Facet-Dependent Photoelectrochemistry on Single Crystal Organic-Inorganic Halide Perovskite Electrodes.

Organometallic halide perovskites have garnered significant attention in various fields of material science, particularly solar energy conversion, due to their desirable optoelectronic properties and compatibility with scalable fabrication techniques. It is often unclear, however, how carrier generation and transport within complex polycrystalline films are influenced by variations in local structure. Elucidating how distinct structural motifs within these heterogeneous systems affect behavior could help guide the continued improvement of perovskite-based solar cells. Here, we present studies applying scanning electron microscopy (SECCM) to map solar energy harvesting within well-defined model systems of organometallic halide perovskites. Methylammonium lead bromide (MAPbBr3) single crystals were prepared via a low-temperature solution-based route, and their photoelectrochemical properties were mapped via SECCM using p-benzoquinone (BQ) in dichloromethane as a redox mediator. Correlated SECCM mapping and electron microscopy studies enabled facet-to-facet variations in photoelectrochemical performance to be revealed and carrier transport lengths to be evaluated. The photoelectrochemical behavior observed within individual single crystals was quite heterogeneous, attributable to local variations in crystal structure/orientations, intrafacet junctions, and the presence of other structural defects. These observations underscore the significance of controlling the microstructure of single perovskite crystals, presenting a promising avenue for further enhancement of perovskite-based solar cells.

On-Demand Electrochemical Fabrication of Ordered Nanoparticle Arrays using Scanning Electrochemical Cell Microscopy.

Well-ordered nanoparticle arrays are attractive platforms for a variety of analytical applications, but the fabrication of such arrays is generally challenging. Here, it is demonstrated that scanning electrochemical cell microscopy (SECCM) can be used as a powerful, instantly reconfigurable tool for the fabrication of ordered nanoparticle arrays. Using SECCM, Ag nanoparticle arrays were straightforwardly fabricated via electrodeposition at the interface between a substrate electrode and an electrolyte-filled pipet. By dynamically monitoring the currents flowing in an SECCM cell, individual nucleation and growth events could be detected and controlled to yield individual nanoparticles of controlled size. Characterization of the resulting arrays demonstrate that this SECCM-based approach enables spatial control of nanoparticle location comparable with the terminal diameter of the pipet employed and straightforward control over the volume of material deposited at each site within an array. These results provide further evidence for the utility of probe-based electrochemical techniques such as SECCM as tools for surface modification in addition to analysis.

Multi-dimensional designer catalysts for negative emissions science (NES): bridging the gap between synthesis, simulations, and analysis.

Negative emissions technologies will play a critical role in limiting global warming to sustainable levels. Electrocatalytic and/or photocatalytic CO2 reduction will likely play an important role in this field moving forward, but efficient, selective catalyst materials are needed to enable the widespread adoption of these processes. The rational design of such materials is highly challenging, however, due to the complexity of the reactions involved as well as the large number of structural variables which can influence behavior at heterogeneous interfaces. Currently, there is a significant disconnect between the complexity of materials systems that can be handled experimentally and those that can be modeled theoretically with appropriate rigor and bridging these gaps would greatly accelerate advancements in the field of Negative Emissions Science (NES). Here, we present a perspective on how these gaps between materials design/synthesis, characterization, and theory can be resolved, enabling the rational development of improved materials for CO2 conversion and other NES applications.

Electrochemically probing exciton transport in monolayers of two-dimensional semiconductors.

Two-dimensional semiconductors (2DSCs) are attractive for a variety of optoelectronic and catalytic applications due to their ability to be fabricated as wide-area, monolayer-thick films and their unique optical and electronic properties which emerge at this scale. One important class of 2DSCs are the transition metal dichalcogenides (TMDs), which are of particular interest as absorbing layers in ultrathin optoelectronic devices. While TMDs are known to exhibit excellent photovoltaic properties at the bulk level, it is not yet clear how carriers are transported in these materials at thicknesses approaching the monolayer limit, where distinct changes in band structure and the nature of photogenerated carriers occur. Here, it is demonstrated that electrochemical microscopy techniques can be employed as powerful tools for visualizing these processes in 2DSCs, even within individual monolayers. Carrier generation-tip collection scanning electrochemical cell microscopy (CG-TC SECCM), which utilizes spatially-offset optical and pipet-based electrochemical probes to locally generate and detect photogenerated carriers, was applied to visualize carrier generation and transport within well-defined n-WSe2 samples prepared via mechanical exfoliation. Data from these experiments directly reveal how carrier transport varies within complex 2DSC structures as layer thicknesses approach the monolayer limit. These results not only provide valuable new insights into carrier transport within monolayer TMD materials, but also demonstrate electrochemical imaging to be a powerful, yet underutilized approach for visualizing solid-state processes in semiconducting materials.

Directly visualizing carrier transport and recombination at individual defects within 2D semiconductors.

Two-dimensional semiconductors (2DSCs) are promising materials for a wide range of optoelectronic applications. While the fabrication of 2DSCs with thicknesses down to the monolayer limit has been demonstrated through a variety of routes, a robust understanding of carrier transport within these materials is needed to guide the rational design of improved practical devices. In particular, the influence of different types of structural defects on transport is critical, but difficult to interrogate experimentally. Here, a new approach to visualizing carrier transport within 2DSCs, Carrier Generation-Tip Collection Scanning Electrochemical Cell Microscopy (CG-TC SECCM), is described which is capable of providing information at the single-defect level. In this approach, carriers are locally generated within a material using a focused light source and detected as they drive photoelectrochemical reactions at a spatially-offset electrolyte interface created through contact with a pipet-based probe, allowing carrier transport across well-defined, µm-scale paths within a material to be directly interrogated. The efficacy of this approach is demonstrated through studies of minority carrier transport within mechanically-exfoliated n-type WSe2 nanosheets. CG-TC SECCM imaging experiments carried out within pristine basal planes revealed highly anisotropic hole transport, with in-plane and out-of-plane hole diffusion lengths of 2.8 µm and 5.8 nm, respectively. Experiments were also carried out to probe recombination across individual step edge defects within n-WSe2 which suggest a significant surface charge (∼5 mC m-2) exists at these defects, significantly influencing carrier transport. Together, these studies demonstrate a powerful new approach to visualizing carrier transport and recombination within 2DSCs, down to the single-defect level.

Investigating the Redox Properties of Two-Dimensional MoS2 Using Photoluminescence Spectroelectrochemistry and Scanning Electrochemical Cell Microscopy.

Control over photophysical and chemical properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) is the key to advance their applications in next-generation optoelectronics. Although chemical doping and surface modification with plasmonic metals have been reported to tune the photophysical and catalytic properties of 2D TMDs, there have been few reports of tuning optical properties using dynamic electrochemical control of electrode potential. Herein, we report (1) the photoluminescence (PL) enhancement and red-shift in the PL spectrum of 2D MoS2, synthesized by chemical vapor deposition and subsequent transfer onto an indium tin oxide electrode, upon electrochemical anodization and (2) spatial heterogeneities in its photoelectrochemical (PEC) activities. Spectroelectrochemistry shows that positive electrochemical bias causes an initial ten-fold increase in the PL intensity followed by a quick decrease in the enhancement. The PL enhancement and spectrum red-shift are associated with the decrease in nonradiative decay rates of excitons formed upon electrochemical anodization of 2D MoS2. Additionally, scanning electrochemical cell microscopy (SECCM) study shows that the 2D MoS2 crystal is spatially sensitive to PEC oxidation at positive potentials. SECCM also shows a photocurrent increase caused by spatially heterogeneous edge-type defect sites of the crystal.

Directly Mapping Photoelectrochemical Behavior within Individual Transition Metal Dichalcogenide Nanosheets.

Spatial variations in photoelectrochemical reaction rates within individual p-type WSe2 nanosheets were mapped through the application of scanning electrochemical cell microscopy (SECCM). The simultaneous topographical and electrochemical information provided via SECCM directly revealed how both sheet thickness and the presence of defect structures affect the local rate of photoelectrochemical reactions for both outer sphere and inner sphere redox couples. Sheet thickness was found to play a dramatic role in reaction rates, with onset potentials shifting by as much as 0.5 V over thicknesses of 20-120 nm, attributable to the inability of thin sheets to support independent space charge layers. Step/edge features were found to play a detrimental role for the outer sphere redox couple investigated (Ru(NH3)63+ reduction), with taller steps having larger effects on performance. Shorter step features were found to be beneficial for hydrogen evolution, showing a controlled density of defect features is desirable for inner sphere processes. The studies presented here not only provide valuable, quantitative insights into the behavior of transitional metal dichalcogenide materials but also demonstrate the power of applying SECCM to the study of photoelectrochemical systems, particularly those involving two-dimensional (2D) materials.

Probing Electrocatalysis at Individual Au Nanorods via Correlated Optical and Electrochemical Measurements.

A novel analytical methodology based on correlated optical and electroanalytical measurements was developed to probe electrocatalytic reactions at individual nanoparticles (NPs) with well-defined geometries. The developed methodology, Optically Targeted ElectroChemical Cell Microscopy (OTECCM), relies on a combination of optical hyperspectral imaging, to locate individual NPs and provide structural information, and Scanning ElectroChemical Cell Microscopy (SECCM), to provide direct information on the electrochemical behavior of the same NPs. This complementary strategy allows for SECCM measurements to be carried out in a "targeted" fashion, offering significant throughput advantages over conventional, scanning-based approaches. The developed methodology was applied to study the electrocatalytic oxidation of hydrazine at individual Au nanorods (NRs). Correlated electron microscopy investigations were carried out to conclusively demonstrate the ability of the proposed methodology to probe electrochemical reactions at individual NRs. A wide variety in behavior of the individual NRs was observed, with surface reactions at Au playing a prominent role in the observed response. In situ spectroscopic investigations at individual NRs suggest surface restructuring and/or residual ligand desorption leads to significant changes in catalytic activity over time. Results from the correlated electron microscopy investigations as well as the statistical analyses of data obtained for hundreds of individual nanostructures suggest that the gross geometry of a NR is a poor predictor of its electrocatalytic performance.

Electrochemical Nonadiabatic Electron Transfer via Tunneling to Solution Species through Thin Insulating Films.

Described here is a semiquantitative theoretical treatment of the kinetics of outer sphere electrochemical reactions. The framework presented here, which is based on simple physical arguments, predicts heterogeneous rate constants consistent with previous experimental observations (k0 > 10 cm/s). This theory is applied to the analysis of voltammetry experiments involving ultramicroelectrodes modified with thin, insulating oxide films where electronic tunneling between the electrode and redox species in solution (metal-insulator-solution tunneling) is expected to play a prominent role. It is shown that analysis of the voltammetric response of an outer sphere redox couple can be used to track changes in the structure of the adsorbed insulating layer.

Electrochemistry at a Metal Nanoparticle on a Tunneling Film: A Steady-State Model of Current Densities at a Tunneling Ultramicroelectrode.

Here, a new methodology is proposed for treating electrochemical current densities in metal-insulator-metal nanoparticle (M-I-MNP) systems. The described model provides broad, practical insights about MNP-mediated electron transfer to redox species in solution, where electron transfer from the underlying electrode to a MNP via tunneling and heterogeneous electron transfer from the MNP to redox species in solution are treated as sequential steps. Tunneling is treated through an adaptation of the Simmons model of tunneling in metal-insulator-metal structures, and explicit equations are provided for tunneling currents, which demonstrate the effect of various experimental parameters, such as insulator thickness and MNP size. Overall, a general approach is demonstrated for determining experimental conditions where tunneling will have a measurable impact on the electrochemistry of M-I-MNP systems.

Interfacial charge transfer events of BODIPY molecules: single molecule spectroelectrochemistry and substrate effects.

We present single molecule fluorescence and spectroelectrochemistry characteristics of 4,4'-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) bearing two carboxylic acid groups at its 2 and 6 positions. Our study shows a heterogeneous half redox potential distribution for the BODIPY molecules embedded in polystyrene film because of the heterogeneity in their charge transfer rates. Single molecules adsorbed onto a TiO2 surface with ordered nanostructures show surprising fluorescence blinking activity with the shortest ON duration time in comparison to bare glass and indium-tin oxide (ITO) surfaces. Single molecule stability tests show longer ON duration time and a stable fluorescence feature when dispersed in polystyrene thin film than molecules exposed to air. Shorter ON times are observed for molecules. In intimate contact with ITO in comparison to glass substrates. Such a decrease in their fluorescence stability or intensity is explained by charge transfer activities from the dye molecules to the metal oxide surface. Electron transfer and back transfer rates are calculated to illustrate the substrate effects by using a well-established model.

Combined optical and electrochemical methods for studying electrochemistry at the single molecule and single particle level: recent progress and perspectives.

We present a review of recent efforts aimed at understanding interfacial charge transfer at the single molecule and single nanoparticle level using the combined methods of traditional electrochemistry and optical spectroscopy with high spatial, spectral, and temporal resolution. Elastic light scattering, surface enhanced Raman scattering (SERS), fluorescence, and electrogenerated chemiluminescence (ECL) techniques have been demonstrated to be powerful tools for the study of interfacial charge transfer events involving a single molecule or nanoparticle and for the characterization of nanostructured electrodes. It is shown that these optical methods enable the exploration of electrochemical events with improved temporal and spatial resolution which are usually obstructed by the ensemble averaging inherent in conventional electrochemical methods. In this report, the current status of the field is reviewed and challenges for future work are discussed.

A dark-field scattering spectroelectrochemical technique for tracking the electrodeposition of single silver nanoparticles.

Dark-field scattering spectroelectrochemistry is used to analyze the electrochemical formation of individual Ag nanoparticles (NPs) at the surface of an indium tin oxide electrode. Heterogeneities in redox potentials among NPs not visible in bulk electrochemical measurements are presented for the first time. Through correlated electron microscopy, single NP light scattering intensity is related to particle size according to Mie theory, enabling rapid particle size determination and the construction of voltammetric curves for individual NPs.

Electrogenerated chemiluminescence and interfacial charge transfer dynamics of poly(3-hexylthiophene-2,5-diyl) (P3HT)-TiO2 nanoparticle thin film.

We present electrogenerated chemiluminescence (ECL) and photoluminescence (PL) characteristics of poly(3-hexylthiophene-2,5-diyl) (P3HT) thin films incorporated with monodisperse TiO(2) nanoparticles prepared using a hydrothermal reaction in the presence of oleylamine and oleic acid. The ECL turn-on potential decreases in the presence of TiO(2) nanocrystals, accompanied with an increase in ECL intensity. Only a minor ECL quantum efficiency decrease is obtained in the presence of <40 wt% TiO(2), indicating the formation of an effective interpenetrating network of TiO(2) and disordering of polymer packing to allow the ECL coreactant to transport through the film for efficient electroluminescence. In contrast, PL quenching increases with the weight percentage of TiO(2) and significant PL quenching is obtained when the P3HT film contains up to 80 wt% TiO(2) due to charge transfer. Polaron absorption after the photoinduced charge separation in the presence of 80 wt% TiO(2) nanoparticles is significantly enhanced with longer-lived lifetimes of >1000 ps in contrast to the neat P3HT film. The absorption of polarons created at the P3HT-TiO(2) interface is found to increase with the P3HT-TiO(2) interfacial area per unit volume.

Reductive-oxidation electrogenerated chemiluminescence (ECL) generation at a transparent silver nanowire electrode.

We present the fabrication of a conductive, transparent electrode composed of Ag nanowires (NW) for spectroelectrochemical studies. Reductive-oxidation electrogenerated chemiluminescence (ECL) of Ru(bpy)3(2+) is generated at the Ag NW electrode in the presence of hydrogen peroxide and collected through the new transparent electrode. The ECL performance at the new nanostructured electrode is compared with several other electrodes, including bulk silver wire, glassy carbon disk, and thermally reduced transparent graphene oxide (tr-GO) electrodes. The Ag NW electrode is found to be the best electrode for the reductive-oxidation ECL generation because of its catalytic properties with respect to the reduction of hydrogen peroxide and its high surface area.

Fluorescence and electroluminescence quenching evidence of interfacial charge transfer in poly (3-hexylthiophene): graphene oxide bulk heterojunction photovoltaic devices.

We present electrochemical studies of graphene oxide (GO) nanosheets and demonstrate the fluorescence and electrogenerated chemiluminescence quenching capability of GO nanosheets that are transferred into chloroform from aqueous solution utilizing a novel, surfactant-assisted method. Electrochemical studies indicate that GO can be reduced upon charge injection. Fluorescence quenching of the conjugate polymer poly (3-hexylthiophene) (P3HT) in both solution and solid films is demonstrated to show that GO can be used as an electron acceptor in a bulk heterojunction organic photovoltaic (OPV) device. OPV devices were then fabricated with an ITO/PEDOT:PSS/P3HT-GO/Al structure. Devices containing GO exhibited an increase in short-circuit current (I(sc)) and conductivity but a decrease in open circuit potential (V(oc)). These results display the potential for nonorganically functionalized GO to be used as an acceptor material in future OPV devices. The results also indicate that GO can increase the conductivity of the nanocomposite film so that charge recombination is an issue in such a device. The increased conductivity and fluorescence quenching are also supported by electrogenerated chemiluminescence (ECL) of P3HT/GO composite films.