The ability to engineer the thermal conductivity of materials allows us to control the flow of heat and derive novel functionalities such as thermal rectification, thermal switching and thermal cloaking. While this could be achieved by making use of composites and metamaterials at bulk length-scales, engineering the thermal conductivity at micro- and nano-scale dimensions is considerably more challenging. In this work, we show that the local thermal conductivity along a single Si nanowire can be tuned to a desired value (between crystalline and amorphous limits) with high spatial resolution through selective helium ion irradiation with a well-controlled dose. The underlying mechanism is understood through molecular dynamics simulations and quantitative phonon-defect scattering rate analysis, where the behaviour of thermal conductivity with dose is attributed to the accumulation and agglomeration of scattering centres at lower doses. Beyond a threshold dose, a crystalline-amorphous transition was observed.

Abstract

The development of barium strontium titanate-based tunable dielectrics is currently hindered by high losses in the paraelectric phase. Barium strontium titanate (BST) thin films and ceramics show a range of ferroelectric transition behavior, from normal, diffuse, and relaxor-like ferroelectric responses, depending on the sample preparation route. Rayleigh analysis, the temperature-dependent dielectric response, and the optical second harmonic generation were used to characterize the ferroelectric response of bulk and thin film BST. Ferroelectricity is observed to persist in BST for 30°C above the global phase transition temperature in ceramics and over 50°C in thin films. Piezoresponse force microscopy on BST ceramics with extensive residual ferroelectricity reveals the coexistence of nanoscale polar regions, typical of relaxor ferroelectrics, as well as micrometer scale domain structures. The nature of the phase transition was probed using electron energy loss spectroscopy and found to correlated with the nanoscale A-site chemical inhomogeneity in the samples.

Atomic force microscopy is widely used for nanoscale characterization of materials by scientists worldwide. The long-held belief of ambient AFM is that the tip is generally chemically inert but can be functionalized with respect to the studied sample. This implies that basic imaging and scanning procedures do not affect surface and bulk chemistry of the studied sample. However, an in-depth study of the confined chemical processes taking place at the tip−surface junction and the associated chemical changes to the material surface have been missing as of now. Here, we used a hybrid system that combines time-of-flight secondary ion mass spectrometry with an atomic force microscopy to investigate the chemical interactions that take place at the tip−surface junction. Investigations showed that even basic contact mode AFM scanning is able to modify the surface of the studied sample. In particular, we found that the silicone oils deposited from the AFM tip into the scanned regions and spread to distances exceeding 15 μm from the tip. These oils were determined to come from standard gel boxes used for the storage of the tips. The explored phenomena are important for interpreting and understanding results of AFM mechanical and electrical studies relying on the state of the tip−surface junction.

The pursuit of more advanced electronics, and finding solutions to energy needs often hinges upon the discovery and optimization of new functional materials. However, the discovery rate of these materials is alarmingly low. Much of the information that could drive this rate higher is scattered across tens of thousands of papers in the extant literature published over several decades but is not in an indexed form, and cannot be used in entirety without substantial effort. Many of these limitations can be circumvented if the experimentalist has access to systematized collections of prior experimental procedures and results. Here, we investigate the property-processing relationship during growth of oxide films by pulsed laser deposition. To do so, we develop an enabling software tool to (1) mine the literature of relevant papers for synthesis parameters and functional properties of previously studied materials, (2) enhance the accuracy of this mining through crowd sourcing approaches, (3) create a searchable repository that will be a communitywide resource enabling material scientists to leverage this information, and (4) provide through the Jupyter notebook platform, simple machine-learning-based analysis to learn the complex interactions between growth parameters and functional properties (all data/codes available on https://github.com/ORNL-DataMatls). The results allow visualization of growth windows, trends and outliers, and which can serve as a template for analyzing the distribution of growth conditions, provide starting points for related compounds and act as feedback for first-principles calculations.Such tools will comprise an integral part of the materials design schema in the coming decade.

The next generation optical, electronic, biological, and sensing devices as well as platforms will inevitably extend their architecture into the 3rd dimension to enhance functionality. In focused ion beam induced deposition (FIBID), a helium gas field ion source can be used with an organometallic precursor gas to fabricate nanoscale structures in 3D with high-precision and smaller critical dimensions than focused electron beam induced deposition (FEBID), traditional liquid metal source FIBID, or other additive manufacturing technology. In this work, we report the effect of beam current, dwell time, and pixel pitch on the resultant segment and angle growth for nanoscale 3D mesh objects. We note subtle beam heating effects, which impact the segment angle and the feature size. Additionally, we investigate the competition of material deposition and sputtering during the 3D FIBID process, with helium ion microscopy experiments and Monte Carlo simulations. Our results show complex 3D mesh structures measuring ~300 nm in the largest dimension, with individual features as small as 16 nm at full width half maximum (FWHM). These assemblies can be completed in minutes, with the underlying fabrication technology compatible with existing lithographic techniques, suggesting a higher-throughput pathway to integrating FIBID with established nanofabrication techniques.

We performed multiscale molecular dynamics (MD) simulations of bottlebrush polymers with fluorinated side chains to investigate the influence of the bottlebrush architecture on the spatial distribution of fluorinated moieties. In thin films, coarse-grained MD simulations reveal that interfaces are characterized by backbone depletion with side chains at the interface oriented parallel to the surface. At the molecular level, atomistic MD simulations show that fluorine atoms in the bottlebrush are preferentially located at air–film interfaces. Both simulation results indicate enrichment of fluorinated moieties at the air–film interface. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirms the enhancement of fluorinated moieties in both bottlebrush and linear copolymer films. ToF-SIMS also shows that for long linear chains the difference between the concentration of fluorinated moieties at the air–film interface and the concentration at the bulk or at the middle of the film is relatively higher than those observed in shorter linear chains (macromonomers) or bottlebrushes. Although there are differences in the distributions of fluorine moieties between linear chains and bottlebrushes, simulations suggest that the effect of polymer architecture on contact angle and surface energy is only significant at low molecular weights. Measurements of the contact angle of films composed of different modestly high molecular weights of linear chains and bottlebrushes do not show a significant difference in the value of the contact angle, in a way restricting the tunability of surface energy and contact angle via polymer architecture. With these results, our study provides insights into the effective use of partially fluorinated bottlebrush polymer for directed self-assemblies at surfaces in thin films. Specifically, achieving a high degree of difference in surface energies for fluorinated thin films is limited to films with low molecular weight constituents, and the effect of molecular architecture is subtle, suggesting it is insufficient to only rely on this strategy to further lower the surface energy of these films for applications directed toward tuned wettability, adhesive interactions, and fouling resistance.

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