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Harvesting solar energy as a carbon free source can be a promising solution to the energy crisis and environmental pollution. Biophotovoltaics seek to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. In the current study, we report on a combination of zinc oxide (ZnO) nanowires with monolayers of photosynthetic reaction centers which are self-assembled, via a cytochrome c linker, as photoactive electrode. In a three-probe biophotovoltaics cell, a photocurrent density of 5.5 μA cm and photovoltage of 36 mV was achieved, using methyl viologen as a redox mediator in the electrolyte. Using ferrocene as a redox mediator a transient photocurrent density of 8.0 μA cm was obtained, which stabilized at 6.4 μA cm after 20 s. In-depth electronic structure characterization using photoemission spectroscopy in conjunction with electrochemical analysis suggests that the fabricated photoactive electrode can provide a proper electronic path for electron transport all the way from the conduction band of the ZnO nanowires, through the protein linker to the RC, and ultimately via redox mediator to the counter electrode.

Analyzing and manipulating the electronic band line-up of interfaces in novel micro- and nanoelectronic devices is important to achieve further advancement in this field. Such band alignment modifications can be achieved by introducing thin conformal interfacial dipole layers. Atomic layer deposition (ALD), enabling angstrom-precise control over thin film thickness, is an ideal technique for this challenge. Ruthenium (Ru0) and its oxide (RuO2) have gained interest in the past decade as interfacial dipole layers because of their favorable properties like metal-equivalent work functions, conductivity, etc. In this study, initial results of the electronic structure investigation of ALD Ru0 and RuO2 films via photoemission spectroscopy are presented. These experiments give insight into the band alignment, growth behavior, surface structure termination, and dipole formation. The experiments were performed in an integrated vacuum system attached to a home-built, stop-flow type ALD reactor without exposing the samples to the ambient in between deposition and analysis. Bis(ethylcyclopentadienyl)ruthenium(II) was used as precursor and oxygen as reactant. The analysis chamber was outfitted with X-ray photoemission spectroscopy (LIXPS, XPS). The determined growth modes are consistent with a strong growth inhibition situation with a maximum average growth rate of 0.21 Å/cycle for RuO2 and 0.04 Å/cycle for Ru.0 An interface dipole of up to −0.93 eV was observed, supporting the assumption of a strongly physisorbed interface. A separate experiment where the surface of a RuO film was sputtered suggests that the surface is terminated by an intermediate, stable, non-stoichiometric RuO2/OH compound whose surface is saturated with hydroxyl groups.

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Microplasma-assisted gas-phase nucleation has emerged as an important new approach to produce high-purity, nanometer-sized, and narrowly dispersed particles. This study aims to integrate this technique with vacuum conditions to enable synthesis and deposition in an ultrahigh vacuum compatible environment. The ultimate goal is to combine nanoparticle synthesis with photoemission spectroscopy-based electronic structure analysis. Such measurements require in vacuo deposition to prevent surface contamination from sample transfer, which can be deleterious for nanoscale materials. A homebuilt microplasma reactor was integrated into an existing atomic layer deposition system attached to a surface science multi-chamber system equipped with photoemission spectroscopy. As proof-of-concept, we studied the decomposition of ferrocene vapor in the microplasma to synthesize iron oxide nanoparticles. The injection parameters were optimized to achieve complete precursor decomposition under vacuum conditions, and nanoparticles were successfully deposited. The stoichiometry of the deposited samples was characterized in situ using X-ray photoelectron spectroscopy indicating that iron oxide was formed. Additional transmission electron spectroscopy characterization allowed the determination of the size, shape, and crystal lattice of the particles, confirming their structural properties.