Nanomaterials for highly selective and sensitive sensors toward specific gas molecules of volatile organic compounds (VOCs) are most important in developing new-generation of detector devices, for example, for biomarkers of diseases as well as for continuous air quality monitoring. Here, we present an innovative preparation approach for engineering sensors, which allow for full control of the dopant concentrations and the nanoparticles functionalization of columnar material surfaces. The main outcome of this powerful design concept lies in fine-tuning the reactivity of the sensor surfaces toward the VOCs of interest. First, nanocolumnar and well-distributed Ag-doped zinc oxide (ZnO:Ag) thin films are synthesized from chemical solution, and, at a second stage, noble nanoparticles of the required size are deposited using a gas aggregation source, ensuring that no percolating paths are formed between them. Typical samples that were investigated are Ag-doped and Ag nanoparticle-functionalized ZnO:Ag nanocolumnar films. The highest responses to VOCs, in particular to (CH3)2CHOH, were obtained at a low operating temperature (250 °C) for the samples synergistically enhanced with dopants and nanoparticles simultaneously. In addition, the response times, particularly the recovery times, are greatly reduced for the fully modified nanocolumnar thin films for a wide range of operating temperatures. The adsorption of propanol, acetone, methane, and hydrogen at various surface sites of the Ag-doped Ag8/ZnO­(0001) surface has been examined with the density functional theory (DFT) calculations to understand the preference for organic compounds and to confirm experimental results. The response of the synergistically enhanced sensors to gas molecules containing certain functional groups is in excellent agreement with density functional theory calculations performed in this work too. This new fabrication strategy can underpin the next generation of advanced materials for gas sensing applications and prevent VOC levels that are hazardous to human health and can cause environmental damages.

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Alloy nanoparticles with variable compositions add a new dimension to nanoscience and have many applications. Here we suggest a novel approach for the fabrication of variable composition alloy nanoparticles that is based on a Haberland type gas aggregation cluster source with a custom-made multicomponent target for magnetron sputtering. The approach, which was demonstrated here for gold-rich AgAu nanoparticles, combines a narrow nanoparticle size distribution with in operando variation of composition via the gas pressure as well as highly efficient usage of target material. The latter is particularly attractive for precious metals. Varying argon pressure during deposition, we achieved in operando changes of AgAu alloy nanoparticle composition of more than 13 at%. The alloy nanoparticles were characterized by x-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy. The characteristic plasmon resonances of multilayer nanoparticle composites were analyzed by UV-vis spectroscopy. Tuning of the number of particles per unit area (particle densities) within individual layers showed an additional degree of freedom to tailor the optical properties of multilayer nanocomposites. By extension of this technique to more complex systems, the presented results are expected to encourage and simplify further research based on plasmonic multi-element nanoparticles. The present method is by no means restricted to plasmonics or nanoparticle based applications, but is also highly relevant for conventional magnetron sputtering of alloys and can be extended to in operando control of alloy concentration by magnetic field.