Block copolymers (BCP) self-assemble into a variety of microstructures and controlling the orientation of these structures relative to the substrate surface allows for their use in lithographic techniques. Control over the orientation is non-trivial and requires chemical treatment of the substrate or external fields that can interact and orient these BCP microstructure domains. With this research we highlight a facile thin film casting methodology that produces and orients diblock copolymer microstructure perpendicular to the substrate in the casting process itself. The films are cast from a solvent mixture with a block selective Ionic Liquid (IL) that plasticizes the BCP, enhances repulsive interactions between blocks, and screens preferential interactions between the BCP and the substrate. With a well-developed and fully perpendicular microstructure these films can find applications in sub-20nm lithography processes and as ultrafiltration membranes after selectively etching out the assembled domains.
Long-period parallel lamellar morphologies for block copolymers (BCP) require long thermal annealing (TA) times or sensitive equipment for control. Direct immersion annealing (DIA) rapidly produces parallel microstructure but with smaller domains. We studied the transition between ordered states obtained by TA and DIA to understand the dynamics of the process, analyzed in terms of chain swelling, diffusion, and in-plane vs. out-of-plane interfacial evolution. We propose an alternate processing route for accelerated BCP assembly with large lamellar domain sizes. In addition, we report a transition morphology between the two lamellar states with characteristics of high surface roughness and surface area.
The unique functional characteristics of nanostructured material are stemming mainly from a large surface-to-volume-ratio and on quantum effects; can yield numerous potential space defense applications. The objective of this study is to explore the polarimetric characterization of polymer nanomaterials, using Mueller matrix and Stokes parameters analysis. Specifically, gold nanoparticles were dispersed within a matrix of two-different polymer domains and their polarimetric response to infrared light was studied.
Direct patterning of low-dielectric constant (low-k) materials via nanoimprint lithography (NIL) has the potential to
simplify fabrication processes and significantly reduce the manufacturing costs for semiconductor devices. We report
direct imprinting of sub-100 nm features into a high modulus methylsilsesquioxane-based organosilicate glass (OSG)
material. An excellent fidelity of the pattern transfer process is quantified with nm precision using critical dimension
small angle X-ray scattering (CD-SAXS) and specular X-ray reflectivity (SXR). X-ray porosimetry (XRP) and positron
annihilation lifetime spectroscopy (PALS) measurements indicate that imprinting increases the inherent microporosity of
the methylsilsequioxane-based OSG material. When a porogen (pore generating material) is added, imprinting decreases
the population of mesopores associated with the porogen while retaining the enhanced microporosity. The net effect is a
decrease the pore interconnectivity. There is also evidence for a sealing effect that is interpreted as an imprint induced
dense skin at the surface of the porous pattern.
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.
Directly patterning dielectric insulator materials for semiconductor devices via nanoimprint lithography has the
potential to simplify fabrication processes and reduce manufacturing costs. However, the prospect of mechanically
forming these materials, especially when they are highly porous, raises concerns about their physical integrity. We
report the direct imprinting of 100 nm parallel line-space patterns into a high modulus poly(methylsilsesquioxane)-based
organosilicate thin film that is capable, in its non-patterned form, of meeting the ultra-low dielectric constant
requirement of k ≈ 2.3. Immediately after imprinting a (5 to 10) % shrinkage in the pattern height of the partially
vitrified patterns relative to the mold is quantified using X-ray reflectivity. Nanoscopic pores with an average diameter
of approximately 2.2 nm are then generated in the patterns at high temperatures, through the volatilization a second
phase porogen, while the material simultaneously vitrifies into a glassy organosilicate network. Pattern shape changes
upon vitrification are also quntified and indicating that a 12 % reduction in the pattern height of the porogen-loaded
imprint is observed with very little change in the pattern width. For a imprint without the added porogen, the shrinkage
is still anisotropic in the height direction, but reduced approximately by 4 %. Our results show that nanoporous low-k
patterns can be replicated via nanoimprint lithography with very little loss in the pattern quality.
The thermal embossing form of nanoimprint lithography is used to pattern arrays of nanostructures into several different polymer films. The shape of the imprinted patterns is characterized with nm precision using both X-ray scattering and reflectivity techniques. By studying the time dependent response of the pattern shape at temperatures near the glass transition temperature, we are able to perceive large levels of residual stress induced by the imprinting process. The large shear fields that result as the viscous polymer flows into the mold leads to residual stresses. At elevated temperatures in the freestanding structures (once the mold has been separated from the imprint), there is an accelerated reduction in pattern height in the reverse direction from which the material originally flowed into the mold. Two factors that influence this residual stress include the molecular mass of the polymer resist and the amount of time the pattern is annealed at high temperature in the presence of the mold.
To address several of the challenges associated with nanoimprint lithography, new measurement techniques that can correlate the physical structure of an imprinted nanostructure with the materials used and the imprinting conditions are critical for optimizing imprint processes. Specular X-ray reflectivity (SXR) is a widely used technique to quantify the thickness, density, and roughness of the non-patterned films. Here we extend the applicability of SXR to imprinted nanostructures by characterizing the pattern height, the line-to-space ratio as a function of pattern height, the residual layer thickness, and the fidelity of pattern transfer.
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