Characterization of highly-oriented ferroelectric Pb_xBa_(1-x)TiO_3

Pb_xBa_(1-x)TiO_3 (0.2 ≾ x ≾ 1) thin films were deposited on single-crystal MgO as well as amorphous Si_3N_4/Si substrates using biaxially textured MgO buffer templates, grown by ion beam-assisted deposition (IBAD). The ferroelectric films were stoichiometric and highly oriented, with only (001) and (100) orientations evident in x-ray diffraction (XRD) scans. Films on biaxially textured templates had smaller grains (60 nm average) than those deposited on single-crystal MgO (300 nm average). Electron backscatter diffraction (EBSD) has been used to study the microtexture on both types of substrates and the results were consistent with x-ray pole figures and transmission electron microscopy (TEM) micrographs that indicated the presence of 90° domain boundaries, twins, in films deposited on single-crystal MgO substrates. In contrast, films on biaxially textured substrates consisted of small single-domain grains that were either c or a oriented. The surface-sensitive EBSD technique was used to measure the tetragonal tilt angle as well as in-plane and out-of-plane texture. High-temperature x-ray diffraction (HTXRD) of films with 90° domain walls indicated large changes, as much as 60%, in the c and a domain fractions with temperature, while such changes were not observed for Pb_xBa_(1-x)TiO_3 (PBT) films on biaxially textured MgO/Si_3N_4/Si substrates, which lacked 90° domain boundaries

Graded ferroelectric capacitors with robust temperature characteristics

Ferroelectric thin films offer the possibility of engineering the dielectric response for tunable components in frequency-agile rf and microwave devices. However, this approach often leads to an undesired temperature sensitivity. Compositionally graded ferroelectric films have been explored as a means of redressing this sensitivity, but experimental observations vary depending on geometry and other details. In this paper, we present a continuum model to calculate the capacitive response of graded ferroelectric films with realistic electrode geometries by accurately accounting for the polarization distribution and long-range electrostatic interactions. We show that graded c-axis poled BaxSr_(1−xT)iO_3 BST parallel plate capacitors are ineffective while graded a-axis poled BST coplanar capacitors with interdigitated electrodes are extremely effective in obtaining high and temperature-stable dielectric properties

Biogenic Control of Manganese Doping in Zinc Sulfide Nanomaterial Using Shewanella oneidensis MR-1

Bacteria naturally alter the redox state of many compounds and perform atom-by-atom nanomaterial synthesis to create many inorganic materials. Recent advancements in synthetic biology have spurred interest in using biological systems to manufacture nanomaterials, implementing biological strategies to specify the nanomaterial characteristics such as size, shape, and optical properties. Here, we combine the natural synthetic capabilities of microbes with engineered genetic control circuits toward biogenically synthesized semiconductor nanomaterials. Using an engineered strain of Shewanella oneindensis with inducible expression of the cytochrome complex MtrCAB, we control the reduction of manganese (IV) oxide. Cytochrome expression levels were regulated using an inducer molecule, which enabled precise modulation of dopant incorporation into manganese doped zinc sulfide nanoparticles (Mn:ZnS). Thereby, a synthetic gene circuit controlled the optical properties of biogenic quantum dots. These biogenically assembled nanomaterials have similar physical and optoelectronic properties to chemically synthesized particles. Our results demonstrate the promise of implementing synthetic gene circuits for tunable control of nanomaterials made by biological systems

Plasmon-Assisted Chemical Vapor Deposition

We introduce a new chemical vapor deposition (CVD) process that can be used to selectively deposit materials of many different types. The technique makes use of the plasmon resonance in nanoscale metal structures to produce the local heating necessary to initiate deposition when illuminated by a focused low-power laser. We demonstrate the technique, which we refer to as plasmon-assisted CVD (PACVD), by patterning the spatial deposition of PbO and TiO_2 on glass substrates coated with a dispersion of 23 nm gold particles. The morphology of both oxide deposits is consistent with local laser-induced heating of the gold particles by more than 150 °C. We show that temperature changes of this magnitude are consistent with our analysis of the heat-loss mechanisms. The technique is general and can be used to spatially control the deposition of virtually any material for which a CVD process exists

Ultrastructure of Shewanella oneidensis MR-1 nanowires revealed by electron cryotomography

Bacterial nanowires have garnered recent interest as a proposed extracellular electron transfer (EET) pathway that links the bacterial electron transport chain to solid-phase electron acceptors away from the cell. Recent studies showed that Shewanella oneidensis MR-1 produces outer membrane (OM) and periplasmic extensions that contain EET components and hinted at their possible role as bacterial nanowires. However, their fine structure and distribution of cytochrome electron carriers under native conditions remained unclear, making it difficult to evaluate the potential electron transport (ET) mechanism along OM extensions. Here, we report high-resolution images of S. oneidensis OM extensions, using electron cryotomography (ECT). We developed a robust method for fluorescence light microscopy imaging of OM extension growth on electron microscopy grids and used correlative light and electron microscopy to identify and image the same structures by ECT. Our results reveal that S. oneidensis OM extensions are dynamic chains of interconnected outer membrane vesicles (OMVs) with variable dimensions, curvature, and extent of tubulation. Junction densities that potentially stabilize OMV chains are seen between neighboring vesicles in cryotomograms. By comparing wild type and a cytochrome gene deletion mutant, our ECT results provide the likely positions and packing of periplasmic and outer membrane proteins consistent with cytochromes. Based on the observed cytochrome packing density, we propose a plausible ET path along the OM extensions involving a combination of direct hopping and cytochrome diffusion. A mean-field calculation, informed by the observed ECT cytochrome density, supports this proposal by revealing ET rates on par with a fully packed cytochrome network

A Mechanistic Study of Carbonic Anhydrase Enhanced Calcite Dissolution

Carbonic anhydrase (CA) has been shown to promote calcite dissolution (Liu, 2001, https://doi.org/10.1111/j.1755-6724.2001.tb00531.x; Subhas et al., 2017, https://doi.org/10.1073/pnas.1703604114), and understanding the catalytic mechanism will facilitate our understanding of the oceanic alkalinity cycle. We use atomic force microscopy (AFM) to directly observe calcite dissolution in CA‐bearing solution. CA is found to etch the calcite surface only when in extreme proximity (~1 nm) to the mineral. Subsequently, the CA‐induced etch pits create step edges that serve as active dissolution sites. The possible catalytic mechanism is through the adsorption of CA on the calcite surface, followed by proton transfer from the CA catalytic center to the calcite surface during CO2 hydration. This study shows that the accessibility of CA to particulate inorganic carbon (PIC) in the ocean is critical in properly estimating oceanic CaCO3 and alkalinity cycles

A Mechanistic Study of Carbonic Anhydrase Enhanced Calcite Dissolution

Carbonic anhydrase (CA) has been shown to promote calcite dissolution (Liu, 2001, https://doi.org/10.1111/j.1755-6724.2001.tb00531.x; Subhas et al., 2017, https://doi.org/10.1073/pnas.1703604114), and understanding the catalytic mechanism will facilitate our understanding of the oceanic alkalinity cycle. We use atomic force microscopy (AFM) to directly observe calcite dissolution in CA‐bearing solution. CA is found to etch the calcite surface only when in extreme proximity (~1 nm) to the mineral. Subsequently, the CA‐induced etch pits create step edges that serve as active dissolution sites. The possible catalytic mechanism is through the adsorption of CA on the calcite surface, followed by proton transfer from the CA catalytic center to the calcite surface during CO2 hydration. This study shows that the accessibility of CA to particulate inorganic carbon (PIC) in the ocean is critical in properly estimating oceanic CaCO3 and alkalinity cycles