The photoacid diffusion length is a critical issue for extreme ultraviolet (EUV) lithography because it governs the critical
dimension (CD), line-edge-roughness (LER), and line-width-roughness (LWR) of photoresist materials. Laboratorybased
experimental methods that complement full lithographic testing would enable a rapid screening of materials and
process conditions. This paper provides an approach to characterize the photoacid diffusion length by applying a bilayer
stack technique. The method involves quantitative measurements of the deprotection kinetics as well as film thickness at
each process step: radiation exposure, post-exposure bake, and development. Analogous to a contrast curve, by
comparing the film thickness of the bilayer before and after development, the photoacid diffusion length was deduced in
a commercial EUV photoresist and compared to EUV lithography. Further, by combining the experiments with kinetics
modeling, the measured photoacid diffusion length was predicted. Lastly, based upon the measured kinetics parameters,
a criterion was developed that next-generation resists must meet to achieve a 16 nm photoacid diffusion length. These
guidelines are discussed in terms of correlations and contributions from the photoacid and resist properties. In particular,
the trapping kinetics of the photoacid provides a route to reduce LER and the CD at low dose.
It has been recently postulated that sub-22 nm photolithography with polymeric photoresists has reached a materials design barrier due to its large molecular mass and distribution. In this argument, the "pixel" size, which is related to the smallest molecular unit, determines the feature fidelity and resolution of the lithographic process. This hypothesis remains unproven, but molecular glass photoresists can provide a test because they can share similar chemical functionality to polymer resists, but with low molecular mass and a monodisperse molecular mass distribution. The low molecular mass leads to the smaller pixel size compared to the radius of gyration of the polymer photoresist. In this work, we compare the deprotection reaction-diffusion kinetics of a common photoacid generator in a polymer and molecular glass resist with similar resist chemistry to elucidate effects of molecular architecture on photoresist performance. We determine the mechanism of reaction, photoacid trapping behavior, and diffusivity by measuring and comparing the reaction kinetics parameters as a function of temperature and exposure dose. These results permit an analysis of the latent image formation which is a crucial factor in resolution and line-edge roughness. Further, knowledge of the reaction-diffusion parameters of each type of resist provides a quantitative approach to predict line-space features, crucial for design for resolution-enhancement features.
Current extreme ultraviolet (EUV) photoresist materials do not yet meet performance requirements on exposure-dose sensitivity, line-width roughness, and resolution. In order to quantify how these trade-offs are related to the materials properties of the resist and processing conditions, advanced measurements and fundamental studies are required that consider EUV-resist specific problems. In this paper, we focus on the correlations between the latent image and developed image in EUV exposed line/space features. The latent images of isolated lines produced by EUV lithography are characterized by atomic force microscopy through the change in topology caused by change in film thickness that occurs upon deprotection. The resulting latent-image deprotection gradient (DGL), based on line cross-sections, and latent-image line-width roughness (LWRL) provide metrics and insight into ways to optimize the lithographic process. The results from a model poly(hydroxystyrene-co-tert-butylacrylate) resist and a model calix[4]resorcinarene molecular glass type resist show the general applicability of the metric before development.
Specular X-ray reflectivity (SXR) can be used, in the limit of the effective medium approximation (EMA), as a highresolution
shape metrology for periodic patterns on a planar substrate. The EMA means that the density of the solid
pattern and the space separating the periodic patterns are averaged together. In this limit the density profile as a
function of pattern height obtained by SXR can be used to extract quantitative pattern profile information. Here we
explore the limitations of SXR as a pattern shape metrology by studying a series of linear grating structures with
periodicities ranging from 300 nm to 16 &mgr;m. The applicability of the EMA is related to the coherence length of the Xray
source. For our slit-collimated X-ray source, the coherence length in the direction parallel to the long axis of the
slit is on the order of 900 nm while the coherence along the main axis of the beam appears to be much greater than
16 &mgr;m. Limitations of the SXR pattern shape metrology are discussed and examples of determining quantitative
pattern profiles provided.
A general approach to characterize compositional heterogeneity in polymer thin films using Fourier transform
infrared (FTIR) spectroscopy has been demonstrated Polymer films with varying degrees of heterogeneity were
prepared using a model chemically amplified photoresist where a photoacid catalyzed reaction-diffusion process results
in the formation of methacrylic acid (MAA)-rich domains. Within these domains, the carboxylic acid groups dimerize
through hydrogen bonding. FTIR measurements of the relative fraction of hydrogen-bonded versus free carboxylic
groups are used to quantify the degree of compositional heterogeneity. It was shown that the degree of the spatial
heterogeneity varies with changes in the deprotection level and initial copolymer composition. The degree of
heterogeneity is small at very low and very high deprotection level and maximize when the deprotection level is around
0.25. Increased non-reactive comonomer content decreases the degree of heterogeneity by reducing the hydrogen
bonding efficiency.
The spatial distribution of polymer photoresist and deuterium labeled developer highlights a fraction of material at a
model line edge that swells, but does not dissolve. This residual swelling fraction remains swollen during both the in
situ development and rinse steps uncovering that the final lithographic feature is resolved by a collapse mechanism
during the drying step. We demonstrate that contrast variant neutron reflectivity provides a general method to probe the
nanometer resolved in situ development and rinse process step.
The controlling factors in the formation of the compositional heterogeneity at the deprotection front were
investigated using 3D computer simulation. The results illustrate that the chemical composition fluctuation (CCF)
formed by the photoresist deprotection reaction is an important factor contributing to the line-edge-roughness (LER) in
addition to the deprotection gradient (DG) of the reaction front. The magnitude of the chemical composition fluctuation
and the deprotection gradient are found to depend on the ratio of the deprotection reaction rate constant to diffusion
coefficient (kP/D) and the number of hoping step (n) With this new finding, the influence on LER from various
process/material parameters such as dose/contrast, diffusivity, and reactivity can all be understood through their effects
on kP/D and n.
A correlation between polymer molecular structure and acid catalyzed reaction kinetics is demonstrated by a photoresist copolymer with an acid-labile and a non-reactive monomer. The acid catalyzed deprotection kinetics depend significantly on the composition of the non-reactive comonomer in the polymer chain. The apparent reaction rate constant decreases monotonically with increasing non-reactive comonomer composition. The phenomena are interpreted as the reduction of diffusivity of photoacid in the polymer matrix from a hydrogen-bonding interaction with the polar group in the inert comonomer. In addition, hydrogen-bonding interactions between the photoacid and the reaction product, primarily methacrylic acid, can account for the acid loss or trapping effect observed by various researchers.
An understanding of acid diffusion-reaction in chemically amplified photoresists during the post-exposure bake (PEB) is critical for both critical dimension (CD) and line edge roughness (LER) control. Despite its importance, there remains insufficient understanding of the diffusion-reaction process. This is due in part to the complex interplay between diffusion and reaction where the deprotection of the resin modifies the local acid diffusivity which in turn changes the rate of deprotection. Here, we report the direct measurement of the reaction diffusion front at a model line edge from neutron reflectivity and Fourier transform infrared spectroscopy measurements. The photoacid generator size influences the reaction extent and breath of the deprotection profile. A larger photoacid results in a sharper deprotection profile and a shorter reaction length. Under the same post-exposure bake time and temperature, the smaller photoacid leads to a much broader deprotection profile. These measurements illustrate the complexity of the reaction-diffusion process.
The dissolution of partially deprotected chemically amplified photoresists is the final step in printing lithographic features. Since this process step can be tuned independently from the design of the photoresist chemistry, measurements of the dissolution behavior may provide needed insights towards improving line-edge roughness. We have studied the dissolution behavior of a model 193-nm photoresist, poly (methyladamantyl methacrylate), as a function of deprotection extent and developer strength. The kinetics of the dissolution process is followed using the quartz crystal microbalance technique. These photoresist films exhibit strong swelling without dissolution over a significant range of deprotection levels. At larger extents of deprotection, we observe a combination of swelling with dissolution. Additionally, we find that the degree of film swelling decreases with tetramethylammonium hydroxide developer concentration. These studies provide the insight needed to better understand the fundamentals of the dissolution of the photoresist - a key step in lithographic process.
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