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Electrochemical Atomic Layer Deposition (E-ALD), exploiting surface limited electrodeposition of atomic layers, can easily grow highly ordered ultra-thin films and 2D structures. Among other compounds Cu x Zn y S grown by means of E-ALD on Ag(111) has been found particularly suitable for the solar energy conversion due to its band gap (1.61 eV). However its growth seems to be characterized by a micrometric thread-like structure, probably overgrowing a smooth ultra-thin films. On this ground, a SXRD investigation has been performed, to address the open questions about the structure and the growth of Cu x Zn y S by means of E-ALD. The experiment shows a pseudo single crystal pattern as well as a powder pattern, confirming that part of the sample grows epitaxially on the Ag(111) substrate. The growth of the film was monitored by following the evolution of the Bragg peaks and Debye rings during the E-ALD steps. Breadth and profile analysis of the Bragg peaks lead to a qualitative interpretation of the growth mechanism. This study confirms that Zn lead to the growth of a strained Cu 2 S-like structure, while the growth of the thread-like structure is probably driven by the release of the stress from the epitaxial phase.

In the present study, Au-surfactant core-shell colloidal nanoparticles (NPs) with controlled dimension and composition were synthesized by sacrificial anode electrolysis. Transmission electron microscopy (TEM) revealed that Au NPs core diameter is between 8 and 12 nm, as a function of the electrosynthesis conditions. Moreover, surface spectroscopic characterization by X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of nanosized gold phase. Controlled amounts of Au NPs were then deposited electrophoretically on carbon nanotube (CNT) networked films. The resulting hybrid materials were morphologically and chemically characterized using TEM, SEM (scanning electron microscopy) and XPS analyses, which revealed the presence of nanoscale gold, and its successful deposition on CNTs. Au NP/CNT networked films were tested as active layers in a two-pole resistive NO2 sensor for sub-ppm detection in the temperature range of 100–200 °C. Au NP/CNT exhibited a p-type response with a decrease in the electrical resistance upon exposure to oxidizing NO2 gas and an increase in resistance upon exposure to reducing gases (e.g. NH3). It was also demonstrated that the sensitivity of the Au NP/CNT-based sensors depends on Au loading; therefore, the impact of the Au loading on gas sensing performance was investigated as a function of the working temperature, gas concentration and interfering gases.

A SEM, DRS and XAS study was carried out on ultra-thin films with chemical composition belonging to the Cu-Zn-S ternary system, related to the kesterite-type materials, in the light of their potential application to thin film photovoltaic technology. The films, realized through the layer-by-layer E-ALD electrochemical technique, reveal variable phase composition as a function of the applied E-ALD sequence. In particular, by increasing the Zn cycles per Cu cycle from 1:1 to 9:1, the number of detected phases changes from 3 to 2. In all samples, Cu mainly crystallize in a Cu2S type phase, whereas Zn occurs as ZnS. In the 1:1 sample, additional ZnO is detected. The variable phase composition parallels apparent changes in the sample morphology. In all samples, a sulphide thin film is covered by a net of elongated nanostructures, the length of which decreases with increasing the number of Zn cycles per Cu cycle. All these evidences are interpreted as due to the operating electrochemical route during the synthesis and confirm the lack of miscibility between Cu2S and ZnS, thermodynamically relevant after the E-ALD has stopped. The band gap values exhibited by the three films, modulated by changing the copper:zinc ratio, progressively approach a value useful for solar energy conversion, thus strongly proposing these new sulfide nanomaterials for photovoltaics and photochemical applications.