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.

Polymorphic Control of Solution-Processed Cu2SnS3 Films with Thiol-Amine Ink Formulation.

There is increasing demand for tailored molecular inks that produce phase-pure solution-processed semiconductor films. Within the Cu-Sn-S phase space, Cu2SnS3 belongs to the I2-IV-VI3 class of semiconductors that crystallizes in several different polymorphs. We report the ability of thiol-amine solvent mixtures to dissolve inexpensive bulk Cu2S and SnO precursors to generate free-flowing molecular inks. Upon mild annealing, polymorphic control over phase-pure tetragonal (I4̅2m) and orthorhombic (Cmc21) Cu2SnS3 films was realized simply by switching the identity of the thiol (i.e., 1,2-ethanedithiol vs 2-mercaptoethanol, respectively). Polymorph control is dictated by differences in the resulting molecular metal-thiolate complexes and their subsequent decomposition profiles, which likely seed distinct Cu2-x S phases that template the ternary sulfide sublattice. The p-type tetragonal and orthorhombic Cu2SnS3 films possess similar experimental direct optical band gaps of 0.94 and 0.88 eV, respectively, and strong photoelectrochemical current responses. Understanding how ink formulation dictates polymorph choice should inform the development of other thiol-amine inks for solution-processed films.

Failure Modes of Platinized pn+-GaInP Photocathodes for Solar-Driven H2 Evolution.

The long-term stability for the hydrogen-evolution reaction (HER) of homojunction pn+-Ga0.52In0.48P photocathodes (band gap = 1.8 eV) with an electrodeposited Pt catalyst (pn+-GaInP/Pt) has been systematically evaluated in both acidic and alkaline electrolytes. Electrode dissolution during chronoamperometry was correlated with changes over time in the current density-potential (J-E) behavior to reveal the underlying failure mechanism. Pristine pn+-GaInP/Pt photocathodes yielded an open-circuit photopotential (Eoc) as positive as >1.0 V vs the potential of the reversible hydrogen electrode (RHE) and a light-limited current density (Jph) of >12 mA cm-2 (1-sun illumination). However, Eoc and Jph gradually degraded at either pH 0 or pH 14. The performance degradation was attributed to three different failure modes: (1) gradual thinning of the n+-emitter layer due to GaInP dissolution in acid; (2) active corrosion of the underlying GaAs substrate at positive potentials causing delamination of the upper GaInP epilayers; and (3) direct GaAs/electrolyte contact compromising the operational stability of the device. This work reveals the importance of both substrate stability and structural integrity of integrated photoelectrodes toward stable solar fuel generation.

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.

Strain-Based Chemiresistive Polymer-Coated Graphene Vapor Sensors.

Suspended chemiresistive graphene sensors have been fabricated using well-established nanofabrication techniques to generate sensors that are highly sensitive to pyridine and with excellent discrimination between polar and nonpolar analytes. When coated with a polymer surface layer and suspended on 3-D patterned glass electrodes, a hybrid combination of polymer and graphene yields chemiresistive vapor sensors. Expansion and contraction of the polymer layer produces strain on the suspended graphene (Gr). Hence, when organic vapors permeate into the polymer layer, the high gauge factor of the graphene induces substantial electrical resistive changes as folds and creases are induced in the graphene. The hybrid suspended polymer/Gr sensor exhibits substantial responses to polar organic vapors, especially pyridine, while also exhibiting reversibility and increased discrimination between polar and nonpolar analytes compared to previous approaches. This sensor design also allows for potential tunability in the types of polymers used for the reactive surface layer, allowing for use in a variety of potential applications.

Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS2 and MoS2.

Reductant-activated functionalization is shown to enhance the methylation of chemically exfoliated MoS2 (ceMoS2) and ceWS2 by introducing excess negative charge to facilitate a nucleophilic attack reaction. Relative to methylation in the absence of a reductant, the reaction produces a twofold increase in coverage of ceWS2, from 25 to 52% coverage per WS2. However, at every potential, the methyl coverage on ceWS2 was ∼20% lower than that on ceMoS2. We applied grand canonical density functional theory to show that at constant potential, more negative charge is present on 1T'-MoS2 than on 1T'-WS2, making methylation both thermodynamically and kinetically more favorable for 1T'-MoS2 than 1T'-WS2. This effect was moderated when the reactions were compared at constant charge, emphasizing the importance of comparing the reactivity of materials at nominally identical electrode potentials.

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.

Understanding the Stability of Etched or Platinized p-GaInP Photocathodes for Solar-Driven H2 Evolution.

The long-term stability in acidic or alkaline aqueous electrolytes of p-Ga0.52In0.48P photocathodes, with a band gap of ∼1.8 eV, for the solar-driven hydrogen-evolution reaction (HER) has been evaluated from a thermodynamic, kinetic, and mechanistic perspective. At either pH 0 or pH 14, etched p-GaInP electrodes corroded cathodically under illumination and formed metallic In0 on the photoelectrode surface. In contrast, under the same conditions, electrodeposition of Pt facilitated the HER kinetics and stabilized p-GaInP/Pt photoelectrodes against such cathodic decomposition. When held at 0 V versus the reversible hydrogen electrode, p-GaInP/Pt electrodes in either pH = 0 or pH = 14 exhibited stable current densities (J) of ∼-9 mA cm-2 for hundreds of hours under simulated 1 sun illumination. During the stability tests, the current density-potential (J-E) characteristics of the p-GaInP/Pt photoelectrodes degraded due to pH-dependent changes in the surface chemistry of the photocathode. This work provides a fundamental understanding of the stability and corrosion mechanisms of p-GaInP photocathodes that constitute a promising top light absorber for tandem solar-fuel generators.

Geophysical constraints on the reliability of solar and wind power worldwide.

If future net-zero emissions energy systems rely heavily on solar and wind resources, spatial and temporal mismatches between resource availability and electricity demand may challenge system reliability. Using 39 years of hourly reanalysis data (1980-2018), we analyze the ability of solar and wind resources to meet electricity demand in 42 countries, varying the hypothetical scale and mix of renewable generation as well as energy storage capacity. Assuming perfect transmission and annual generation equal to annual demand, but no energy storage, we find the most reliable renewable electricity systems are wind-heavy and satisfy countries' electricity demand in 72-91% of hours (83-94% by adding 12 h of storage). Yet even in systems which meet >90% of demand, hundreds of hours of unmet demand may occur annually. Our analysis helps quantify the power, energy, and utilization rates of additional energy storage, demand management, or curtailment, as well as the benefits of regional aggregation.

Design of robust 2,2'-bipyridine ligand linkers for the stable immobilization of molecular catalysts on silicon(111) surfaces.

The attachment of the 2,2'-bipyridine (bpy) moieties to the surface of planar silicon(111) (photo)electrodes was investigated using ab initio simulations performed on a new cluster model for methyl-terminated silicon. Density functional theory (B3LYP) with implicit solvation techniques indicated that adventitious chlorine atoms, when present in the organic linker backbone, led to instability at very negative potentials of the surface-modified electrode. In prior experimental work, chlorine atoms were present as a trace surface impurity due to required surface processing chemistry, and thus could plausibly result in the observed surface instability of the linker. Free energy calculations for the Cl-atom release process with model silyl-linker constructs revealed a modest barrier (14.9 kcal mol-1) that decreased as the electrode potential became more negative. A small library of new bpy-derived structures has additionally been explored computationally to identify strategies that could minimize chlorine-induced linker instability. Structures with fluorine substituents are predicted to be more stable than their chlorine analogues, whereas fully non-halogenated structures are predicted to exhibit the highest stability. The behavior of a hydrogen-evolving molecular catalyst Cp*Rh(bpy) (Cp* = pentamethylcyclopentadienyl) immobilized on a silicon(111) cluster was explored theoretically to evaluate differences between the homogeneous and surface-attached behavior of this species in a tautomerization reaction observed under reductive conditions for catalytic H2 evolution. The calculated free energy difference between the tautomers is small, hence the results suggest that use of reductively stable linkers can enable robust attachment of catalysts while maintaining chemical behavior on the electrode similar to that exhibited in homogeneous solution.

Wind and Solar Resource Droughts in California Highlight the Benefits of Long-Term Storage and Integration with the Western Interconnect.

As reliance on wind and solar power for electricity generation increases, so does the importance of understanding how variability in these resources affects the feasible, cost-effective ways of supplying energy services. We use hourly weather data over multiple decades and historical electricity demand data to analyze the gaps between wind and solar supply and electricity demand for California (CA) and the Western Interconnect (WECC). We quantify the occurrence of resource droughts when the daily power from each resource was less than half of the 39-year daily mean for that day of the year. Averaged over 39 years, CA experienced 6.6 days of solar and 48 days of wind drought per year, compared to 0.41 and 19 for WECC. Using a macro-scale electricity model, we evaluate the potential for both long-term storage and more geographically diverse generation resources to minimize system costs. For wind-solar-battery electricity systems, meeting California demand with WECC generation resources reduces the cost by 9% compared to constraining resources entirely to California. Adding long-duration storage lowers system costs by 21% when treating California as an island. This data-driven analysis quantifies rare weather-related events and provides an understanding that can be used to inform stakeholders in future electricity systems.

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.

Primary Corrosion Processes for Polymer-Embedded Free-Standing or Substrate-Supported Silicon Microwire Arrays in Aqueous Alkaline Electrolytes.

Solar fuel devices have shown promise as a sustainable source of chemical fuels. However, long-term stability of light absorbing materials remains a substantial barrier to practical devices. Herein, multiple corrosion pathways in 1 M KOH(aq) have been defined for TiO2-protected Si microwire arrays in a polymer membrane either attached to a substrate or free-standing. Top-down corrosion was observed in both morphologies through defects in the TiO2 coating. For the substrate-based samples, bottom-up corrosion was observed through the substrate and up the adjacent wires. In the free-standing samples, uniform bottom-up corrosion was observed through the membrane with all wire material corroded within 10 days of immersion in the dark in 1 M KOH(aq).

Increased spatial randomness and disorder of nucleates in dark-phase electrodeposition lead to increased spatial order and pattern fidelity in phototropically grown Se-Te electrodeposits.

The role of nucleation was investigated during phototropic growth of Se-Te. Under low levels of mass deposition (mass equivalent of -3.75 mC cm-2 of charge passed) that produced small nucleate spacings, patterns in photoelectrochemically deposited Se-Te films converged at relatively earlier levels of mass deposition and ultimately exhibited higher pattern fidelity throughout pattern development as compared to pattern formation from larger initial nucleate spacings. Consistently, use of an applied striking potential during very early levels of mass deposition produced more spatially random dark-phase electrodeposited nucleates and led to phototropic Se-Te photoelectrodeposited films that exhibited improved pattern fidelity relative to depositions performed with no striking step. Collectively, the data indicate that increases in randomness and spatial disorder of the dispersion of the initial nucleates produces increases in the fidelity and spatial order in the resulting phototropically grown electrodeposits.

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.

Effects of Deep Reductions in Energy Storage Costs on Highly Reliable Wind and Solar Electricity Systems.

We use 36 years (1980-2015) of hourly weather data over the contiguous United States (CONUS) to assess the impact of low-cost energy storage on highly reliable electricity systems that use only variable renewable energy (VRE; wind and solar photovoltaics). Even assuming perfect transmission of wind and solar generation aggregated over CONUS, energy storage costs would need to decrease several hundred-fold from current costs (to ∼$1/kWh) in fully VRE electricity systems to yield highly reliable electricity without extensive curtailment of VRE generation. The role of energy storage changes from high-cost storage competing with curtailment to fill short-term gaps between VRE generation and hourly demand to near-free storage serving as seasonal storage for VRE resources. Energy storage faces "double penalties" in VRE/storage systems: with increasing capacity, (1) the additional storage is used less frequently and (2) hourly electricity costs would become less volatile, thus reducing price arbitrage opportunities for the additional storage.

Atomic force microscopy: Emerging illuminated and operando techniques for solar fuel research.

Integrated photoelectrochemical devices rely on the synergy between components to efficiently generate sustainable fuels from sunlight. The micro- and/or nanoscale characteristics of the components and their interfaces often control critical processes of the device, such as charge-carrier generation, electron and ion transport, surface potentials, and electrocatalysis. Understanding the spatial properties and structure-property relationships of these components can provide insight into designing scalable and efficient solar fuel components and systems. These processes can be probed ex situ or in situ with nanometer-scale spatial resolution using emerging scanning-probe techniques based on atomic force microscopy (AFM). In this Perspective, we summarize recent developments of AFM-based techniques relevant to solar fuel research. We review recent progress in AFM for (1) steady-state and dynamic light-induced surface photovoltage measurements; (2) nanoelectrical conductive measurements to resolve charge-carrier heterogeneity and junction energetics; (3) operando investigations of morphological changes, as well as surface electrochemical potentials, currents, and photovoltages in liquids. Opportunities for research include: (1) control of ambient conditions for performing AFM measurements; (2) in situ visualization of corrosion and morphological evolution of electrodes; (3) operando AFM techniques to allow nanoscale mapping of local catalytic activities and photo-induced currents and potentials.

Defect-Seeded Atomic Layer Deposition of Metal Oxides on the Basal Plane of 2D Layered Materials.

Atomic layer deposition (ALD) on mechanically exfoliated 2D layered materials spontaneously produces network patterns of metal oxide nanoparticles in triangular and linear deposits on the basal surface. The network patterns formed under a range of ALD conditions and were independent of the orientation of the substrate in the ALD reactor. The patterns were produced on MoS2 or HOPG when either tetrakis(dimethylamido)titanium or bis(ethylcyclopentadienyl)manganese were used as precursors, suggesting that the phenomenon is general for 2D materials. Transmission electron microscopy revealed the presence, prior to deposition, of dislocation networks along the basal plane of mechanically exfoliated 2D flakes, indicating that periodical basal plane defects related to disruptions in the van der Waals stacking of layers, such as perfect line dislocations and triangular extended stacking faults networks, introduce a surface reactivity landscape that leads to the emergence of patterned deposition.

Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon.

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH4F (aqueous) have been investigated during either a linear potential sweep or a constant potential hold (E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments revealed the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. The etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiOxFy on the surface. The two-dimensional fractal dimension, Df,2D, of the patterns increased with etching time to a maximum observed value of Df,2D = 1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface.

Macroscale and Nanoscale Photoelectrochemical Behavior of p-Type Si(111) Covered by a Single Layer of Graphene or Hexagonal Boron Nitride.

Two-dimensional (2D) materials may enable a general approach to the introduction of a dipole at a semiconductor surface as well as control over other properties of the double layer at a semiconductor/liquid interface. Vastly different properties can be found in the 2D materials currently studied due in part to the range of the distribution of density-of-states. In this work, the open-circuit voltage (Voc) of p-Si-H, p-Si/Gr (graphene), and p-Si/h-BN (hexagonal boron nitride) in contact with a series of one-electron outer-sphere redox couples was investigated by macroscale measurements as well as by scanning electrochemical cell microscopy (SECCM). The band gaps of Gr and h-BN (0-5.97 eV) encompass the wide range of band gaps for 2D materials, so these interfaces (p-Si/Gr and p-Si/h-BN) serve as useful references to understand the behavior of 2D materials more generally. The value of Voc shifted with respect to the effective potential of the contacting solution, with slopes (ΔVoc/ΔEEff) of -0.27 and -0.38 for p-Si/Gr and p-Si/h-BN, respectively, indicating that band bending at the p-Si/h-BN and p-Si/Gr interfaces responds at least partially to changes in the electrochemical potential of the contacting liquid electrolyte. Additionally, SECCM is shown to be an effective method to interrogate the nanoscale photoelectrochemical behavior of an interface, showing little spatial variance over scales exceeding the grain size of the CVD-grown 2D materials in this work. The measurements demonstrated that the polycrystalline nature of the 2D materials had little effect on the results and confirmed that the macroscale measurements reflected the junction behavior at the nanoscale.