Gila E. Stein

Impact of Film Thickness on the Morphology of Mesoporous Carbon Films Using Organic−Organic Self-Assembly

Mesoporous polymer and carbon thin films are prepared by the organic-organic self-assembly of an oligomeric phenolic resin with an amphiphilic triblock copolymer template, Pluronic F127. The ratio of resin to template is selected such that a body-centered cubic (Im3m) mesostructure is formed in the bulk. However, well-ordered mesoporous films are not always obtained for thin films (<100 nm), and this behavior is found to be directly correlated with the initial phenolic resin to template ratio. Furthermore, the symmetry of ordered phases is highly dependent on the number of layers of spheres in the film: Monolayers and bilayers are characterized by hexagonal close-packed (HCP) symmetry, while films with approximately 5 layers of spheres exhibit a mixture of HCP and face-centered orthorhombic (FCO) structures. Ultrathick films having more than 30 layers of spheres are similar to the bulk body-centered cubic symmetry with a preferential orientation of the closest-packed (110) plane parallel to the substrate. Film thickness and initial composition of the carbonizable precursors in the template are critical factors in determining the morphology of mesoporous carbon films. These results provide insight into why difficulties have been reported in producing ultrathin ordered mesoporous carbon films using cooperative organic-organic self-assembly.

Three-dimensional x-ray metrology for block copolymer lithography line-space patterns

Abstract. We report on the development of a new measurement method, resonant critical-dimension small-angle x-ray scattering (res-CDSAXS), for the characterization of the buried structure of block copolymers (BCP) used in directed self assembly (DSA). We use resonant scattering at the carbon edge to enhance the contrast between the two polymer blocks and allow the determination of the three-dimensional shape of the native lamella in a line–space pattern by CDSAXS. We demonstrate the method by comparing the results from conventional CDSAXS to res-CDSAXS on a 1:1 DSA BCP sample with a nominal 50-nm pitch. The res-CDSAXS method provides substantially improved uncertainty in the fit of the line shape and allows the determination of the buried structure.

Control of Ordering and Structure in Soft Templated Mesoporous Carbon Films by Use of Selective Solvent Additives

The structure of ordered mesoporous carbons fabricated using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the template and phenolic resin (resol) as the carbon source can be easily manipulated by inclusion of low concentrations of low volatility selective solvents in the casting solution. Casting from neat methyl ethyl ketone yields a disordered structure even upon thermal annealing. However, addition of both dioctyl phthalate (DOP, PS selective) and dimethyl sulfoxide (DMSO, resol and PSS-DMODA selective) at modest concentrations to this casting solution provides sufficient mobility to produce highly ordered films with cylindrical mesopores. The DOP acts to swell the hydrophobic domain and can more than double the mesopore size, while the DMSO acts to swell the resol phase. Moreover, the surface area of the mesoporous carbons increases significantly as the meosopore size increases. This is a result of the decrease in wall thickness, which can be ascertained by the constant d-spacing of the mesostructure as the pore size increases. This behavior is counter to the typical effect of pore swelling agents that increase the pore size and decrease the surface area. Moreover, with only 4 wt % DOP/DMSO in the solution (20 wt % relative to solids), the scattering profiles exhibit many orders of diffraction, even upon carbonization, which is not typically observed for soft templated films. Variation in the concentration of DOP and DMSO during casting enables facile tuning of the structure of mesoporous carbon films.

Spatial coherence in electron-beam patterning

The authors demonstrate a simple method to identify noise sources in electron-beam systems and accurately quantify the resulting errors in feature placement. Line gratings with a 46 nm average pitch were patterned with electron-beam lithography and measured with transmission x-ray diffraction (XRD) and scanning electron microscopy (SEM). All SEM micrographs were analyzed in Fourier space to facilitate comparison with the XRD data. Diffraction profiles and Fourier transforms of SEM micrographs contained numerous “satellite” peaks, meaning weak peaks adjacent to the strong primary nodes, that are characteristic of periodic extensions and compressions in the grating pitch. The wavelength and amplitude of these pitch variations were calculated with a simple scaling law by comparing the positions and intensities of satellite peaks relative to their neighboring primary nodes. This approach is remarkably easy to implement because it does not require any modeling of electron density profiles. Data were used to ca...

High-Resolution, High-Throughput, Positive-Tone Patterning of Poly(ethylene glycol) by Helium Beam Exposure through Stencil Masks

In this work, a collimated helium beam was used to activate a thiol-poly(ethylene glycol) (SH-PEG) monolayer on gold to selectively capture proteins in the exposed regions. Protein patterns were formed at high throughput by exposing a stencil mask placed in proximity to the PEG-coated surface to a broad beam of helium particles, followed by incubation in a protein solution. Attenuated Total Reflectance–Fourier Transform Infrared Spectroscopy (ATR–FTIR) spectra showed that SH-PEG molecules remain attached to gold after exposure to beam doses of 1.5–60 µC/cm2 and incubation in PBS buffer for one hour, as evidenced by the presence of characteristic ether and methoxy peaks at 1120 cm−1 and 2870 cm−1, respectively. X-ray Photoelectron Spectroscopy (XPS) spectra showed that increasing beam doses destroy ether (C–O) bonds in PEG molecules as evidenced by the decrease in carbon C1s peak at 286.6 eV and increased alkyl (C–C) signal at 284.6 eV. XPS spectra also demonstrated protein capture on beam-exposed PEG regions through the appearance of a nitrogen N1s peak at 400 eV and carbon C1s peak at 288 eV binding energies, while the unexposed PEG areas remained protein-free. The characteristic activities of avidin and horseradish peroxidase were preserved after attachment on beam-exposed regions. Protein patterns created using a 35 µm mesh mask were visualized by localized formation of insoluble diformazan precipitates by alkaline phosphatase conversion of its substrate bromochloroindoyl phosphate-nitroblue tetrazolium (BCIP-NBT) and by avidin binding of biotinylated antibodies conjugated on 100 nm gold nanoparticles (AuNP). Patterns created using a mask with smaller 300 nm openings were detected by specific binding of 40 nm AuNP probes and by localized HRP-mediated deposition of silver nanoparticles. Corresponding BSA-passivated negative controls showed very few bound AuNP probes and little to no enzymatic formation of diformazan precipitates or silver nanoparticles.

Ordered arrays of polymer droplets with triangular, circular, and rod-like shapes

We demonstrate that topographically patterned oxide surfaces can direct the dewetting of an overlying polystyrene film and produce triangular, circular, or rod-like droplets. Thin films of polystyrene on oxide surfaces are unstable and will rupture by spinodal dewetting. For our studies, spinodal dewetting is suppressed because the dimensions of oxide patterns are smaller than the dominant instability wavelength. Dewetting is initiated at specific points on the surface by modulating the film curvature, and this drives the formation of unstable polymer rims that break apart into discrete droplets. The symmetry of oxide patterns controls the direction of polymer flow during dewetting, and these dynamics determine the locations and shapes of polymer droplets. Patterns with two-fold symmetry generate drops shaped like rods or bullets, and patterns with three-fold symmetry will produce triangles, distorted circles, or perfect circles.

Surprising states of order for linear diblock copolymers

Thermal treatments unlock low-symmetry phases resembling those of metals and alloys Two polymers that are immiscible would separate on a macroscopic scale—like oil and water—to minimize interfacial area. However, when the different polymer chains are linked with a covalent bond to form a linear diblock copolymer, the forced interaction drives a self-assembly into periodic domains at the scale of 10 to 100 nm (1). The shapes and arrangements of these domains are often very simple, such as spherical micelles in a body-centered cubic (bcc) lattice. One notable exception was the discovery that spherical micelles can assemble into a Frank-Kasper (FK) σ phase (2), a complex low-symmetry structure common in metals and alloys. Many other metallurgical FK structures are known, so if similar principles govern lattice selection in these distinct materials classes, then it is possible that many linear diblock copolymer phases remain undiscovered. On page 520 of this issue, Kim et al. (3) predict that several FK phases have nearly degenerate free energies, and show how clever thermal treatments can control the ordering pathway to access two of these previously undocumented structures.

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show that MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. The evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.

Modeling acid transport in chemically amplified resist films

The acid-catalyzed deprotection of glassy poly(4-hydroxystyrene-co-tert butyl acrylate) films was studied with infrared absorbance spectroscopy and stochastic simulations. Experimental data were interpreted with a simple description of subdiffusive acid transport coupled to second-order acid loss. This model predicts key attributes of observed deprotection rates, such as fast reaction at short times, slow reaction at long times, and a non-linear dependence on acid loading. The degree of anomalous character is reduced by increasing the post-exposure bake temperature or adding plasticizing agents to the polymer resin. These findings indicate that the acid mobility and overall deprotection kinetics are coupled to glassy matrix dynamics. Furthermore, the acid diffusion lengths were calculated from the anomalous transport model and compared with nanopattern line widths. The consistent scaling between experiments and simulations suggests that the anomalous diffusion model could be further developed into a predictive lithography tool.

Characterizing acid diffusion lengths in chemically amplified resists from measurements of deprotection kinetics

Abstract. The acid-catalyzed deprotection of glassy poly(4-hydroxystyrene-co-tertbutyl acrylate) films was studied with infrared absorbance spectroscopy and stochastic simulations. Experimental data were interpreted with a simple description of subdiffusive acid transport coupled to second-order acid loss. This model predicts key attributes of observed deprotection rates, such as fast reaction at short times, slow reaction at long times, and a nonlinear dependence on acid loading. Fickian diffusion is approached by increasing the postexposure bake temperature or adding plasticizing agents to the polymer resin. These findings demonstrate that acid mobility and overall deprotection kinetics are coupled to glassy matrix dynamics. To complement the analysis of bulk kinetics, acid diffusion lengths were calculated from the anomalous transport model and compared with nanopattern line widths. The consistent scaling between experiments and simulations suggests that the anomalous diffusion model could be further developed into a predictive lithography tool.