Chemically amplified resists have served as high resolution and high photospeed patterning materials in the fabrication of modern microelectronic devices for more than two decades. A
significant amount of research during that time, and in particular more recently, has focused on minimizing line width roughness and on improving the achievable resolution and sensitivity of resist
materials. While these lithographic parameters are certainly important, the distortion of the resist pattern during wet processing and subsequent drying can have significant negative impacts on performance and is often relatively overlooked as a major resist resolution and performance limiter. Resist pattern distortion after development and during drying is mainly due to the unbalanced
capillary forces created due to pattern asymmetries which give rise to variations in liquid meniscus radii of curvature as the final rinse liquid is dried from the pattern. These capillary forces are
dependent upon the surface tension of the final rinsing solvent, the contact angle of the rinse liquid with the side wall of the resist line, and the pattern space widths and sidewall angles. The demand
for resist films with smaller feature sizes has led to a reduction in resist pattern dimensions resulting in overall poor mechanical strength and a decrease in the adhesion forces at the resist line/substrate interface. In this work, the pattern collapse behavior of a hydroxystyrene-based resist copolymer is studied. Ultra-thin film effects and the role of the feature width of the resist line on pattern collapse are also investigated.
Chemically amplified resists (CAR) have successfully facilitated the development of deep ultra-violet (DUV) and 193 nm lithography techniques for more than two decades due to their acid-catalyzed deprotection scheme that enhances their photospeed. This acid-catalyzed mechanism provides a method for amplifying the initial chemical reactions caused by interaction of radiation with the resist film, thus making each interaction event between radiation and resist more productive. However, when switching from low energy photolysis to high energy radiolysis, changes in the manner in which the radiation interacts with the resist material can alter the acid generation efficiency and mechanism of PAG excitation. In high energy radiation cases where the radiation energy exceeds the ionization potential of the PAG and the polymer resin, the radiation absorption in the resist film becomes non-selective. The ratio of PAG excited by direct excitation as compared to polymer or matrix sensitization pathways can shift heavily in favor of matrix sensitization in such high energy exposure cases. Such sensitization pathways may become a potential method for enhancing resist sensitivity under high energy radiation through careful selection of matrix and PAG materials. A better understanding and study the efficiency of acid generation through direct and indirect PAG excitation pathways and the effect of PAG and matrix structure on these pathways would be extremely valuable for the design of future high sensitivity resist materials. In this work, the acid generation of typical ionic (onium salt) and non-ionic PAGs under DUV (248 nm) and electron-beam exposure in polymer film have been studied. The effect of PAG type and structure on its acid generation under photolysis and radiolysis has been determined. The effect of polymer resin structure on PAG photoacid generation under photolysis and radiolysis has also been investigated. Concepts for PAG and polymer design for producing enhanced sensitivity resists for excitational and ionizational exposure is discussed.
An ionic and non-ionic single molecule chemically amplified resist have been synthesized, characterized, and imaged under high resolution e-beam. The ionic single molecule resist is based on a tBoc protected triarylsulfonium (TAS) core that generates a free superacid upon exposure. TAS demonstrates a low LER (3&sgr;) of 3.9 nm under 100 keV e-beam exposures with a resolution of 55 nm. Under EUV exposures, it exhibits a LER of 5.2 nm with a sensitivity of 60 mJ/cm2 and 50 nm half-pitch resolution. The non-ionic single molecule resist is based on a sulfonic acid containing molecular glass core that uses a norbornene dicarboximide PAG. It images with a low LER of 3.9 nm and a resolution of 40 nm. The non-ionic resist shows multiple improvements over the ionic system including improved resolution, reduced dark loss, and improved solubility. Both resists successfully demonstrate the feasibility of using a single component molecular resist system with high PAG loading. They also show that single molecule resists provide improved LER compared to conventional PAG blended systems, even for unoptimized systems.
Chemically amplified resists (CARs) are likely to continue to be the main resist materials platform for next generation lithography using shorter wavelength and higher energy radiation sources, such as extreme ultra-violet (EUV) and electron-beam (EB) lithography, to pattern features at and below the 32 nm technology node. As the cost of generating and manipulating high energy radiation in these techniques increases dramatically, photoacid generators (PAGs) with high sensitivities to these exposure sources are required to efficiently utilize such radiation and maintain high lithography tool throughputs. On the other hand, the high energy radiation used in current and next generation lithography tools can increasingly interact non-selectively with the PAG and polymer resin. Photoacid generation from PAG sensitization pathways involving the photoresist resin (e.g. polymer) becomes another potential route for boosting the photospeed of CARs if the PAG and matrix resin chemistry is selected properly. In this work, a fast, convenient, and material saving method which can measure the acid generation rate and yield under photolysis and radiolysis, as well as determine the efficiency of acid generation through direct PAG excitation and indirect PAG sensitization pathways has been developed. This method utilizes on-wafer ellipsometry to determine the absorption of protonated Courmarin 6 (C6) dye, which is incorporated into the polymer resin as a proton indicator. In this work, triphenylsulfonium triflate PAG is used in two different matrix resins, poly(methyl methacrylate) and poly(hydroxystyrene), to illustrate this point that matrix sensitization of the PAG can be important and can be studied using the method developed in this work. This study serves as the starting point for building the structure property relationships needed for intelligent PAG and matrix design to optimize exposure energy utilization in CARs. The validity of this new analytical method is verified by comparing our results in selected PAG-polymer combinations with results obtained from previous studies using different techniques. The potential measurement errors possible when using dye as the proton indicator in a solid-state medium, such as the probability of proton-dye contact and acid generation through dye radiation absorption and sensitization of the PAG, are also analyzed and discussed in this paper.
A water developable, non-chemically amplified, negative tone single molecule resist (tris(4-hydroxy-3,5-dimethylphenyl)sulfonium tosylate, otherwise referred to as TAS-tBoc-Ts) was synthesized, characterized, and imaged using high resolution electron beam lithography. The solubility switching in the negative tone imaging mode in this material, which occurs for no or low temperature post-exposure bakes, occurs through photolytic conversion of some fraction of the ionic PAG molecules into non-ionic photoproducts which act as strong dissolution inhibitors to the remaining unreacted molecules in the film. It was also shown that this resist system can dmonstrate positive tone chemically amplified imaging behavior under different processing conditions, i.e. when using higher temperature post-exposure bakes above 100 °C . Pure water was found to be the preferential developer as compared to conventional aqueous alkaline TMAH developers in this particular system for negative tone imaging. Under 100 keV e-beam imaging and water development, a sensitivity of 66 &mgr;C/cm2 and contrast of 7.9 was obtained. TAS-tBoc-Ts obtained 40 nm 1:2 line-space resolutions with a low LER of 5.3 nm using electron beam imaging with no apparent swelling or residue problems. This new material and its negative tone imaging process provide a possible path forward for designing non-chemically amplified resists that may obtain higher resolutions than current chemically amplified resists at competitive sensitivities.
A mesoscale model of molecular resists has been created and implemented that allows for the investigation of the effect of material composition and physiochemical properties, such as PAG loading and photoacid diffusion coefficient, on the lithographic performance (i.e. resolution, line edge roughness, and sensitivity or as commonly referred to "RLS") of molecular glass photoresists. This model is shown to produce results that are in good agreement with many of the conventional LER scaling arguments. In cases where critical dimension is not held constant, it was found that higher photoacid diffusion improves LER at low acid concentrations, but induces higher LER at high acid concentration as compared to smaller diffusion coefficients. Increased PAG loadings were found to provide comparatively lower LER at the same resolution and sensitivity as lower PAG loadings, or alternatively to provide better sensitivity at the same resolution and LER as lower PAG loadings. Even at ultra-high PAG loadings, CARs were found to exhibit RLS limitations. By normalizing all PAG loadings by the total amount of acid produced, it is shown that LER is controlled primarily by photoacid concentration in the resist at the imaging dose for the case where constant critical dimension is maintained with no use of base quencher in the resist. Thus, the most direct and functional scaling argument for LER under such cases is, which is similar to the more common scaling arguments that state, but as this work shows it is more universal to state that which automatically normalizes for different PAG loadings and photoreaction rate constants across different resist formulations.
A new series of methacrylate substituted benzene sulfonic photoacid generators (PAGs) and a perfluoro alkanesulfonic
PAG, bound polymeric resists based on hydroxystyrene (HS) and 2-ethyl-2-adamantyl methacrylate (EA) were prepared
and characterized. The acid yield of these PAG bound polymer resists was among the range of 54-81% under deep
ultraviolet exposure (254 nm) that agrees well with the electron withdrawing effect of the substituents on the PAG anion
for enhancing acid generation efficiency. The intrinsic lithography performance of these polymer-bound PAG resists
showed sub-50 nm half-pitch resolution and < 5 nm LER (3σ).
Substantially improved photoresist material designs, which can provide higher photosensitivity and precise critical
dimension and edge roughness control, will be required to enable the application of next generation lithography
technology to the production of future sub-65 nm node IC device generations. The development and characterization of
novel material platforms that solve the aforementioned basic problems with chemically amplified resists (CARs) is
essential and is already one of the major subjects of modern lithography research. In that regard, we have pursued
development of a variety of 193 nm and EUV CARs that contain photoacid generator (PAG) units covalently bonded
directly to the resin polymer backbone. However, the detailed structure-property relationships that result from this
direct attachment of the PAG functional group to the polymer have previously not yet been rigorously characterized. In
this work, the lithographic properties of a polymer-bound PAG CAR (GBLMA-co-EAMA-co-F4-MBS.TPS) and its
blended-PAG analog resist (GBLMA-co-EAMA blend F4-IBBS.TPS) were studied and compared. The direct
incorporation of PAG functionality into the resist polymer, where the resulting photoacid remains bound to the polymer,
showed improved photosensitivity, resolution, and lower LER as compared with the analogous blended-PAG resist.
The improved resolution and LER were expected due to the restricted photoacid diffusion and uniform PAG distribution
provided by direct incorporation of the PAG into the polymer backbone to make a single-component resist material.
The ability to load higher levels of PAG into the resist provided by this PAG incorporation into the polymer, as compared
to the low PAG concentrations attainable by traditional blending approaches, overcomes the sensitivity loss that should
result from reduction in photoacid diffusivity and concomitant smaller acid-catalytic chain lengths. In fact, the
polymer-bound PAG resist achieves a faster photospeed than the blended-PAG analog material under DUV radiation in
the case of the materials reported here while still providing all of the aforementioned improvements such as the improved
line edge roughness.
A new series of anionic photoacid generators (PAGs), and corresponding polymers were prepared. The thermostability
of PAG bound polymers was superior to PAG blend polymers. PAG incorporated into the polymer main chain showed
improved resolution when compared with the PAG blend polymers. This was demonstrated by Extreme Ultraviolet
lithography (EUVL) results: the fluorine PAG bound polymer resist gave 45 nm (1:1), 35 nm (1:2), 30 nm (1:3) and 20
nm (1:4) Line/Space as well as the 50 nm (1:1),30 nm (1:2) elbow patterns.
A single molecule photoresist composed of tris(4-(tert-butoxycarbonyloxy)-3,5-dimethylphenyl) sulfonium
hexafluoroantimonate (TAS-tBoc) was successfully synthesized and characterized. The synthesized triarylsulfonium was
found to perform comparably to a commercial triphenylsulfonium triflate photoacid generator (PAG) when used purely
as a PAG in blended molecular glass resist. TAS-tBoc formed excellent amorphous films when spin-coated out of
solution. When exposed to 248 nm UV radiation, TAS-tBoc showed a sensitivity of 4 mJ/cm2 and a contrast ratio
between 6 and 15, depending on development conditions. Its etch rate under standard silicon dioxide etch conditions was
0.87 as standardized to that of tBoc-PHOST in the same RIE plasma conditions. The outgassing level of the resist under
EUV exposure was determined to be 1.08 x 1013 molecules/cm2, well below the maximum outgassing cutoff that is
considered acceptable for EUV imaging. When imaged by e-beam, TAS-tBoc showed a relatively high dose-to-clear of
150 &mgr;C/cm2 as compared to conventional chemically amplified photoresists. Lines down to 50 nm wide with aspect
ratios of 2.5:1 were imaged using e-beam. These lines exhibited an LER of only 3.96 nm, significantly better than the
typical LER for polymeric chemically amplified resist, even when imaged using e-beam, and also one of the lowest
values reported for molecular glass materials in general.
Conventional chemically amplified photoresist formulations are complex mixtures that include a protected polymer resin and a small molecule photoacid generator (PAG). The limited compatibility of the PAG with resist resin and the mobility of the small molecule additive can lead to problems including PAG phase separation, non-uniform initial PAG and photoacid distribution, and acid migration during the post-exposure baking (PEB) processes. The incorporation of PAG units into the main chain of the polymer resin is one possible method to alleviate these problems. Recently, we have investigated methacrylate based resists which incorporate novel PAG functional groups into the polymer main chain. These materials have demonstrated good resolution performance for both 193 nm and EUV exposure for sub-100 nm patterning. However, limited information is available on the effect of binding the PAG to the polymer on PAG photoreactivity and photoacid diffusivity. In this work, the photoacid generation rate constant (commonly referred to as the Dill C parameter for the PAG) of both triflate polymer-bound PAG and blended PAG photoresists based on poly(γ-butyrolactone methacrylate -co-2-ethyl-2-adamantyl methacrylate ) resists were determined by a new technique utilizing both quantitative FTIR spectroscopy and kinetic model fitting. The results indicate that the polymer-bound PAG resist has a lower photoacid generation rate constant (C=0.0122) than the blend PAG one (C=0.2647). This large difference in Dill C parameters would indicate that the sensitivity of the polymer-bound PAG resist is substantially lower than that of the analogous blended sample which is consistent with contrast curve data for these two samples.
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