Synthesis of Submicron PEDOT Particles of High Electrical Conductivity via Continuous Aerosol Vapor Polymerization.

Current state-of-the-art synthetic strategies produce conducting polymers suffering from low processability and unstable chemical and/or physical properties stifling research and development. Here, we introduce a platform for synthesizing scalable submicron-sized particles of the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). The synthesis is based on a hybrid approach utilizing an aerosol of aqueous oxidant droplets and monomer vapor to engineer a scalable synthetic scheme. This aerosol vapor polymerization technology results in bulk quantities of discrete solid-state submicron particles (750 nm diameter) with the highest reported particle conductivity (330 ± 70 S/cm) so far. Moreover, particles are dispersible in organics and water, obviating the need for surfactants, and remain electrically conductive and doped over a period of months. This enhanced processability and environmental stability enable their incorporation in thermoplastic and cementitious composites for engineering chemoresistive pH and temperature sensors.

Revealing the Bonding Environment of Zn in ALD Zn(O,S) Buffer Layers through X-ray Absorption Spectroscopy.

Zn(O,S) buffer layer electronic configuration is determined by its composition and thickness, tunable through atomic layer deposition. The Zn K and L-edges in the X-ray absorption near edge structure verify ionicity and covalency changes with S content. A high intensity shoulder in the Zn K-edge indicates strong Zn 4s hybridized states and a preferred c-axis orientation. 2-3 nm thick films with low S content show a subdued shoulder showing less contribution from Zn 4s hybridization. A lower energy shift with film thickness suggests a decreasing bandgap. Further, ZnSO4 forms at substrate interfaces, which may be detrimental for device performance.

Enhancing Cycling Stability of Aqueous Polyaniline Electrochemical Capacitors.

Electrochemical capacitors fabricated with polyaniline nanofibers are cycled 150 000 times with 98% capacitance retention. These devices maintain an energy density of 11.41 Wh/kg at a power density of 4000 W/kg, 64 times greater than that of an identically fabricated device based on activated carbon (0.177 Wh/kg at 4600 W/kg). For applications requiring a higher specific energy, 33.39 Wh/kg at a specific power of 600 W/kg is obtained by widening the voltage window; this device retains 93% capacitance after 10 000 cycles. We achieve a high cycling stability through careful device engineering paired with a renewed focus on the electrochemical processes occurring at the positive and negative electrodes during cycling.

ALD Zn(O,S) Thin Films' Interfacial Chemical and Structural Configuration Probed by XAS.

The ability to precisely control interfaces of atomic layer deposited (ALD) zinc oxysulfide (Zn(O,S)) buffer layers to other layers allows precise tuning of solar cell performance. The O K- and S K-edge X-ray absorption near edge structure (XANES) of ∼2-4 nm thin Zn(O,S) films reveals the chemical and structural influences of their interface with ZnO, a common electrode material and diffusion barrier in solar cells. We observe that sulfate formation at oxide/sulfide interfaces is independent of film composition, a result of sulfur diffusion toward interfaces. Leveraging sulfur's diffusivity, we propose an alternative ALD process in which the zinc precursor pulse is bypassed during H2S exposure. Such a process yields similar results to the nanolaminate deposition method and highlights mechanistic differences between ALD sulfides and oxides. By identifying chemical species and structural evolution at sulfide/oxide interfaces, this work provides insights into increasing thin film solar cell efficiencies.

Relating Electronic and Geometric Structure of Atomic Layer Deposited BaTiO3 to its Electrical Properties.

Atomic layer deposition allows the fabrication of BaTiO3 (BTO) ultrathin films with tunable dielectric properties, which is a promising material for electronic and optical technology. Industrial applicability necessitates a better understanding of their atomic structure and corresponding properties. Through the use of element-specific X-ray absorption near edge structure (XANES) analysis, O K-edge of BTO as a function of cation composition and underlying substrate (RuO2 and SiO2) is revealed. By employing density functional theory and multiple scattering simulations, we analyze the distortions in BTO's bonding environment captured by the XANES spectra. The spectral weight shifts to lower energy with increasing Ti content and provides an atomic scale (microscopic) explanation for the increase in leakage current density. Differences in film morphologies in the first few layers near substrate-film interfaces reveal BTO's homogeneous growth on RuO2 and its distorted growth on SiO2. This work links structural changes to BTO thin-film properties and provides insight necessary for optimizing future BTO and other ternary metal oxide-based thin-film devices.

Variation of energy density of states in quantum dot arrays due to interparticle electronic coupling.

Subnanometer-resolved local electron energy structure was measured in PbS quantum dot superlattice arrays using valence electron energy loss spectroscopy with scanning transmission electron microscopy. We found smaller values of the lowest available transition energies and an increased density of electronic states in the space between quantum dots with shorter interparticle spacing, indicating extension of carrier wave functions as a result of interparticle electronic coupling. A quantum simulation verified both trends and illustrated the wave function extension effect.

Vortex-pattern self-assembly in Mn-doped ZnSe nanorods.

Spontaneous patterning of anisotropic nanostructures into ordered assemblies remains a challenging quest, which requires controlled innovative approaches. One way to achieve such ordering of 1D nanorods is by manipulating the varieties of interactions (attractive and repulsive forces) present in colloidal solutions of anisotropic nanocrystals. The other ingenuous pathway is solvent-evaporation-mediated self-organization of the 1D nanorods. By following the second protocol, we have achieved exclusive pillar self-assembled patterns of visible-light-emitting Mn-doped ZnSe nanorods. The nanorods also exhibit intriguing vortex patterning observed by directional solvent evaporation from the nanorod solution. The effect of solvent evaporation to generate such unique morphologies on the TEM grid is discussed and the reported procedure to obtain the assembled patterns of visible-light-emitting, doped nanorods might be useful for future technological applications.

Subnanometer Thin ß-Indium Sulfide Nanosheets.

Nanosheets are a peculiar kind of nanomaterials that are grown two-dimensionally over a micrometer in length and a few nanometers in thickness. Wide varieties of inorganic semiconductor nanosheets are already reported, but controlling the crystal growth and tuning their thickness within few atomic layers have not been yet explored. We investigate here the parameters that determine the thickness and the formation mechanism of subnanometer thin (two atomic layers) cubic indium sulfide (In2S3) nanosheets. Using appropriate reaction condition, the growth kinetics is monitored by controlling the decomposition rate of the single source precursor of In2S3 as a function of nucleation temperature. The variation in the thickness of the nanosheets along the polar [111] direction has been correlated with the rate of evolved H2S gas, which in turn depends on the rate of the precursor decomposition. In addition, it has been observed that the thickness of the In2S3 nanosheets is related to the nucleation temperature.

Prevention of photooxidation in blue-green emitting Cu doped ZnSe nanocrystals.

This communication highlights unstable blue-green emitting Cu doped ZnSe nanocrystals stabilized by diluting the surface Se with a calculated amount of S.