerization reaction. The main reaction is seemed to be due to the ester structure decomposed reaction. The selection of the basic polymer structure, ester ratio in the backbone and protecting group are very important for a low outgassing resist design.
Our results show resist which contain PGME, MAK, and MMP as the solvent, have lower outgassing characteristics under the EUV irradiation. This characteristic is own to the low residual solvent content in resist film prior to the EUV irradiation. As for results, the high annealing type CA resist based on the PHS polymer and PGME solvent have the lowest outgassing characteristics under the EUV irradiation.
Various resists, which consisted of polymer systems, such as methacrylate, acrylate and cycloolefin/maleic anhydride (COMA), were investigated in the viewpoint of etching resistance, lithographic performance and shelf life. The oxide etching rate was in order of acrylate < methacrylate << COMA. The surface roughness of the acrylate type resist after oxide etching was the smallest among all samples. The methacrylate type resist showed high resolution capability as a line and space resist. On the other hand, pattern collapse was observed in the acrylate type resist, and low resolution was shown in the COMA type resist because of the large resist thickness loss. In the case of contacts, the acrylate type resist showed better linearity. The sensitivity of the acrylate and methacrylate type resists kept at room temperature did not changed in 20 days, while the sensitivity of the COMA type resist changed. It was found that the methacrylate type resist was the most suitable as a line and space resist and the acrylate type resist was the most promising as a contact hole resist.
Utilizing ETS-1 laboratory tool in Himeji Institute of Technology (HIT), as for the fine pattern replicated by using the Cr mask in static exposure, it is replicated in the exposure area of 10 mm by 2 mm in size that the line and space pattern width of 60 nm, the isolated line pattern width of 40 nm, and hole pattern width of 150 nm. According to the synchronous scanning of the mass and wafer with EUVL laboratory tool with reduction optical system which consisted of three-aspherical-mirror in the NewSUBARU facilities succeeded in the line of 60 nm and the space pattern formation in the exposure region of 10mm by 10mm. From the result of exposure characteristics for positive- tone resist for KrF and EB, KrF chemically amplified resist has better characteristics than EB chemically amplified resist.
The single layer chemically amplified resists are investigated for the extreme ultra-violet lithography. From the results of the sensitivity curve, the positive-tone resist of DP603 and the negative-tone resist of SAL601 have high sensitivities and high gamma values to the EUV exposure wavelength. Furthermore, by the optimization of both the dosage and the wafer focusing position, we succeed in replicating 0.056-micrometer-resist- pattern width on the exposure-field size of 10 mm X 1 mm on an 8-inches-diameter wafer. We confirm the resolution capability of the three-aspherical mirror imaging system that has been developed by the Himeji Institute of Technology.
We report the development of a novel acryl polymer with an (alpha) -hydroxymethyl acrylate in the application to 193nm chemically amplified negative-tone resist. This new polymer structure consists of ((alpha) -hydroxymethyl)acrylate and MAA. The ester and alcohol group in the polymer contribute to an intramolecule and/or intermolecular hybrid crosslinking reactions without crosslinker and in the presence of a photo generated acid as a catalysis. In an intramolecular crosslink reaction, the ester group reacts to a neighboring hydroxymethyl group within the polymer chain. As a result, a lactone group is made in the main polymer chain. On the other hand, in an intermolecular crosslink reaction, the ester group reacts to a hydroxymethyl group of another polymer chain to make an ester chain. In this reaction, the new polymer is densely crosslinked and fine resist pattern is obtained without having any swelling problem. Consequently, the resist is optimized and contains the new polymer, photoacid generator and a small amount of crosslinker. Under conventional illumination condition, 180nm line and space pattern are achieved without any kind of swelling problem. The sensitivity is 40 mJ/cm2 with the standard developer, NMD-3 2.38 percent.
Access to the requested content is limited to institutions that have purchased or subscribe to SPIE eBooks.
You are receiving this notice because your organization may not have SPIE eBooks access.*
*Shibboleth/Open Athens users─please
sign in
to access your institution's subscriptions.
To obtain this item, you may purchase the complete book in print or electronic format on
SPIE.org.
INSTITUTIONAL Select your institution to access the SPIE Digital Library.
PERSONAL Sign in with your SPIE account to access your personal subscriptions or to use specific features such as save to my library, sign up for alerts, save searches, etc.