Azhar I. Carim

Electrocatalysis of the hydrogen-evolution reaction by electrodeposited amorphous cobalt selenide films†

Using an electrochemical method under ambient conditions, crystallographically amorphous films of cobalt selenide have been deposited from aqueous solution onto planar Ti supports. These films have been evaluated as electrocatalysts for the hydrogen-evolution reaction. In 0.500 M H2SO4, the cobalt selenide films required an overpotential of ∼135 mV to drive the hydrogen-evolution reaction at a benchmark current density of −10 mA cm−2. Galvanostatic measurements indicated stability of the electrocatalytic films for >16 h of continuous operation at −10 mA cm−2. The facile preparation method, and the activity of the cobalt selenide films, suggest that electrodeposited metal chalcogenides are potentially attractive earth-abundant electrocatalysts for the hydrogen-evolution reaction.

Stabilization of n-cadmium telluride photoanodes for water oxidation to O2(g) in aqueous alkaline electrolytes using amorphous TiO2 films formed by atomic-layer deposition

Although II–VI semiconductors such as CdS, CdTe, CdSe, ZnTe, and alloys thereof can have nearly ideal band gaps and band-edge positions for the production of solar fuels, II–VI photoanodes are well-known to be unstable towards photocorrosion or photopassivation when in contact with aqueous electrolytes. Atomic-layer deposition (ALD) of amorphous, “leaky” TiO2 films coated with thin films or islands of Ni oxide has been shown to robustly protect Si, GaAs, and other III–V materials from photocorrosion and therefore to facilitate the robust, solar-driven photoelectrochemical oxidation of H2O to O2(g). We demonstrate herein that ALD-deposited 140 nm thick amorphous TiO2 films also effectively protect single crystalline n-CdTe photoanodes from corrosion or passivation. An n-CdTe/TiO2 electrode with a thin overlayer of a Ni-oxide based oxygen-evolution electrocatalyst produced 435 ± 15 mV of photovoltage with a light-limited current density of 21 ± 1 mA cm−2 under 100 mW cm−2 of simulated Air Mass 1.5 illumination. The ALD-deposited TiO2 films are highly optically transparent and electrically conductive. We show that an n-CdTe/TiO2/Ni oxide electrode enables the stable solar-driven oxidation of H2O to O2(g) in strongly alkaline aqueous solutions, where passive, intrinsically safe, efficient systems for solar-driven water splitting can be operated.

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.

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.

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.

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.

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.

Preparation of photoactive ZnGeP2 nanowire films

Photoactive ZnGeP2 nanowires have been prepared by solid-source sublimation chemical vapor deposition using Sn catalysts. Nanowire films with areas >0.5 cm2 on Si(100) and Si(111) substrates were deposited with variable nanowire length and diameter. Transmission electron microscopy (TEM), scanning TEM (STEM), and polarized Raman microscopy indicated nanowires exhibited single-crystal character and compositional homogeneity. Photoelectrochemical measurements performed in an aqueous electrolyte indicated the as-prepared ZnGeP2 nanowires were p-type and capable of passing sustained cathodic photocurrents under white light illumination. The presented results identify a straight-forward approach to the preparation of II–IV–V2 nanowire films with features suitable for optical and photoelectrochemical energy conversion/storage applications.

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.

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.