Directed self-assembly (DSA) of block copolymers (BCP) could enable high resolution patterning beyond the
capabilities of current optical lithography methods via pitch multiplication from lower resolution primary lithographic
patterns. For example, DSA could enable dense feature production with pitches less than 80 nm from patterns generated
using 193 nm exposure tools without the need for double patterning or other schemes. According to theory, microphase
separation of diblock copolymers occurs when the critical condition that χN>10.5 is met while the pitch of the resulting
polymer features scale as ~N2/3, where χ is the Flory Huggins interaction parameter and N is the total degree of
polymerization for the diblock copolymer. In order to generate patterns with smaller pitches, N must be decreased while
maintaining a χN>10.5 to allow for phase separation. This requires utilization of polymers with higher χ values as N is decreased. Current materials, such as PS-b-PMMA, exhibit a relatively low χ value of ~0.04, which limits the practical pitch of DSA line-space patterns produced using PS-b-PMMA to approximately 20 nm. In this paper, we investigate alternative materials, namely poly(styrene)-b-poly(hydroxystyrene) (PS-b-PHOST), which exhibits a high χ value via hydrogen bonding interactions that can allow for production of sub-20nm pitch DSA patterns. In order to utilize any diblock copolymer for DSA, a neutral underlayer and a method for annealing the block copolymer are required. Here, a random copolymer, poly(styrene-co-hydroxystyrene-co-glycidyl methacrylate), is developed and reported for use as a neutral underlayer for PS-b-PHOST. Furthermore, a solvent annealing method for PS-b-PHOST is developed and
optimized using ethyl acetate to allow for uniform microphase separation of PS-b-PHOST.
As an alternative lithography technique, directed self-assembly (DSA) of block copolymers has shown to be promising
for next generation high resolution patterning. PS-b-PMMA has been widely studied for its use as a block copolymer in directed self-assembly and has demonstrated patterned features down to size scales on the order of 20 nm pitch.
However, due to the modest χ value for PS-b-PMMA (χ=0.038), this 20 nm feature pitch representes roughly the limiting capability of PS-b-PMMA. To achieve smaller pitch features, new block copolymers with higher χ values must be developed for use in DSA lithography. Here, poly(styrene)-b-poly(hydroxyehtylmethacrylate) or PS-b-PHEMS is
introduced as one possible such high χ polymer. PS-b-PHEMA with controlled Mw and PDI was successfully
synthesized via ATRP and fully characterized by NMR, GPC and FTIR. As a first demonstration of sub-20 nm pitch
capability in PS-b-PHEMA, a 15 nm pitch size lamella structure in PS-b-PHEMA is shown. PS-b-PHEMA has good
thermal stability, allowing it to be rapidly annealed thermally. PS-b-PHEMA also is shown to have improved etch
contrast between the two blocks as compared to PS-b-PMMA. The χ value for PS-b-PHEMA is estimated to be 0.37
based on experimental pitch scaling studies, which is almost 10 times of the χ value for PS-b-PMMA.
Poly(styrene)-b-poly(acrylic acid) copolymers (PS-b-PAA) was shown to be one promising material for achieving
substantially smaller pitch patterns than PS-b-PMMA while still retaining high etch contrast and application for chemoepitaxy.
Phase separation of acetone vapor annealed PS-b-PAA (Mw=16,000 g/mol with 50:50 volume ratio of PS: PAA)
on PS brush achieved a lamellar morphology with a pattern pitch size (L0) of 30 nm. However the thermal annealing of
the same PS-b-PAA generated a dramatically larger pitch size of 43 nm. SEM and GPC analysis revealed that the
intermolecular crosslinking during thermal annealing process has increased the effective N (degree of polymerization),
which suggests that even a small amount of crosslinking would lead to big pitch change. Thus, PS-b-PAA is not suitable for fast thermal annealing process as it loses pitch size control due to PAA crosslinking.
Directed self assembly (DSA) of block copolymers (BCP) could enable high resolution secondary patterning via pitch
multiplication from lower resolution primary lithographic patterns. For example, DSA could enable dense feature production at
pitches less than 20 nm from patterns generated using 193 nm exposure tools. According to theory, microphase separation of
block copolymers can only occur when the critical condition that χN>10.5 is met, where χ is the Flory Huggins interaction parameter and N is the total degree of polymerization for the block copolymer. In order to generate smaller DSA pattern pitches, the degree of polymerization of the block copolymer is reduced since this reduces the characteristic length scale for the polymer (e.g. radius of gyration). Thus, as N is reduced, the effect of this reduction on χN must be balanced by increasing χ to maintain a given level of phase separation. Currently, most DSA work has focused on the use of poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) copolymers whose low χ value (i.e. ~0.04) limits the practical DSA pitch using such materials to approximately 20nm. The general goal of this work has been to explore new higher χ block copolymer systems, develop DSA patterning schemes based on such materials, and test their ultimate pitch resolution. This paper discusses the synthesis and characterization of poly(styrene)-b-poly(hydroxystyrene) (PS-b-PHOST) copolymers made via nitroxide mediated radical polymerization. The formation of lamellar fingerprint structures in PS-b-PHOST using solvent annealing is demonstrated. Using this fingerprint data, initial estimates of χ for PS-b-PHOST are made which show that it appears to be at least one order of magnitude larger than the χ for PS-b-PMMA . Finally, graphoepitaxy of self-assembled lamellar structures in PS-b-PHOST is demonstrated using SU-8 guiding patterns on cross-linked neutral underlayers.
Directed self-assembly (DSA) of block copolymers is a promising technology for extending the patterning capability of
current lithographic exposure tools. For example, production of sub-40 nm pitch features using 193nm exposure
technologies is conceivably possible using DSA methods without relying on time consuming, challenging, and
expensive multiple patterning schemes. Significant recent work has focused on demonstration of the ability to produce
large areas of regular grating structures with low numbers of defects using self-assembly of poly(styrene)-b-poly(methyl
methacrylate) copolymers (PS-b-PMMA). While these recent results are promising and have shown the ability to print
pitches approaching 20 nm using DSA, the ability to advance to even smaller pitches will be dependent upon the ability
to develop new block copolymers with higher χ values and the associated alignment and block removal processes
required to achieve successful DSA with these new materials. This paper reports on work focused on identifying higher
χ block copolymers and their associated DSA processes for sub-20 nm pitch patterning. In this work, DSA using
polystyrene-b-polyacid materials has been explored. Specifically, it is shown that poly(styrene)-b-poly(acrylic acid)
copolymers (PS-b-PAA) is one promising material for achieving substantially smaller pitch patterns than those possible
with PS-b-PMMA while still utilizing simple hydrocarbon polymers. In fact, it is anticipated that much of the learning
that has been done with the PS-b-PMMA system, such as development of highly selective plasma etch block removal
procedures, can be directly leveraged or transferred to the PS-b-PAA system. Acetone vapor annealing of PS-b-PAA
(Mw=16,000 g/mol with 50:50 mole ratio of PS:PAA) and its self-assembly into a lamellar morphology is demonstrated
to generate a pattern pitch size (L0) of 21 nm. The χ value for PS-b-PAA was estimated from fingerprint pattern pitch
data to be approximately 0.18 which is roughly 4.5 times greater than the χ for PS-b-PMMA (χPS-b-PMMA ~ 0.04).
One of the problems for lithographic processes at very small feature scales is pattern collapse caused by unbalanced
capillary forces experienced by the photoresist patterns during the final deionized water rinse and drying process. The
use of surfactants or super critical fluids to reduce collapse problems has been proposed and studied by many research
groups. However, the patterns rinsed with low surface tension fluids appear in many cases to shrink or such treatments
cause other feature deformations. Super critical fluid processing requires major changes to the ways in which current
track systems operate and can result in swelling and deformation of the resist features as well. Instead of utilizing super
critical fluids or adding surfactants to the rinse liquid, one general methodology we have pursued for alleviating such
pattern collapse problems involves the actual strengthening of the resist feature itself during wet processing in the
development and rinse cycle. One method we have investigated extensively is the use of post-development resist surface
crosslinking reactions while the resist structures are still in their wet state, a process we term "reactive rinsing". Such
reactive rinse processes have shown significant impact on improving resist pattern collapse. However, previous
chemistries used for such reactive rinse processes have either: (1) been complex mixtures that potentially have long term
stability problems (i.e. thus making their application in a fab environment more difficult) or (2) been specific to a certain
resist types in that the chemistries react with only certain resist functional groups that may not be present in all resists of
interest (e.g. some chemistries only work with phenolic resins such as those found in DUV or EUV resists). Therefore,
the goal of this work has been to investigate other novel reactive rinse chemistries that are both more robust and which
can function with different families of resist materials. Poly-functional aziridines offer one potential such family of
compounds that could be the basis for a reactive rinse chemistry. Such aziridines are often used industrially in both
aqueous and nonaqueous coatings, inks and adhesives to promote both physical and chemical properties and are known
to react with carboxylic acid functional groups such as those commonly found in many 193 nm resists. The goal of this
specific study was to determine if poly-functional aziridine chemistry could be used as a reactive rinse for preventing
photoresist pattern collapse in 193nm type resists. Contact angle studies and x-ray photoelectron spectroscopy (XPS)
were used to characterize the surface crosslinking reaction using aziridine treatments of model resists containing
carboxylic acid functionality. Pattern collapse test structures were fabricated and analyzed using a PMMA/PMAA copolymer
resist commonly employed for e-beam lithography. SEM studies of the resulting patterns confirm that use of
multifunctional aziridine crosslinkers during a post-development process can significantly reduce pattern collapse and
enable production of higher resolution features.
As the semiconductor industry continues to push to smaller critical dimensions, pattern collapse during lithographic
processing caused by unbalanced capillary forces during the final rinse and drying process has become an important
problem that can limit the practical resolution of a resist material to feature sizes larger than its intrinsic resolution limit.
One of the primary modes of pattern collapse is via elastoplastic pattern deformation which is strongly related to the
mechanical properties of the resist. One approach to mitigating such collapse problems is to enhance the mechanical
properties of the resist features. Since such modification of resist physical properties for pattern collapse purposes is
difficult to achieve through modified formulation of the resist itself (i.e. due to the complex set of requirements that a
resist must satisfy and the complex set of physical and chemical phenomena that underlie the imaging processing itself),
we have pursued an alternative strategy for improving the resist mechanical properties after features are developed in the
film but before they are rinsed and dried. The family of techniques being developed in this work function through the
use of aqueous compatible reactive rinse solutions that can be applied to developed resist features while they are wet
during normal rinse processing on a track system. By applying these techniques during the rinse process, the resist
features can be strengthened before they are subjected to significant capillary forces during the final drying step. In this
work, the use of diamine compounds to reactively crosslink the surface of resists containing carboxylic acid groups
through formation of amide bonds using carbodiimide chemistry has been explored. One advantage of this approach is
that it is an aqueous process that should be easily compatible with high volume, track-based lithographic processes.
Contact angle studies and x-ray photoelectron spectroscopy (XPS) were used to characterize the surface crosslinking
reaction using such diamine surface rinse treatments. Pattern collapse test structures were fabricated and analyzed to
measure the amount of mechanical property improvement imparted by such treatments. Application of such amine
reactive rinses was found to clearly result in an improvement in the resistance of resists to pattern collapse as observed
by SEM. A comparison of the critical stress at the point of pattern collapse as a function of resist feature size also
clearly shows a significant improvement in mechanical resilience of resist samples processed with the reactive rinse
treatment.
Directed self-assembly (DSA) of block copolymers has gained significant attention in recent years as a possible
alternative for large area fabrication of future sub-30 nm lithographic patterns. To achieve this patterning, at least three
critical pieces are needed: (1) a block copolymer with sufficient immiscibility of the two blocks to drive phase separation
at the low molecular weights required to achieve such small phase domains, (2) a method for selectively removing one
of the blocks after phase separation to achieve formation of a relief pattern, and (3) a method for producing the templated
surfaces used to guide and register the phase separated patterns on the substrate of interest. Current methods for
achieving the patterned substrate template, whether they are of chemoepitaxial or graphoepitaxial nature, are generally
complex involving a large number of steps that are not easily applied to a variety of different substrate surfaces. For
example, numerous substrates have been studied to provide neutral wettability to the styrene-methacrylate (PS-b-
PMMA) block copolymers, such as random styrene-methacrylate copolymer films (PS-r-PMMA) or self-assembled
monolayer (SAM) modified surfaces, which induce perpendicularly oriented morphologies for PS-b-PMMA self-assembly.
In the case of chemical epitaxy processes, a layer of photoresist is generally then coated on such neutral
substrate films and patterned to render commensurability to the periodicity of the PS-b-PMMA being used. The open
(i.e. space) regions in the resist are then exposed to alter their chemistry, e.g. soft X-ray or oxygen plasma exposures
have been used, to achieve hydrophilicity which should preferentially wet PMMA. Finally, the resist is stripped and the
block copolymer is coated and assembled on the template surface. Obviously such multi-step processes would not be
preferred if alternatives existed. As a step toward that goal of making DSA processes simpler, a photodefinable substrate
film that can be used for PS-b-PMMA self-assembly has been developed in this work that is coated, exposed, and baked
in a manner analogous to current optical photoresists. The polymer resin for this material is a form of protected
poly(hydroxystyrene) that is cross-linkable. The new material is suitable for DSA processes using both solvent and
thermal annealing methods. Results of PS-b-PMMA DSA on this new material will be discussed.
As the semiconductor industry continues to push the limits of the lithography processes used to fabricate integrated
circuits, pattern collapse during development and drying can have a substantial impact on process viability. This pattern
collapse in general is caused by unbalanced capillary forces present during the drying step of the lithographic process.
Significant research has focused on developing methods to reduce such capillary forces and improve the pattern collapse
of photoresists. However, it appears that relatively little attention has been paid to other process dependent factors
which may also significantly impact such collapse behavior. For example, another potential factor which may affect
pattern collapse is the length of time during which the resist features are actually stressed during drying. As such,
processes which result in different drying rates may be expected to yield different levels of pattern collapse. In this
work, e-beam lithography was used to generate high resolution line-space pair arrays which contain different size spaces
between a pair of adjacent lines in a model chemically amplified resist. Such line pairs present an excellent tool for
studying pattern collapse and quantifying the level of stress required to cause collapse and failure of resist features.
After development and rinse, such pattern collapse test structures were dried using a variety of different processes
possessing a variety of different drying rates, and the impact of these different drying methods on pattern collapse was
quantified. It was indeed found that drying rate has a dramatic impact on pattern collapse, with spin drying techniques
performing better than most other techniques. However, it was discovered that such spin drying methods also yield a
significant pattern orientation dependence of the degree of pattern collapse. Such behavior is explained in terms of
additional mechanical forces caused by the centrifugal forces exerted during spin drying methods.
As integrated circuit fabrication continues to advance towards the 22 nm node and below, it has become clear that
although line edge roughness and resolution are important, other issues such as pattern collapse must be addressed in
order for technology to continue to progress. One of the primary modes of pattern collapse at small feature sizes is
adhesion failure caused by loss of adhesion of the resist to the substrate during the drying process. The main forces
which govern pattern collapse by adhesion failure are related to substrate/resist interactions. Significant research has
been conducted to find methods for reducing capillary forces, such as use of surfactants in rinses, to reduce pattern
collapse. However, the use of spin drying has also been observed to exhibit other collapse related effects that are not
sensitive to such treatments. To this end, in this work a reactive adhesion promoter capable of covalently attaching to
hydroxystyrene-based positive tone resist copolymers has been developed and demonstrated. A vinyl-ether-modified
silane was prepared and effectively applied using a solution silanization reaction. A model hydroxystyrene-based
positive tone resist was applied and subjected to post apply bake to cause reaction of the surface modifier with the
photoresist to occur prior to patterning using e-beam lithography. Contact angle studies and ellipsometry were used to
characterize the surface silanization reaction. Pattern collapse test structures were fabricated and analyzed after
development and drying on the different surfaces to quantify the impact of the use of the covalent surface linker and
compare it to more standard adhesion promoter processes such as those utilizing hexamethyldilazane (HMDS). The
effect of soft bake condition on the performance of the reactive adhesion promoter has also been studied. Ultimately, the
results of critical stress analysis and SEM studies of the resulting patterns confirm that use of surface priming agents that
covalently attach the resist to the substrate can significantly enhance resist-substrate adhesion and dramatically reduce
pattern collapse.
Pattern collapse has become an issue of increasing importance in semiconductor lithography as the size of critical
features continues to shrink. Although models have been proposed to explain the observed pattern collapse behavior, the
ability of such models to quantitatively predict the collapse behavior has been limited without significant model fitting to
experimental pattern collapse behavior. Such a need to collect extensive collapse data before these models can provide
any predictive capability limits their use and in general does not provide further insight into the underlying root causes of
the observed behavior in many cases. This is particularly true at small feature sizes for resist lines smaller than
approximately 70 nm in width. In this work, a comprehensive pattern collapse model that accounts for both adhesion
based pattern failure and elastoplastic deformation-based failure is used. Furthermore, the required model parameters
are extracted from basic experiments on the resist materials and substrates themselves without the need for actual
patterning experiments. For example, the resist mechanical modulus behavior is determined from simple thin film
buckling experiments. The results of these simple tests are quantitatively predictive pattern collapse models for a
particular resist-substrate combination that capture complex effects such as the dependence of the collapse behavior on
resist film thickness and feature size due to feature size dependent polymer modulus behavior. Application of these
models and experimental methods to an experimental resist and comparisons of the model predictions versus actual
experimental pattern collapse data are shown and discussed to validate the methodology.
It has become clear that although line edge roughness and resolution are important for future lithographic technology
nodes, other issues such as pattern collapse must be addressed as well. One of the primary modes of pattern collapse is
pattern collapse caused by loss of adhesion of the resist from the substrate. The main forces which govern pattern
collapse by adhesion failure are related to substrate/resist interactions. Though several methodologies to improve pattern
collapse have been investigated, such as the use of surfactants during the final rinse, the use of such methods virtually all
suffer from some serious drawback. To this end, we have developed a reactive surface modifier capable of covalently
attaching to a positive tone resists containing hydroxystyrene groups. A vinyl-ether-modified silane was prepared and
effectively applied using a solution silanization reaction. A hydroxystyrene-based positive tone copolymer resist was
applied and subjected to a post apply bake to allow sufficient time for reaction with the surface modifier to occur prior to
patterning using e-beam lithography. Ultimately, it was determined that covalent attachment of the surface modifier to
the photoresist during the post apply bake resulted in enhanced resist/substrate adhesion of photoresist lines as evidenced
by improved pattern collapse performance in high resolution imaging experiments.
As integrated circuit fabrication continues to advance towards the 32 nm node and below, it has become increasingly
apparent that the use of ultrathin films and polymer features will be required. Though it has been widely accepted that
the properties of polymers on the nanoscale can differ significantly from their bulk counterparts, the extent of such
deviation is the subject of much debate and concern. Furthermore, most studies have focused on elucidating the
differences in the thermal properties of micro- and nano-scale polymer films as determining the mechanical properties of
ultrathin films can be somewhat cumbersome. In order to study the modulus of polymer thin films we have implemented
a thin film buckling technique wherein a polymer film is floated onto a pre-strained PDMS substrate. Release of the
strain, results in the buckling of the polymer film and provides the opportunity to accurately determine the modulus of
polymer thin films with thicknesses down to 20 nm. This thin film buckling strategy was also used to probe the effect of
thickness on the modulus of the ESCAP-1 thin films. Finally, a reactive rinse method was employed whereby the hydroxyl functional groups of the resist were cross-linked via a dicarboxylic acid using carbodiimide chemistry as a potential method to ultimately enhance lithographic patterning performance. The effect of the reactive rinse on the modulus of the ESCAP-1 thin films was analyzed and it was found that the application of the reactive rinse resulted in a clear increase in the modulus of the polymer films. Also, quartz crystal microbalance (QCM) supporting the confinement of the crosslinking agents to the surface will be discussed.
Pattern collapse is becoming a critical issue as integrated circuit fabrication continues to advance towards the 32 nm
node and below. Though line edge roughness and resolution are certainly important in moving forward, pattern collapse
by both deformation and adhesion failure must be addressed. In this work, a post-development strategy to reduce pattern
collapse by bending was developed whereby the hydroxyl functional groups on the surface of the resist were crosslinked
via a dicarboxylic acid using carbodiimide chemistry. The pattern collapse of a hydroxystyrene-based, positive tone
resist was then studied before and after the application of the reactive rinse. SEM analysis of the samples showed that
application of the reactive rinse resulted in a clear increase in the printing capabilities of the resist, as the photoresist
lines could be printed with smaller space widths corresponding to higher stresses after the rinse treatment.
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