Conventional chemically amplified resists have several issues that can potentially limit their capability for sub-40 nm imaging. One of the major issues at this size scale is that the mechanical strength of positive tone CARs limits the amount of stress they can withstand during development, rinse, and drying, thus leading to problems with pattern collapse due to the high capillary forces generated during drying. This problem is exasperated by the fact that linear polymers show dramatically reduced modulus at sub-50 nm features sizes. To improve on this problem, we have made a positive tone resist based on network depolymerization of molecular resists. The resist thermally cross-links after being spin cast into thin film form through reactions between vinyl ether groups and carboxylic acid groups. By cross-linking the resist to form a dense three dimensional polymer network, the mechanical strength of the resist is greatly improved compared to linear polymers. The network is depolymerized using an acid catalyzed reaction to create development contrast that allows for patterning of the resist via development in either aqueous base or organic solvent. One drawback of the current resist design is that the free carboxylic acids on the resist molecule appear to react in solution at room temperature with both the vinyl ether groups on adjacent molecules and with any added base quencher. These reactions cause reduced effectiveness of the base quencher and produce a noticeable resist shelf life problem. Despite these limitations, the material was used to compare the effect of development in aqueous base versus organic solvent. The resist formulated in this work showed a DUV sensitivity of 7 mJ/cm2 and a contrast of 5.2 for development in either solvent or aqueous base. Under 100 keV e-beam imaging, the material showed 40 nm resolution for both development types. In standard 0.26 N TMAH, the dose-to-size was 84 μC/cm2 with 3σ LER of 14.2 nm. Using methyl isobutyl ketone for organic solvent development, the dose-to-size was 104 μC/cm2 with 3σ LER of 7.4 nm.
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).
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.
Two different types of non-traditional molecular resists were synthesized and characterized. A positive-tone cross-linked
molecular resist was made that functions by first forming an etch resistant film via thermal cross-linking of vinyl ether
functionalized small molecules followed by patterning of the film via acid catalyzed cleavage of the resulting acetal
bonds. DPA-2VE, a single multi-functional molecular resist of this type, showed DUV sensitivity of 7 mJ/cm2 and a
contrast of 5.2 for development in either organic solvent or aqueous base. Using high resolution patterning with a 100
keV e-beam, it was possible to demonstrate feature resolutions down to 40 nm. When 0.26N TMAH was used as a
developer, the dose-to-size was 84 μC/cm2 with a 3σ LER of 14.2 nm. Using MIBK as a developer, the dose-to-size was 104 μC/cm2 and the 3σ LER was 7.4 nm. A series of non-chemically amplified molecular resists based on using 2-
nitrobenzyl ethers as photosensitive protecting groups were also made. One formulation showed a DUV sensitivity of 1 mJ/cm2, while another formulation which showed the best contrast of 8.3 obtained at a sensitivity of 10 mJ/cm2.
However, under 100 keV e-beam patterning, the 2-nitrobenzyl ether protected materials showed little to no response even up to 3000 μC/cm2.
KEYWORDS: Molecules, Electron beam lithography, Deep ultraviolet, Line edge roughness, Polymers, Polymerization, Glasses, Dewetting, Optical lithography, Scanning electron microscopy
A series of negative tone molecular resists was investigated for use in both organic solvent and aqueous base
development. Molecular resists designed purely for solvent development showed half-pitch resolution down to 25 nm
with sensitivities of 50 μC/cm2 and LER (3σ) down to 2.3 nm. Aqueous developable designs that used epoxide
functionalized molecules that are intrinsically water soluble showed improved contrast and comparable sensitivity, but
suffered from significant dewetting during baking due to their low molecular weight and high polarity. This inability to
form high quality films prevented their use as high resolution resists. Aqueous developable designs that used molecules
with both cross-linking and base solubilizing groups were also investigated; the initial example of this design is DPA-
2Ep, a molecular resist containing two epoxides and one carboxylic acid per molecule. It formed high quality films and
showed improved contrast compared to the purely solvent developed designs. Even after complete cross-linking of the
epoxide groups, several free carboxylic acids still remained in the network. These free acids tend to imbibe developer and appear to retain the tetramethylammonium carboxylates even after rinsing and drying the film. This imbibing of developer leads to significant failure during high resolution patterning due to swelling.
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.