Metal Oxide Semiconductors for Solar Energy Harvesting

The correlation between energy consumption and human development illustrates the importance of this societal resource. We will consume more energy in the future. In light of issues with the status quo, such as climate change, long-term supply and security, solar energy is an attractive source. It is plentiful, virtually inexhaustible, and can provide more than enough energy to power society. However, the issue with producing electricity and fuels from solar energy is that it is expensive, primarily from the materials: silicon) used in building the cells. Metal oxide semiconductors are an attractive class of materials that are extremely low cost and can be produced at the scale needed to meet widespread demand. An industrially attractive thin film synthesis process based on aerosol deposition was developed that relies on self-assembly to afford rational control over critical materials parameters such as film morphology and nanostructure. The film morphology and nanostructure were found to have dramatic effects on the performance of TiO2-based photovoltaic dye-sensitized solar cells. Taking a cue from nature, to overcome the spatial and temporal mismatch between the supply of sunlight and demand for energy consumption, it is desirable to produce solar fuels such as hydrogen from photoelectrochemical water splitting. The source of water is important -- seawater is attractive. The fundamental reaction mechanism for TiO2-based cells is discussed in the context of seawater splitting. There are two primary issues with producing hydrogen by photoelectrochemical water splitting using metal-oxide semiconductors: visible light activity and spontaneous activity. To address the light absorption issue, a combined theory-experiment approach was taken to understand the fundamental role of chemical composition in determining the visible light absorption properties of mixed metal-oxide semiconductors. To address the spontaneous activity issue, self-biasing all oxide p/n bulk-heterojunctions were synthesized and the nanostructure was systematically varied to understand the fundamental role of various characteristic length scales in the nanostructured region of the device on performance. The conclusion of this work is that solar energy harvesting by metal oxide semiconductors is highly promising. All of the scientific concepts have been proven, and steady gains in efficiency are being achieved as researchers continue to tackle the problem

Visualizing current flow at the mesoscale in disordered assemblies of touching semiconductor nanocrystals

The transport of electrons through assemblies of nanocrystals is important for the performance of these materials in optoelectronic applications. The transport of electrons has primarily been studied by focusing on single nanocrystals or transitions between pairs of nanocrystals. There is a gap in knowledge of how large numbers of nanocrystals in an assembly behave collectively, and how this collective behavior manifests at the mesoscale. In this work, the transport of electrons in assemblies of touching, heavily doped ZnO nanocrystals was visualized as a function of temperature at the mesoscale theoretically using the model of Skinner, Chen and Shklovskii (SCS); and experimentally by conductive atomic force microscopy on ultrathin films only a few particle layers thick. Agreement was obtained between the model and experiments, with a few notable exceptions. The SCS model predicts that a single network within the nanocrystal assembly, comprised of sites connected by small resistances, dominates conduction - namely the well-known optimum band from variable range hopping theory. However, our experiments revealed that in addition to the optimum band, there are subnetworks that appear as additional peaks in the resistance histogram; which were not observed in the model calculations. Furthermore, the connections of these subnetworks to the optimum band changes in time. As time proceeds, some isolated subnetworks become connected to the optimum band; while some of the connected subnetworks become disconnected and then isolated from the optimum band. The subset of nanocrystals comprising the optimum band is dynamic

Synthesis and Characterization of High-Photoactivity Electrodeposited Cu2O solar absorber by photoelectrochemistry and ultrafast spectroscopy

We present a systematic study on the effects of electrodeposition parameters on the photoelectrochemical properties of Cu2O. The influence of deposition variables (temperature, pH, and deposition current density) on conductivity has been widely explored in the past for this semiconductor, but the optimization of the electrodeposition process for the photoelectrochemical response in aqueous solutions under AM 1.5 illumination has received far less attention. In this work, we analyze the photoactivity of Cu2O films deposited at different conditions and correlate the photoresponse to morphology, film orientation, and electrical properties. The photoelectrochemical response was measured by linear sweep voltammetry under chopped simulated AM 1.5 illumination. The highest photocurrent obtained was −2.4 mA cm−2 at 0.25 V vs RHE for a film thickness of 1.3 μm. This is the highest reported value reached so far for this material in an aqueous electrolyte under AM 1.5 illumination. The optical and electrical properties of the most photoactive electrode were investigated by UV−vis spectroscopy and electrochemical impedance, while the minority carrier lifetime and diffusion length were measured by optical-pump THz-probe spectroscopy

Single-Step Aerosol Synthesis and Deposition of Au Nanoparticles with Controlled Size and Separation Distributions

Immobilized noble metal nanoparticles are being explored for a variety of applications where control over the particle size and separation distance on the substrate is important for performance. A proof of concept is presented that Au nanoparticles can be deposited in a single step with control over the size and separation distributions using an aerosol process. Samples were deposited with mean particle diameters in the range from 15 to 43 nm, and mean separation distances from 11 to 39 nm. Depending on the separation distance, particles exhibited localized surface plasmon resonance dominated by either intra- or interparticle resonances, as determined by ultraviolet-visible extinction spectroscopy. Ultrathin TiO2 shells of different thicknesses, in the range from 0 to 24 nm, were deposited on the Au nanoparticles by atomic layer deposition to determine the sensing distance into the surrounding dielectric medium for these materials, which was estimated to be 10 nm

Single-Step Aerosol Synthesis and Deposition of Au Nanoparticles with Controlled Size and Separation Distributions

Immobilized noble metal nanoparticles are being explored for a variety of applications where control over the particle size and separation distance on the substrate is important for performance. A proof of concept is presented that Au nanoparticles can be deposited in a single step with control over the size and separation distributions using an aerosol process. Samples were deposited with mean particle diameters in the range from 15 to 43 nm, and mean separation distances from 11 to 39 nm. Depending on the separation distance, particles exhibited localized surface plasmon resonance dominated by either intra- or interparticle resonances, as determined by ultraviolet–visible extinction spectroscopy. Ultrathin TiO₂ shells of different thicknesses, in the range from 0 to 24 nm, were deposited on the Au nanoparticles by atomic layer deposition to determine the sensing distance into the surrounding dielectric medium for these materials, which was estimated to be 10 nm

Nanostructured thin films produced in flame aerosol reactors for photosplitting of water

The paper describes methodologies for deposition of nanostructured films in single step processes using flame aerosol reactors. An understanding of the process parameters such as precursor feed rate, temperature histories and residence times that control resultant film parameters such as thickness, crystallinity and morphology are developed. Control of temperature profiles allow control of sintering rates to produce desired nanostructured thin films. These films are then tested for photocurrent generation under uv light illumination - and overall conversion efficiencies of around 5 % are readily obtained. Results of the study indicate that conditions could be optimized to improve water splitting efficiencies