Electrical properties of strained off-stoichiometric Cu-Cr-O delafossite thin films.

Off-stoichiometric Cu-Cr-O delafossite thin films with different thicknesses were grown by metal organic chemical vapor deposition on substrates with different coefficients of thermal expansion. Seebeck thermoelectric coefficient and resistivity measurements were performed on the range of 300-850 K. A qualitative change in the temperature-dependence of the resistivity is observed at the temperature corresponding to the deposition process, where the transition from tensile to compressive strain takes place. Arrhenius plots reveal different slopes in these two thermal ranges. The fact that the shift is more pronounced for the thinner films might indicate the induced strain plays a role in changing electrical behaviour. Furthermore, changes below 0.1% in electrical mobility were measured when the strain is induced by mechanical bending.

Iron oxide/graphene oxide nanocomposite synthesis using atmospheric cold plasma.

Herein, we demonstrate the use of an atmospheric pressure plasma with a Dielectric Barrier Discharge (DBD) for the synthesis of FeOx nanoparticles with a simultaneous formation of graphene oxide domains at low substrate temperature. For that, the interaction of the plasma to control good decomposition of the Fe precursor is essential and this is demonstrated by FTIR analyses. Thanks to a fine tuning of the plasma conditions, a homogeneous spatial distribution around 5 nm nanoparticles (NPs) was obtained, whereas without plasma, in the same configuration of the process, a heterogeneity regarding size and shape for the NPs was obtained. The Raman spectrum of the plasma deposit confirmed the presence of graphene oxide as the characteristic G and D bands were observed with I(D)/I(G) = 0.92. Thanks to optical emission spectroscopy (OES) measurements, it is proposed that the carbon deposition on FeOx nanoparticles is produced on the near plasma post discharge. XPS studies showed that the main contribution of iron was in Fe2+ form, corresponding to the FeO phase. No metallic Fe or carbide were detected. As there are many studies reporting the synergetic effect of FeOx NPs and graphene oxide, we believe that this new one-step simultaneous synthesis method may be of high interest for applications requiring direct deposition on temperature labile substrates such as polymers.

A Polymer-Derived Co(Fe)Ox Oxygen Evolution Catalyst Benefiting from the Oxidative Dehydrogenative Coupling of Cobalt Porphyrins.

Thin films of cobalt porphyrin conjugated polymers bearing different substituents are prepared by oxidative chemical vapor deposition (oCVD) and investigated as heterogeneous electrocatalysts for the oxygen evolution reaction (OER). Interestingly, the electrocatalytic activity originates from polymer-derived, highly transparent Co(Fe)Ox species formed under operational alkaline conditions. Structural, compositional, electrical, and electrochemical characterizations reveal that the newly formed active catalyst greatly benefited from both the polymeric conformation of the porphyrin-based thin film and the inclusion of the iron-based species originating from the oCVD reaction. High-resolution mass spectrometry analyses combined with density functional theory (DFT) calculations showed that a close relationship exists between the porphyrin substituent, the extension of the π-conjugated system cobalt porphyrin conjugated polymer, and the dynamics of the polymer conversion leading to catalytically active Co(Fe)Ox species. This work evidences the precatalytic role of cobalt porphyrin conjugated polymers and uncovers the benefit of extended π-conjugation of the molecular matrix and iron inclusion on the formation and performance of the true active catalyst.

Gold nanoparticles synthesis and immobilization by atmospheric pressure DBD plasma torch method.

Herein, we report the impact of plasma on gold nanoparticles synthesis. We used an atmospheric plasma torch fed with an aerosolized tetrachloroauric(iii) acid trihydrate (HAuCl4·3H2O) solution. The investigation showed that using pure ethanol as a solvent for the gold precursor enabled a better dispersion compared to a water-containing solution. We demonstrated here that the deposition parameters are easy to control, presenting the influence of solvent concentration and deposition time. The advantage of our method is that no capping agent was used. We assume that plasma creates a carbon-based matrix around the gold nanoparticles preventing them to agglomerate. The XPS results revealed the impact of using plasma. Metallic gold was detected in the plasma-treated sample, whereas the no-plasma sample revealed only Au(i) and Au(iii) contributions originating from the HAuCl4 precursor. Detailed HRTEM, EDS mapping, and SAED analyses led to more insights into the structure.

Widely Tuneable Composition and Crystallinity of Graded Na1+xTaO3±Î´ Thin Films Fabricated by Chemical Beam Vapor Deposition.

Combinatorial approach has been widely recognized as a powerful strategy to develop new-higher performance materials and shed the light on the stoichiometry-dependent properties of known systems. Herein, we take advantage of the unique features of chemical beam vapor deposition to fabricate compositionally graded Na1+xTaO3±Î´ thin films with −0.6 < x < 0.5. Such a varied composition was enabled by the ability of the employed technique to deliver and combine an extensive range of precursors flows over the same deposition area. The film growth occurred in a complex process, where precursor absolute flows, flow ratios, and substrate temperature played a role. The deviation of the measured Na/Ta ratios from those predicted by flow simulations suggests that a chemical-reaction limited regime underlies the growth mechanism and highlights the importance of the Ta precursor in assisting the decomposition of the Na one. The crystallinity was observed to be strongly dependent on its stoichiometry. High under-stoichiometries (e.g., Na0.5TaO3−δ) compared to NaTaO3 were detrimental for the formation of a perovskite framework, owing to the excessive amount of sodium vacancies and oxygen vacancies. Conversely, a well-crystallized orthorhombic perovskite structure peculiar of NaTaO3 was observed from mildly under-stoichiometric (e.g., Na0.9TaO3−δ) to highly over-stoichiometric (e.g., Na1.5TaO3+δ) compositions.

Waste- and Cd-Free Inkjet-Printed Zn(O,S) Buffer for Cu(In,Ga)(S,Se)2 Thin-Film Solar Cells.

Thin film semiconductors grown using chemical bath methods produce large amounts of waste solvent and chemicals that then require costly waste processing. We replace the toxic chemical bath deposited CdS buffer layer from our Cu(In,Ga)(S,Se)2 (CIGS)-based solar cells with a benign inkjet-printed and annealed Zn(O,S) layer using 230 000 times less solvent and 64 000 times less chemicals. The wetting and final thickness of the Zn(O,S) layer on the CIGS is controlled by a UV ozone treatment and the drop spacing, whereas the annealing temperature and atmosphere determine the final chemical composition and band gap. The best solar cell using a Zn(O,S) air-annealed layer had an efficiency of 11%, which is similar to the best conventional CdS buffer layer device fabricated in the same batch. Improving the Zn(O,S) wetting and annealing conditions resulted in the best device efficiency of 13.5%, showing the potential of this method.

Copper-CNT interfacing with Cu-doped polydopamine in CNT carpet: copper nucleation and resistance decrease upon soft annealing.

In recent years, Cu-CNT composites have attracted much attention due to their remarkable properties, in comparison to pure copper, such as higher ampacity and a lower thermal coefficient of resistance. However, the fabrication of an efficient Cu-CNT composite is still challenging, mainly due to the high cuprophobicity of CNTs. To strengthen the chemical interactions between Cu and CNTs, we propose using a Cu-doped polydopamine coating as an interface between CNTs and metallic copper. This work reports on the nucleation of copper particles on the surface of MWCNTs that are coated with Cu-doped polydopamine after annealing in an inert atmosphere at 573, 673 and 773 K. We show, for the first time to the best of our knowledge, that the polydopamine coating oxidizes during annealing and efficiently reduces Cu ions into metallic Cu. Interestingly, the sheet resistance of coated CNT carpets can be reduced by 33 and 37.6% after annealing at 573 and 773 K, respectively. Furthermore, the sheet resistance decrease does not depend on the size of copper particles (diameter ranging from 13 to 27 nm) or their surface density (from 2.27 × 1010 to 5.7 × 108 particles per cm2). This sheet resistance drop is mainly attributed to the appearance of pyridinic nitrogen in the Cu-doped polydopamine structure after annealing at 673 K and above. Finally, we measure a negative temperature coefficient of resistance for all of the CNT carpets.

Mesoporous TiO2 anatase films for enhanced photocatalytic activity under UV and visible light.

Mesoporous TiO2 films with enhanced photocatalytic activity in both UV and visible wavelength ranges were developed through a non-conventional atomic layer deposition (ALD) process at room temperature. Deposition at such a low temperature promotes the accumulation of by-products in the amorphous TiO2 films, caused by the incomplete hydrolysis of the TiCl4 precursor. The additional thermal annealing induces the fast recrystallisation of amorphous films, as well as an in situ acidic treatment of TiO2. The interplay between the deposition parameters, such as purge time, the amount of structural defects introduced and the enhancement of the photocatalytic properties from different mesoporous films clearly shows that our easily upscalable non-conventional ALD process is of great industrial interest for environmental remediation and other photocatalytic applications, such as hydrogen production.

Crystal Growth Mechanisms of BiFeO3 Nanoparticles.

A wet-chemical synthesis process was designed to obtain reproducible single-phase multiferroic BiFeO3 nanoparticles. The phase purity, single crystallinity, and size of the nanoparticles are confirmed through the analysis of X-ray diffraction patterns, Raman spectroscopy, and high resolution transmission electron microscopy experiments. Crystal nucleation happens within the amorphous-rich area in multiple seeds, leading to the formation of single crystalline nanoparticles with no preferential faceting. Crystallization mechanisms of BiFeO3 nanoparticles were investigated following the Kissinger-Akahira-Sunose approach, indicating that two crystallization steps are responsible of the complete BiFeO3 nanoparticle formation. The first crystallization step involves a maximum of 70% of the final crystal volume, arising from nanocrystal nucleation and growth. The second step occurs above this threshold crystal volume fraction, and it is related to the nanocrystallite coalescence process. Analysis of the thermodynamic process of the crystallization of BiFeO3 nanoparticles following Ostwald rules suggests a relatively low energy barrier for crystal nucleation, highlighting that phase pure, single crystalline BiFeO3 nanoparticles are obtained using the present optimized wet-chemical synthesis process, with temperatures as low as 450 °C.

Influence of polymerisation on the reversibility of low-energy proton exchange reactions by Para-Aminothiolphenol.

The reversibility of redox processes is an important function for sensing and molecular electronic devices such as pH reporters or molecular switches. Here we report the electrochemical behaviour and redox reversibility of para-aminothiolphenol (PATP) after different polymerisation methods. We used electrochemical and photo-polymerisation in neutral buffers and plasma polymerisation in air to induce reversible redox states. The chemical stoichiometry and surface coverage of PATP in the polymerized layers were characterized by X-ray photoelectron spectroscopy (XPS), while cyclic voltammetry (CV) was used to measure the charge transfer, double layer capacitance and electrochemical rate of the layers during successive potential cycles. Our results show that the surface coverage of the redox active species is higher on electro-polymerised samples, however, after consecutive cycles all the methods converge to the same charge transfer, while the plasma polymerised samples achieve higher efficiency per molecule and UV polymerised samples have a higher electron transfer rate.

Deliberate and Accidental Gas-Phase Alkali Doping of Chalcogenide Semiconductors: Cu(In,Ga)Se2.

Alkali metal doping is essential to achieve highly efficient energy conversion in Cu(In,Ga)Se2 (CIGSe) solar cells. Doping is normally achieved through solid state reactions, but recent observations of gas-phase alkali transport in the kesterite sulfide (Cu2ZnSnS4) system (re)open the way to a novel gas-phase doping strategy. However, the current understanding of gas-phase alkali transport is very limited. This work (i) shows that CIGSe device efficiency can be improved from 2% to 8% by gas-phase sodium incorporation alone, (ii) identifies the most likely routes for gas-phase alkali transport based on mass spectrometric studies, (iii) provides thermochemical computations to rationalize the observations and (iv) critically discusses the subject literature with the aim to better understand the chemical basis of the phenomenon. These results suggest that accidental alkali metal doping occurs all the time, that a controlled vapor pressure of alkali metal could be applied during growth to dope the semiconductor, and that it may have to be accounted for during the currently used solid state doping routes. It is concluded that alkali gas-phase transport occurs through a plurality of routes and cannot be attributed to one single source.