Interplay Effects in the Co-Doping of ZnO Nanowires with Al and Ga Using Chemical Bath Deposition.

The simultaneous co-doping of ZnO nanowires grown by chemical bath deposition is of high interest for a large number of engineering devices, but the process conditions required and the resulting physicochemical processes are still largely unknown. Herein, we show that the simultaneous co-doping of ZnO nanowires with Al and Ga following the addition of Al(NO3)3 and Ga(NO3)3 in the chemical bath operates in a narrow range of conditions in the high-pH region, where the adsorption processes of respective Al(OH)4- and Ga(OH4)- complexes on the positively charged m-plane sidewalls are driven by attractive electrostatic forces. The structural morphology and properties of ZnO nanowires are significantly affected by the co-doping and mainly governed by the effect of Al(III) species. The incorporation processes of Al and Ga dopants are characterized by significant interplay effects, and the amount of incorporated Ga dopants into ZnO nanowires is found to be larger than the amount of incorporated Al dopants owing to energetic considerations. The Al and Ga dopants are located in the bulk of ZnO nanowires, but a part of Al and Ga lies on their surfaces, their incorporation processes in the bulk being enhanced by thermal annealing under oxygen atmosphere. Eventually, the Al and Ga dopants directly affect the incorporation of hydrogen-related defects, notably by annihilating the formation of VZn-nH defect complexes. These findings present an efficient strategy to proceed with the co-doping of ZnO nanowires grown by chemical bath deposition, opening perspectives to control their electronic structure properties with a higher precision.

Alcohol Vapor Sensor Based on Quasi-2D Nb2O5 Derived from Oxidized Nb2CTz MXenes.

MXenes are two-dimensional (2D) materials with a great potential for sensor applications due to their high aspect ratio and fully functionalized surface that can be tuned for specific gas adsorption. Here, we demonstrate that the Nb2CTz-based sensor exhibits high performance towards alcohol vapors at temperatures up to 300-350 °C, with the best sensitivity towards ethanol. We attribute the observed remarkable chemiresistive effect of this material to the formation of quasi-2D Nb2O5 sheets as the result of the oxidation of Nb-based MXenes. These findings are supported by synchrotron X-ray photoelectron spectroscopy studies together with X-ray diffraction and electron microscopy observations. For analyte selectivity, we employ a multisensor approach where the gas recognition is achieved by linear discriminant analysis of the vector response of the on-chip sensor array. The reported protocol demonstrates that MXene layers are efficient precursors for the derivation of 2D oxide architectures, which are suitable for developing gas sensors and sensor arrays.

The Path of Gallium from Chemical Bath into ZnO Nanowires: Mechanisms of Formation and Incorporation.

ZnO nanowires grown by chemical bath deposition (CBD) are of high interest, but their doping with extrinsic elements including gallium in aqueous solution is still challenging despite its primary importance for transparent electrodes and electronics, and for mid-infrared plasmonics. We elucidate the formation mechanisms of ZnO nanowires by CBD using zinc nitrate and hexamethylenetetramine as standard chemical precursors, as well as gallium nitrate and ammonia as chemical additives. A complete growth diagram, revealing the effects of both the relative concentration of gallium nitrate and pH, is gained by combining a thorough experimental approach with thermodynamic computations yielding theoretical solubility plots as well as Zn(II) and Ga(III) speciation diagrams. The role of Ga(OH)4- complexes is specifically shown as capping agents on the m-plane sidewalls of ZnO nanowires, enhancing their development and hence decreasing their aspect ratio. Additionally, the gallium incorporation into ZnO nanowires is investigated in detail by chemical analyses and Raman scattering. They show the predominant formation of gallium substituting for zinc atoms (GaZn) in as-grown ZnO nanowires and their partial conversion into GaZn-VZn complexes after postdeposition annealing under oxygen atmosphere. The conversion is further related to a significant relaxation of the strain level in ZnO nanowires. These findings reporting the physicochemical processes at work during the formation of ZnO nanowires and the related gallium incorporation mechanisms offer a general strategy for their extrinsic doping and open the way for carefully controlling their physical properties as required for nanoscale device engineering.

SnO2 Films Deposited by Ultrasonic Spray Pyrolysis: Influence of Al Incorporation on the Properties.

Aluminum-doped tin oxide (SnO 2:Al) thin films were produced by an ultrasonic spray pyrolysis method. The effect of aluminum doping on structural, optical, and electrical properties of tin oxide thin films synthesized at 420 ∘C was investigated. Al doping induced a change in the morphology of tin oxide films and yielded films with smaller grain size. SnO 2 thin films undergo a structural reordering and have a texture transition from (301) to (101), and then to (002) preferred cristallographic orientation upon Al doping. The lattice parameters (a and c) decreases with Al doping, following in a first approximation Vegard's law. The optical transmission does not change in the visible region with an average transmittance value of 72-81%. Conversely, in the near infrared (NIR) region, the plasmon frequency shifts towards the IR region upon increasing Al concentration in the grown films. Nominally undoped SnO 2 have a conductivity of ∼1120 S/cm, which is at least two orders of magnitude larger than what is reported in literature. This higher conductivity is attributed to the Cl- ions in the SnCl 4.5(H 2 O) precursor, which would act as donor dopants. The introduction of Al into the SnO 2 lattice showed a decrease of the electrical conductivity of SnO 2 due to compensating hole generation. These findings will be useful for further studied tackling the tailoring of the properties of highly demanded fluorine doped tin oxide (FTO) films.

Effects of the pH on the Formation and Doping Mechanisms of ZnO Nanowires Using Aluminum Nitrate and Ammonia.

The elucidation of the fundamental processes in aqueous solution during the chemical bath deposition of ZnO nanowires (NWs) using zinc nitrate and hexamethylenetetramine is of great significance: however, their extrinsic doping by foreign elements for monitoring their optical and electrical properties is still challenging. By combining thermodynamic simulations yielding theoretical solubility plots and speciation diagrams with in situ pH measurements and structural, chemical, and optical analyses, we report an in-depth understanding of the pH effects on the formation and aluminum doping mechanisms of ZnO NWs. By the addition of aluminum nitrate with a given relative concentration for the doping and of ammonia over a broad range of concentrations, the pH is shown to strongly influence the shape, diameter, length, and doping magnitude of ZnO NWs. Tuning the dimensions of ZnO NWs by inhibition of their radial growth only proceeds over a specific pH range, where negatively charged Al(OH)4- complexes are predominantly formed and act as capping agents by electrostatically interacting with the positively charged m-plane sidewalls. These complexes further favor the aluminum incorporation and doping of ZnO NWs, which only operate over the same pH range following thermal annealing above 200 °C. These findings reporting a full chemical synthesis diagram reveal the significance of carefully selecting and following the pH to control the morphology of ZnO NWs as well as to achieve their thermally activated extrinsic doping, as required for many nanoscale engineering devices.

Identifying and mapping the polytypes and orientation relationships in ZnO/CdSe core-shell nanowire arrays.

Identifying and mapping the crystalline phases and orientation relationships on the local scale in core-shell ZnO nanowire heterostructures are of primary importance to improve the interface quality, which governs the performances of the nanoscale devices. However, this represents a major difficulty, especially when the expected polytypes exhibit very similar properties as in the case of CdSe. In the present work, we address that issue in ZnO nanowire heterostructures involving a uniform and highly conformal CdSe shell grown by molecular beam epitaxy. It is shown by x-ray diffraction and Raman spectroscopy through the occurrence of the (101̄0) and (101̄1) diffraction peaks and of the [Formula: see text] mode at 34 cm-1, respectively, that the CdSe shell is mostly crystallized into the wurtzite phase. By using automated crystal phase and orientation mapping with precession (ASTAR) in a transmission electron microscope and thus by benefiting from highly precise electron diffraction patterns, the CdSe shell is found to crystallize also into the minority zinc blende phase. The wurtzite CdSe shell is epitaxially grown on the top of ZnO nanowires, and some specific orientation relationships are mapped and revealed when grown on their vertical sidewalls. Zinc blende CdSe domains are also formed exclusively in the center of wurtzite CdSe grains located on the vertical sidewalls; both wurtzite and zinc blende CdSe crystalline phases have a strong orientation relationship. These findings reveal that ASTAR is a powerful technique to elucidate the structural properties on the local scale and to gain a deeper insight into their crystalline phases and orientation relationships, which is highly promising for many types of semiconducting nanowire heterostructures.

Sunlight-Driven Photocatalytic Degradation of Methylene Blue with Facile One-Step Synthesized Cu-Cu2O-Cu3N Nanoparticle Mixtures.

Sunlight-driven photocatalytic degradation is an effective and eco-friendly technology for the removal of organic pollutants from contaminated water. Herein, we describe the one-step synthesis of Cu-Cu2O-Cu3N nanoparticle mixtures using a novel non-aqueous, sol-gel route and their application in the solar-driven photocatalytic degradation of methylene blue. The crystalline structure and morphology were investigated with XRD, SEM and TEM. The optical properties of the as-prepared photocatalysts were investigated with Raman, FTIR, UV-Vis and photoluminescence spectroscopies. The influence of the phase proportions of Cu, Cu2O and Cu3N in the nanoparticle mixtures on the photocatalytic activity was also investigated. Overall, the sample containing the highest quantity of Cu3N exhibits the highest photocatalytic degradation efficiency (95%). This enhancement is attributed to factors such as absorption range broadening, increased specific surface of the photocatalysts and the downward band bending in the p-type semiconductors, i.e., Cu3N and Cu2O. Two different catalytic dosages were studied, i.e., 5 mg and 10 mg. The higher catalytic dosage exhibited lower photocatalytic degradation efficiency owing to the increase in the turbidity of the solution.

Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3-Ce0.8Sm0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications.

The use of nanostructured interfaces and advanced functional materials opens up a new playground in the field of solid oxide fuel cells. In this work, we present two all-ceramic thin-film heterostructures based on samarium-doped ceria and lanthanum strontium chromite manganite as promising functional layers for electrode application. The films were fabricated by pulsed laser deposition as bilayers or self-assembled intermixed nanocomposites. The microstructural characterization confirmed the formation of dense, well-differentiated, phases and highlighted the presence of strong cation intermixing in the case of the nanocomposite. The electrochemical properties─solid/gas reactivity and in-plane conductivity─are strongly improved for both heterostructures with respect to the single-phase constituents under anodic conditions (up to fivefold decrease of area-specific resistance and 3 orders of magnitude increase of in-plane conductivity with respect to reference single-phase materials). A remarkable electrochemical activity was also observed for the nanocomposite under an oxidizing atmosphere, with no significant decrease in performance after 400 h of thermal aging. This work shows how the implementation of nanostructuring strategies not only can be used to tune the properties of functional films but also results in a synergistic enhancement of the electrochemical performance, surpassing the parent materials and opening the field for the fabrication of high-performance nanostructured functional layers for application in solid oxide fuel cells and symmetric systems.

Chemical deposition of Cu2O films with ultra-low resistivity: correlation with the defect landscape.

Cuprous oxide (Cu2O) is a promising p-type semiconductor material for many applications. So far, the lowest resistivity values are obtained for films deposited by physical methods and/or at high temperatures (~1000 °C), limiting their mass integration. Here, Cu2O thin films with ultra-low resistivity values of 0.4 Ω.cm were deposited at only 260 °C by atmospheric pressure spatial atomic layer deposition, a scalable chemical approach. The carrier concentration (7.1014-2.1018 cm-3), mobility (1-86 cm2/V.s), and optical bandgap (2.2-2.48 eV) are easily tuned by adjusting the fraction of oxygen used during deposition. The properties of the films are correlated to the defect landscape, as revealed by a combination of techniques (positron annihilation spectroscopy (PAS), Raman spectroscopy and photoluminescence). Our results reveal the existence of large complex defects and the decrease of the overall defect concentration in the films with increasing oxygen fraction used during deposition.

Silver Nanowire Networks: Ways to Enhance Their Physical Properties and Stability.

Silver nanowire (AgNW) networks have been intensively investigated in recent years. Thanks to their attractive physical properties in terms of optical transparency and electrical conductivity, as well as their mechanical performance, AgNW networks are promising transparent electrodes (TE) for several devices, such as solar cells, transparent heaters, touch screens or light-emitting devices. However, morphological instabilities, low adhesion to the substrate, surface roughness and ageing issues may limit their broader use and need to be tackled for a successful performance and long working lifetime. The aim of the present work is to highlight efficient strategies to optimize the physical properties of AgNW networks. In order to situate our work in relation to existing literature, we briefly reported recent studies which investigated physical properties of AgNW networks. First, we investigated the optimization of optical transparency and electrical conductivity by comparing two types of AgNWs with different morphologies, including PVP layer and AgNW dimensions. In addition, their response to thermal treatment was deeply investigated. Then, zinc oxide (ZnO) and tin oxide (SnO2) protective films deposited by Atmospheric Pressure Spatial Atomic Layer Deposition (AP-SALD) were compared for one type of AgNW. We clearly demonstrated that coating AgNW networks with these thin oxide layers is an efficient approach to enhance the morphological stability of AgNWs when subjected to thermal stress. Finally, we discussed the main future challenges linked with AgNW networks optimization processes.

Optimization of GOPS-Based Functionalization Process and Impact of Aptamer Grafting on the Si Nanonet FET Electrical Properties as First Steps towards Thrombin Electrical Detection.

Field effect transistors (FETs) based on networks of randomly oriented Si nanowires (Si nanonets or Si NNs) were biomodified using Thrombin Binding Aptamer (TBA-15) probe with the final objective to sense thrombin by electrical detection. In this work, the impact of the biomodification on the electrical properties of the Si NN-FETs was studied. First, the results that were obtained for the optimization of the (3-Glycidyloxypropyl)trimethoxysilane (GOPS)-based biofunctionalization process by using UV radiation are reported. The biofunctionalized devices were analyzed by atomic force microscopy (AFM) and scanning transmission electron microscopy (STEM), proving that TBA-15 probes were properly grafted on the surface of the devices, and by means of epifluorescence microscopy it was possible to demonstrate that the UV-assisted GOPS-based functionalization notably improves the homogeneity of the surface DNA distribution. Later, the electrical characteristics of 80 devices were analyzed before and after the biofunctionalization process, indicating that the results are highly dependent on the experimental protocol. We found that the TBA-15 hybridization capacity with its complementary strand is time dependent and that the transfer characteristics of the Si NN-FETs obtained after the TBA-15 probe grafting are also time dependent. These results help to elucidate and define the experimental precautions that must be taken into account to fabricate reproducible devices.

Versatility of bilayer metal oxide coatings on silver nanowire networks for enhanced stability with minimal transparency loss.

Silver nanowire (AgNW) networks have been lately much investigated thanks to their physical properties and are therefore foreseen to play a key role in many industrial devices as transparent electrodes, but their stability can be an issue. Although it has been shown that thin metal oxide coatings enhance the stability of AgNW networks, such stabilization is achieved at the expense of transparency. We demonstrate that by depositing a second oxide coating, which acts as an antireflective layer, it is possible to obtain highly stable and transparent composite electrodes. AgNW networks were deposited by the airbrush method, and zinc oxide (ZnO) and aluminum oxide (Al2O3) coatings were deposited, by Atmospheric Pressure Spatial Atomic Layer Deposition (AP-SALD), using both glass and plastic substrates; therefore, the proposed fabrication method is low-cost and compatible with high-throughput scalable fabrication. The mechanical stability of bare, ZnO and ZnO/Al2O3-coated AgNWs upon bending is also presented. The obtained nanocomposites exhibit highly homogeneous and conformal oxide coatings with average thicknesses of a few tens of nanometers. Samples with bilayer coatings of 70 nm ZnO/70 nm Al2O3 still exhibit very good stability after annealing in air up to 450 °C for 6 repetitive cycles.

Integration of LaMnO3+δ films on platinized silicon substrates for resistive switching applications by PI-MOCVD.

The next generation of electronic devices requires faster operation velocity, higher storage capacity and reduction of the power consumption. In this context, resistive switching memory chips emerge as promising candidates for developing new non-volatile memory modules. Manganites have received increasing interest as memristive material as they exhibit a remarkable switching response. Nevertheless, their integration in CMOS-compatible substrates, such as silicon wafers, requires further effort. Here the integration of LaMnO3+δ as memristive material in a metal-insulator-metal structure is presented using a silicon-based substrate and the pulsed injection metal organic chemical vapour deposition technique. We have developed three different growth strategies with which we are able to tune the oxygen content and Mn oxidation state moving from an orthorhombic to a rhombohedral structure for the active LaMnO3+δ material. Furthermore, a good resistive switching response has been obtained for LaMnO3+δ-based devices fabricated using optimized growth strategies.

The initial stages of ZnO atomic layer deposition on atomically flat In0.53Ga0.47As substrates.

InGaAs is one of the III-V active semiconductors used in modern high-electron-mobility transistors or high-speed electronics. ZnO is a good candidate material to be inserted as a tunneling insulator layer at the metal-semiconductor junction. A key consideration in many modern devices is the atomic structure of the hetero-interface, which often ultimately governs the electronic or chemical process of interest. Here, a complementary suite of in situ synchrotron X-ray techniques (fluorescence, reflectivity and absorption) as well as modeling is used to investigate both structural and chemical evolution during the initial growth of ZnO by atomic layer deposition (ALD) on In0.53Ga0.47As substrates. Prior to steady-state growth behavior, we discover a transient regime characterized by two stages. First, substrate-inhibited ZnO growth takes place on InGaAs terraces. This leads eventually to the formation of a 1 nm-thick, two-dimensional (2D) amorphous layer. Second, the growth behavior and its modeling suggest the occurrence of dense island formation, with an aspect ratio and surface roughness that depends sensitively on the growth condition. Finally, ZnO ALD on In0.53Ga0.47As is characterized by 2D steady-state growth with a linear growth rate of 0.21 nm cy-1, as expected for layer-by-layer ZnO ALD.

The quest towards epitaxial BaMgF4 thin films: exploring MOCVD as a chemical scalable approach for the deposition of complex metal fluoride films.

Conventional and Pulsed Liquid Injection MOCVD processes (C-MOCVD and PLI-MOCVD) have been explored as synthetic routes for the growth of BaMgF4 on Si (100) and single crystalline SrTiO3 (100) substrates. For the two applied approaches, the volatile, thermally stable ß-diketonate complexes Ba(hfa)2tetraglyme and Mg(hfa)2(diglyme)2(H2O)2 have been used as single precursors (C-MOCVD) or as a solution multimetal source (PLI-MOCVD). Structural characterization through X-ray diffraction (XRD) measurements and transmission electron microscopy (TEM) analyses confirmed the formation of epitaxial BaMgF4 films on SrTiO3 substrates. Energy dispersive X-ray (EDX) analyses have been used to confirm composition and purity of deposited films. The impact of process parameters on film properties has been addressed, highlighting the strong influence of precursor ratio, deposition temperature and oxygen partial pressure on composition, microstructure and morphology of the films. Both methods appear well suited for the growth of the BaMgF4 phase, but while PLI-MOCVD yields a more straightforward control of the precursor composition that reflects on film stoichiometry, C-MOCVD provides easier control of the degree of texturing as a function of temperature.

Hybrid nickel manganese oxide nanosheet-3D metallic dendrite percolation network electrodes for high-rate electrochemical energy storage.

This work reports the fabrication, by electrodeposition and post-thermal annealing, of hybrid electrodes for high rate electrochemical energy storage composed of nickel manganese oxide (Ni0.86Mn0.14O) nanosheets over 3D open porous dendritic NiCu foams. The hybrid electrodes are made of two different percolation networks of nanosheets and dendrites, and exhibit a specific capacitance value of 848 F g(-1) at 1 A g(-1). The electrochemical tests revealed that the electrodes display an excellent rate capability, characterized by capacitance retention of approximately 83% when the applied current density increases from 1 A g(-1) to 20 A g(-1). The electrodes also evidenced high charge-discharge cycling stability, which attained 103% after 1000 cycles.

Improvement of the physical properties of ZnO/CdTe core-shell nanowire arrays by CdCl2 heat treatment for solar cells.

CdTe is an important compound semiconductor for solar cells, and its use in nanowire-based heterostructures may become a critical requirement, owing to the potential scarcity of tellurium. The effects of the CdCl2 heat treatment are investigated on the physical properties of vertically aligned ZnO/CdTe core-shell nanowire arrays grown by combining chemical bath deposition with close space sublimation. It is found that recrystallization phenomena are induced by the CdCl2 heat treatment in the CdTe shell composed of nanograins: its crystallinity is improved while grain growth and texture randomization occur. The presence of a tellurium crystalline phase that may decorate grain boundaries is also revealed. The CdCl2 heat treatment further favors the chlorine doping of the CdTe shell with the formation of chlorine A-centers and can result in the passivation of grain boundaries. The absorption properties of ZnO/CdTe core-shell nanowire arrays are highly efficient, and more than 80% of the incident light can be absorbed in the spectral range of the solar irradiance. The resulting photovoltaic properties of solar cells made from ZnO/CdTe core-shell nanowire arrays covered with CuSCN/Au back-side contact are also improved after the CdCl2 heat treatment. However, recombination and trap phenomena are expected to operate, and the collection of the holes that are mainly photo-generated in the CdTe shell from the CuSCN/Au back-side contact is presumably identified as the main critical point in these solar cells.

In situ synthesis of gold nanoparticles in exponentially-growing layer-by-layer films.

In situ synthesis of inorganic nanoparticles (NPs) in polyelectrolytes multilayers (PEMs) has recently gained much attention. Due to the versatility of their composition, PEMs offer a unique opportunity to synthesize a variety of NPs. So far, mostly cationic precursors have been used and only few studies have investigated the possibility of using amine groups to bind anionic precursors. Here, we use exponentially growing poly(L-lysine)/hyaluronan (PLL/HA) films as a nanoreservoir to bind and sequester aurochlorate (AuCl(4)(-)) anions thanks to the large number of free amine groups. The polypeptide-polysaccharide reactive template enabled the formation in a spatially-confined environment of gold NP at a very high yield. The synthesized gold NPs were homogenous and well-dispersed in the nanocomposite. Importantly, there was no particular effect of the film-ending layer (either PLL or HA). The largest particles of ~9 nm and the largest amount of gold were obtained at acidic pH of 3. When the pH was increased, smaller and more numerous NPs were synthesized but the total amount of gold was lower. Based on UV-visible spectrometry, FTIR and TEM data, we finally propose a scheme for the mechanism of gold NPs formation, in which several groups of PLL and HA contribute to the binding of gold ions, the nucleation and growth of NPs, and their stabilization in the "bulk" of the film.