Catalysis of the Oxygen-Evolution Reaction in 1.0 M Sulfuric Acid by Manganese Antimonate Films Synthesized via Chemical Vapor Deposition.

Manganese antimonate (MnySb1-yOx) electrocatalysts for the oxygen-evolution reaction (OER) were synthesized via chemical vapor deposition. Mn-rich rutile Mn0.63Sb0.37Ox catalysts on fluorine-doped tin oxide (FTO) supports drove the OER for 168 h (7 days) at 10 mA cm-2 with a time-averaged overpotential of 687 ± 9 mV and with >97% Faradaic efficiency. Time-dependent anolyte composition analysis revealed the steady dissolution of Mn and Sb. Extended durability analysis confirmed that Mn-rich MnySb1-yOx materials are more active but dissolve at a faster rate than previously reported Sb-rich MnySb1-yOx alloys.

Inclination of polarized illumination increases symmetry of structures grown via inorganic phototropism.

Inclination of unpatterned, linearly polarized illumination in the plane of the electric field oscillation effected increased directional feature alignment and decreased off-axis order in Se-Te deposits generated by inorganic phototropic growth relative to that produced using normal incidence. Optically based growth simulations reproduced the experimental results indicating a photonic basis for the morphology change. Modeling of the light scattering at the growth interface revealed that illumination inclination enhances scattering that localizes the optical field along the polarization plane and suppresses cooperativity in defect-driven scattering. Thus, the symmetry of the deposited structures increased as the asymmetry of the illumination increased, as measured by the inclination of the illumination incidence away from the surface normal.

Plastic Morphological Response to Spectral Shifts during Inorganic Phototropic Growth.

Plants exhibit phototropism in which growth is directed toward sunlight and demonstrate morphological plasticity in response to changes in the spectral distribution of the incident illumination. Inorganic phototropic growth via template-free, light-directed electrochemical deposition of semiconductor material can spontaneously generate highly ordered mesostructures with anisotropic, nanoscale lamellar features that exhibit a pitch proportional to the wavelength (λ) of the stimulating illumination. In this work, Se-Te films were generated via a two-step inorganic phototropic growth process using a series of narrowband light-emitting diode sources with discrete output wavelengths (λ0 ≠ λ1). Analogous to the plasticity observed in plants, changes in illumination wavelength from λ0 to λ1 resulted in morphological changes including feature branching, termination, and/or fusion along the growth direction. The interfacial feature pitch changed with the growth duration, in some cases in a notably nonmonotonic fashion, and eventually matched that obtained for growth using only λ1. Simulated morphologies generated by modeling light-material interactions at the growth interface closely matched the evolved structures observed experimentally, indicating that the characteristics of the optical stimulation produce the observed plastic response during inorganic phototropic growth. Examination of the interfacial electric field modulation for λ1 illumination of simplified structures, representative of those generated experimentally, revealed the interfacial light scattering and concentration behavior that directed phototropic growth away from equilibrium, as well as the emergent nature of the phenomena that reestablish equilibrium.

Selective-Area, Water-Free Atomic Layer Deposition of Metal Oxides on Graphene Defects.

Passivating defective regions on monolayer graphene with metal oxides remains an active area of research for graphene device integration. To effectively passivate these regions, a water-free atomic layer deposition (ALD) recipe was developed and yielded selective-area ALD (sa-ALD) of mixed-metal oxides onto line defects in monolayer graphene. The anisotropically deposited film targeted high-energy defect sites that were formed during synthesis or transfer of the graphene layer. The passivating layer exceeded 10 nm thickness with minimal deposition onto the basal plane of graphene. The mixed-metal oxide film was of comparable quality to films deposited using nonselective water-based ALD methods, as shown by X-ray photoelectron spectroscopy. The development of sa-ALD techniques to target defect regions on the graphene sheet, while keeping the basal plane intact, will provide a new mechanism to passivate graphene defects and modify the electronic and physical properties of graphene.

Assessing Effects of Near-Field Synergistic Light Absorption on Ordered Inorganic Phototropic Growth.

We report herein that synergistic light absorption in the optical near-field enables nanoscale self-organization during inorganic phototropic growth. Se-Te was grown electrochemically under illumination from an incoherent, unstructured light source in geometrically constrained, wavelength scale areas. Despite the limited dimensions, with as few as two discrete features produced in a single sub-micron dimension, the deposit morphology exhibited defined order and anisotropy. Computer modeling analysis of light absorption in simulated structures revealed a synergy wherein light capture in a nanoscale feature was enhanced by the presence of additional adjacent features, with the synergistic effect originating predominantly from nearest neighbor contributions. Modeling moreover indicated that synergistic absorption is produced by scattering of the incident illumination by individual nanoscale features, leading to a local increase in the near-field intensity and consequently increasing the absorption in neighboring features. The interplay between these optical processes establishes the basis for spontaneous order generation via inorganic phototropic growth.

Path-Dependent Morphological Evolution of Se-Te Mesostructures Prepared by Inorganic Phototropic Growth.

We describe herein a path-dependent "history" effect wherein the film morphology generated in the second step of a two-step inorganic phototropic growth process depends on a preexisting structure that has been first grown under different optical stimulation conditions. Se-Te generated with static illumination exhibited a highly anisotropic lamellar morphology with a characteristic feature pitch proportional to the input wavelength. Growth using first a short wavelength of light, followed by growth using a longer wavelength, resulted in the second-stage morphology exhibiting termination of lamellae formed during the first growth step. The lamellar pitch at the end of the second growth step was larger than that effected in the first step. In contrast, use of the same input wavelengths but in the opposite order produced no change in the feature pitch but rather only linear feature extension. Analysis of light absorption in simulated structures, in tandem with the empirical data, indicated that the history effect and asymmetric path dependence are a result of emergent nanophotonic processes at the growth interface that dynamically shape the optical field and direct morphological evolution of the photodeposit in a continuous feedback loop.

Inorganic Phototropism in Electrodeposition of Se-Te.

Photoelectrochemical deposition of Se-Te on isolated Au islands using an unstructured, incoherent beam of light produces growth of Se-Te alloy toward the direction of the incident light beam. Full-wave electromagnetic simulations of light absorption indicated that the induced spatial growth anisotropy was a function of asymmetric absorption in the evolving deposit. Inorganic phototropic growth is analogous to biological systems such as palm trees that exhibit phototropic growth wherein physical extension of the plant guides the crown toward the time-averaged position of the sun, to maximize solar harvesting.

Template-Free Synthesis of Periodic Three-Dimensional PbSe Nanostructures via Photoelectrodeposition.

Highly periodic, geometrically directed, anisotropic Se-Pb films have been synthesized at room temperature from an isotropic aqueous solution without the use of physical templates by photoelectrodeposition using a series of discrete input illumination polarizations and wavelengths from an unstructured, uncorrelated, incoherent light source. Dark growth did not generate deposits with substantial long-range order, but growth using unpolarized illumination resulted in an ordered, nanoscale, mesh-type morphology. Linearly polarized illumination generated Se-Pb deposits that displayed an ordered, highly anisotropic lamellar pattern wherein the long axes of the lamellae were aligned parallel to the light polarization vector. The pitch of the lamellar features was proportional to the input light wavelength, as confirmed by Fourier analysis. Full-wave electromagnetic and Monte Carlo growth simulations that incorporated only the fundamental light-matter interactions during growth successfully reproduced the experimentally observed morphologies and quantitatively matched the pattern periodicities. Electrochemical postprocessing of the as-deposited Se-Pb structures resulted in the generation of stoichiometric, crystalline PbSe while preserving the nanopatterned morphology, thus broadening the genus of materials that can be prepared with controlled three-dimensional morphologies through maskless photoelectrodeposition.

Operando Spectroscopic Analysis of CoP Films Electrocatalyzing the Hydrogen-Evolution Reaction.

Transition metal phosphides exhibit high catalytic activity toward the electrochemical hydrogen-evolution reaction (HER) and resist chemical corrosion in acidic solutions. For example, an electrodeposited CoP catalyst exhibited an overpotential, η, of -η < 100 mV at a current density of -10 mA cm-2 in 0.500 M H2SO4(aq). To obtain a chemical description of the material as-prepared and also while effecting the HER in acidic media, such electrocatalyst films were investigated using Raman spectroscopy and X-ray absorption spectroscopy both ex situ as well as under in situ and operando conditions in 0.500 M H2SO4(aq). Ex situ analysis using the tandem spectroscopies indicated the presence of multiple ordered and disordered phases that contained both near-zerovalent and oxidized Co species, in addition to reduced and oxygenated P species. Operando analysis indicated that the active electrocatalyst was primarily amorphous and predominantly consisted of near-zerovalent Co as well as reduced P.

Profiling Photoinduced Carrier Generation in Semiconductor Microwire Arrays via Photoelectrochemical Metal Deposition.

Au was photoelectrochemically deposited onto cylindrical or tapered p-Si microwires on Si substrates to profile the photoinduced charge-carrier generation in individual wires in a photoactive semiconductor wire array. Similar experiments were repeated for otherwise identical Si microwires doped to be n-type. The metal plating profile was conformal for n-type wires, but for p-type wires was a function of distance from the substrate and was dependent on the illumination wavelength. Spatially resolved charge-carrier generation profiles were computed using full-wave electromagnetic simulations, and the localization of the deposition at the p-type wire surfaces observed experimentally correlated well with the regions of enhanced calculated carrier generation in the volumes of the microwires. This technique could potentially be extended to determine the spatially resolved carrier generation profiles in a variety of mesostructured, photoactive semiconductors.

Morphological Expression of the Coherence and Relative Phase of Optical Inputs to the Photoelectrodeposition of Nanopatterned Se-Te Films.

Highly anisotropic and ordered nanoscale lamellar morphologies can be spontaneously generated over macroscopic areas, without the use of a photomask or any templating agents, via the photoelectrodeposition of Se-Te alloy films. To form such structures, the light source can be a single, linearly polarized light source that need not necessarily be highly coherent. In this work, the variation in the morphologies produced by this deposition process was evaluated in response to differences in the coherence and relative phase between multiple simultaneous linearly polarized illumination inputs. Specifically, the morphologies of photoelectrodeposits were evaluated when two tandem same-wavelength sources with discrete linear polarizations, both either mutually incoherent or mutually coherent (with defined phase differences), were used. Additionally, morphologies were simulated via computer modeling of the interfacial light scattering and absorption during the photoelectrochemical growth process. The morphologies that were generated using two coherent, in-phase sources were equivalent to those generated using only a single source. In contrast, the use of two coherent, out-of-phase sources produced a range of morphological patterns. For small out-of-phase addition of orthogonal polarization components, lamellar-type patterns were observed. When fully out-of-phase orthogonal sources (circular polarization) were used, an isotropic, mesh-type pattern was instead generated, similar to that observed when unpolarized illumination was utilized. In intermediate cases, anisotropic lamellar-type patterns were superimposed on the isotropic mesh-type patterns, and the relative height between the two structures scaled with the amount of out-of-phase addition of the orthogonal polarization components. Similar results were obtained when two incoherent sources were utilized. In every case, the long axis of the lamellar-type morphology component aligned parallel to the intensity-weighted average polarization orientation. The observations consistently agreed with computer simulations, indicating that the observed morphologies were fully determined by the nature of the illumination utilized during the growth process. The collective data thus indicated that the photoelectrodeposition process exhibits sensitivity toward the coherency, relative phase, and polarization orientations of all optical inputs and that this sensitivity is physically expressed in the morphology of the deposit.

Polarization Control of Morphological Pattern Orientation During Light-Mediated Synthesis of Nanostructured Se-Te Films.

The template-free growth of well ordered, highly anisotropic lamellar structures has been demonstrated during the photoelectrodeposition of Se-Te films, wherein the orientation of the pattern can be directed by orienting the linear polarization of the incident light. This control mechanism was investigated further herein by examining the morphologies of films grown photoelectrochemically using light from two simultaneous sources that had mutually different linear polarizations. Photoelectrochemical growth with light from two nonorthogonally polarized same-wavelength sources generated lamellar morphologies in which the long axes of the lamellae were oriented parallel to the intensity-weighted average polarization orientation. Simulations of light scattering at the solution-film interface were consistent with this observation. Computer modeling of these growths using combined full-wave electromagnetic and Monte Carlo growth simulations successfully reproduced the experimental morphologies and quantitatively agreed with the pattern orientations observed experimentally by considering only the fundamental light-material interactions during growth. Deposition with light from two orthogonally polarized same-wavelength as well as different-wavelength sources produced structures that consisted of two intersecting sets of orthogonally oriented lamellae in which the relative heights of the two sets could be varied by adjusting the relative source intensities. Simulations of light absorption were performed in analogous, idealized intersecting lamellar structures and revealed that the lamellae preferentially absorbed light polarized with the electric field vector along their long axes. These data sets cumulatively indicate that anisotropic light scattering and light absorption generated by the light polarization produces the anisotropic morphology and that the resultant morphology is a function of all illumination inputs despite differing polarizations.

Self-Optimizing Photoelectrochemical Growth of Nanopatterned Se-Te Films in Response to the Spectral Distribution of Incident Illumination.

Photoelectrochemical growth of Se-Te films spontaneously produces highly ordered, nanoscale lamellar morphologies with periodicities that can be tuned by varying the illumination wavelength during deposition. This phenomenon has been characterized further herein by determining the morphologies of photoelectrodeposited Se-Te films in response to tailored spectral illumination profiles. Se-Te films grown under illumination from four different sources, having similar average wavelengths but having spectral bandwidths that spanned several orders of magnitude, all nevertheless produced similar structures which had a single, common periodicity as quantitatively identified via Fourier analysis. Film deposition using simultaneous illumination from two narrowband sources, which differed in average wavelength by several hundred nanometers, resulted in a structure with only a single periodicity intermediate between the periods observed when either source alone was used. This single periodicity could be varied by manipulating the relative intensity of the two sources. An iterative model that combined full-wave electromagnetic effects with Monte Carlo growth simulations, and that considered only the fundamental light-material interactions during deposition, was in accord with the morphologies observed experimentally. Simulations of light absorption and concentration in idealized lamellar arrays, in conjunction with all of the available data, additionally indicated that a self-optimization of the periodicity of the nanoscale pattern, resulting in the maximization of the anisotropy of interfacial light absorption in the three-dimensional structure, is consistent with the observed growth process of such films.

The influence of structure and processing on the behavior of TiO2 protective layers for stabilization of n-Si/TiO2/Ni photoanodes for water oxidation.

Light absorbers with moderate band gaps (1-2 eV) are required for high-efficiency solar fuels devices, but most semiconducting photoanodes undergo photocorrosion or passivation in aqueous solution. Amorphous TiO2 deposited by atomic-layer deposition (ALD) onto various n-type semiconductors (Si, GaAs, GaP, and CdTe) and coated with thin films or islands of Ni produces efficient, stable photoanodes for water oxidation, with the TiO2 films protecting the underlying semiconductor from photocorrosion in pH = 14 KOH(aq). The links between the electronic properties of the TiO2 in these electrodes and the structure and energetic defect states of the material are not yet well-elucidated. We show herein that TiO2 films with a variety of crystal structures and midgap defect state distributions, deposited using both ALD and sputtering, form rectifying junctions with n-Si and are highly conductive toward photogenerated carriers in n-Si/TiO2/Ni photoanodes. Moreover, the photovoltage of these electrodes can be modified by annealing the TiO2 in reducing or oxidizing environments. All of the polycrystalline TiO2 films with compact grain boundaries investigated herein protected the n-Si photoanodes against photocorrosion in pH = 14 KOH(aq). Hence, in these devices, conduction through the TiO2 layer is neither specific to a particular amorphous or crystalline structure nor determined wholly by a particular extrinsic dopant impurity. The coupled structural and energetic properties of TiO2, and potentially other protective oxides, can therefore be controlled to yield optimized photoelectrode performance.

Template-free preparation of crystalline Ge nanowire film electrodes via an electrochemical liquid-liquid-solid process in water at ambient pressure and temperature for energy storage.

The direct electrodeposition of crystalline germanium (Ge) nanowire film electrodes from an aqueous solution of dissolved GeO(2) using discrete 'flux' nanoparticles capable of dissolving Ge(s) has been demonstrated. Electrodeposition of Ge at inert electrode substrates decorated with small (<100 nm), discrete indium (In) nanoparticles resulted in crystalline Ge nanowire films with definable nanowire diameters and densities without the need for a physical or chemical template. The Ge nanowires exhibited strong polycrystalline character as-deposited, with approximate crystallite dimensions of 20 nm and a mixed orientation of the crystallites along the length of the nanowire. Energy dispersive spectroscopic elemental mapping of individual Ge nanowires showed that the In nanoparticles remained at the base of each nanowire, indicating good electrical communication between the Ge nanowire and the underlying conductive support. As-deposited Ge nanowire films prepared on Cu supports were used without further processing as Li(+) battery anodes. Cycling studies performed at 1 C (1624 mA g(-1)) indicated the native Ge nanowire films supported stable discharge capacities at the level of 973 mA h g(-1), higher than analogous Ge nanowire film electrodes prepared through an energy-intensive vapor-liquid-solid nanowire growth process. The cumulative data show that ec-LLS is a viable method for directly preparing a functional, high-activity nanomaterials-based device component. The work presented here is a step toward the realization of simple processes that make fully functional energy conversion/storage technologies based on crystalline inorganic semiconductors entirely through benchtop, aqueous chemistry and electrochemistry without time- or energy-intensive process steps.

Wet chemical functionalization of III-V semiconductor surfaces: alkylation of gallium arsenide and gallium nitride by a Grignard reaction sequence.

Crystalline gallium arsenide (GaAs) (111)A and gallium nitride (GaN) (0001) surfaces have been functionalized with alkyl groups via a sequential wet chemical chlorine activation, Grignard reaction process. For GaAs(111)A, etching in HCl in diethyl ether effected both oxide removal and surface-bound Cl. X-ray photoelectron (XP) spectra demonstrated selective surface chlorination after exposure to 2 M HCl in diethyl ether for freshly etched GaAs(111)A but not GaAs(111)B surfaces. GaN(0001) surfaces exposed to PCl(5) in chlorobenzene showed reproducible XP spectroscopic evidence for Cl-termination. The Cl-activated GaAs(111)A and GaN(0001) surfaces were both reactive toward alkyl Grignard reagents, with pronounced decreases in detectable Cl signal as measured by XP spectroscopy. Sessile contact angle measurements between water and GaAs(111)A interfaces after various levels of treatment showed that GaAs(111)A surfaces became significantly more hydrophobic following reaction with C(n)H(2n-1)MgCl (n = 1, 2, 4, 8, 14, 18). High-resolution As 3d XP spectra taken at various times during prolonged direct exposure to ambient lab air indicated that the resistance of GaAs(111)A to surface oxidation was greatly enhanced after reaction with Grignard reagents. GaAs(111)A surfaces terminated with C(18)H(37) groups were also used in Schottky heterojunctions with Hg. These heterojunctions exhibited better stability over repeated cycling than heterojunctions based on GaAs(111)A modified with C(18)H(37)S groups. Raman spectra were separately collected that suggested electronic passivation by surficial Ga-C bonds at GaAs(111)A. Specifically, GaAs(111)A surfaces reacted with alkyl Grignard reagents exhibited Raman signatures comparable to those of samples treated with 10% Na(2)S in tert-butanol. For GaN(0001), high-resolution C 1s spectra exhibited the characteristic low binding energy shoulder demonstrative of surface Ga-C bonds following reaction with CH(3)MgCl. In addition, 4-fluorophenyl groups were attached and detected after reaction with C(6)H(4)FMgBr, further confirming the susceptibility of Cl-terminated GaN(0001) to surface alkylation. However, the measured hydrophobicities of alkyl-terminated GaAs(111)A and GaN(0001) were markedly distinct, indicating differences in the resultant surface layers. The results presented here, in conjunction with previous studies on GaP, show that atop Ga atoms at these crystallographically related surfaces can be deliberately functionalized and protected through Ga-C surface bonds that do not involve thiol/sulfide chemistry or gas-phase pretreatments.

Benchtop electrochemical liquid-liquid-solid growth of nanostructured crystalline germanium.

An electrochemical liquid-liquid-solid (ec-LLS) process that produces large amounts of crystalline semiconductors with tunable nanostructured shapes without any physical or chemical templating agent is presented. Electrodeposition of Ge from GeO(2)(aq) solutions followed by dissolution into a liquid Hg electrode, saturation of the liquid alloy, and precipitation can yield polycrystalline Ge(s) under ambient conditions. A unique advantage of ec-LLS is that it involves precipitation under electrochemical control, where the applied bias precisely defines the flux of Ge into the liquid electrode. Fidelity of the saturation and precipitation of Ge from liquid electrodes affords a variety of material morphologies, including dense films of oriented nanostructured filaments with large aspect ratios (>10(3)). Electrodeposition involving a liquid electrolyte, a liquid electrode, and a solid deposit under ambient conditions represents a conceptually unexplored direct wet-chemical route for the preparation of bulk quantities of crystalline group-IV semiconductors without the time- and energy-intensive processing steps required in traditional preparations of semiconductor materials.

Overlayer surface-enhanced Raman spectroscopy for studying the electrodeposition and interfacial chemistry of ultrathin ge on a nanostructured support.

Ultrathin films of germanium (Ge) have been electrodeposited onto surface-enhanced raman spectroscopy (SERS)-active, polycrystalline gold (Au) nanoparticle film electrodes from aqueous solutions containing dissolved GeO2. An overlayer SERS strategy was employed to use the SERS-activity of the underlying Au electrode to enhance the Raman signatures separately for the Ge phonon mode and vibrational modes of surface groups. Electrochemical and spectroscopic data are presented that demonstrate monolayer-level detection of the electrodeposited material and the preparation of crystalline Ge films exhibiting quantum-confinement effects. Potential-dependent Raman spectra are shown that identify electrodeposition conditions where Ge films can be deposited with either long- or short-range crystalline order. Raman spectra collected with electrodeposited Ge films immersed in solutions containing CN-(aq) did not indicate a significant presence of pinholes that exposed the underlying Au(s) substrate. Raman spectra were also collected that identified a potential-dependence for Ge hydride formation at the interface of these films. Separate spectra were collected for the oxidative dissolution of Ge in solution and the complete dry oxidation of Ge to GeOx in air. These data sets cumulatively represent the first demonstration of the overlayer SERS strategy to follow surface chemical processes at crystalline, nanostructured, Ge materials in situ and in real time.