Nanocomposites based on Cu2O coated silver nanowire networks for high-performance oxygen evolution reaction.

The development of highly active, low-cost, and robust electrocatalysts for the oxygen evolution reaction (OER) is a crucial endeavor for the clean and economically viable production of hydrogen via electrochemical water splitting. Herein, cuprous oxide (Cu2O) thin films are deposited on silver nanowire (AgNW) networks by atmospheric-pressure spatial atomic layer deposition (AP-SALD). AgNW@Cu2O nanocomposites supported on conductive copper electrodes exhibited superior OER activity as compared to bare copper substrate and bare AgNWs. Moreover, a relationship between Cu2O thickness and OER activity was established. Notably, the most effective catalyst (AgNW@50nm-thick Cu2O) demonstrated very high OER activity with a low overpotential of 409 mV to deliver a current density of 10 mA cm-2 (η 10), a Tafel slope of 47 mV dec-1, a turnover frequency (TOF) of 4.2 s-1 at 350 mV, and good durability in alkaline media (1 M KOH). This highlights the potential of AgNWs as a powerful platform for the formation of highly efficient copper oxide catalysts towards OER. This work provides a foundation for the development of nanostructured Cu-based electrocatalysts for future clean energy conversion and storage systems.

Assessing the Environmental Impact of Atomic Layer Deposition (ALD) Processes and Pathways to Lower It.

Due to concerns on resources depletion, climate change, and overall pollution, the quest toward more sustainable processes is becoming crucial. Atomic layer deposition (ALD) is a versatile technology, allowing for the precise coating of challenging substrates with a nanometer control over thickness. Due to its unique ability to nanoengineer interfaces and surfaces, ALD is widely used in many applications. Although the ALD technique offers the potential to tackle environmental challenges, in particular, considerations regarding the sustainability of renewable energy devices urge for greater efficiency and lower carbon footprint. Indeed, the process itself has currently a consequential impact on the environment, which should ideally be reduced as the technique is implemented in a wider range of products and applications. This paper reviews the studies carried out on the assessment of the environmental impact of ALD and summarizes the main results reported in the literature. Next, the principles of green chemistry are discussed, considering the specificities of the ALD process. This work also suggests future pathways to reduce the ALD environmental impact; in particular, the optimization of the reactor and processing parameters, the use of high throughput processes such as spatial ALD (SALD), and the chemical design of greener precursors are proposed as efficient routes to improve ALD sustainability.

Can We Rationally Design and Operate Spatial Atomic Layer Deposition Systems for Steering the Growth Regime of Thin Films?

Fine control over the growth of materials is required to precisely tailor their properties. Spatial atomic layer deposition (SALD) is a thin-film deposition technique that has recently attracted attention because it allows producing thin films with a precise number of deposited layers, while being vacuum-free and much faster than conventional atomic layer deposition. SALD can be used to grow films in the atomic layer deposition or chemical vapor deposition regimes, depending on the extent of precursor intermixing. Precursor intermixing is strongly influenced by the SALD head design and operating conditions, both of which affect film growth in complex ways, making it difficult to predict the growth regime prior to depositions. Here, we used numerical simulation to systematically study how to rationally design and operate SALD systems for growing thin films in different growth regimes. We developed design maps and a predictive equation allowing us to predict the growth regime as a function of the design parameters and operation conditions. The predicted growth regimes match those observed in depositions performed for various conditions. The developed design maps and predictive equation empower researchers in designing, operating, and optimizing SALD systems, while offering a convenient way to screen deposition parameters, prior to experimentation.

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.

Atmospheric atomic layer deposition of SnO2 thin films with tin(II) acetylacetonate and water.

Due to its unique optical, electrical, and chemical properties, tin dioxide (SnO2) thin films attract enormous attention as a potential material for gas sensors, catalysis, low-emissivity coatings for smart windows, transparent electrodes for low-cost solar cells, etc. However, the low-cost and high-throughput fabrication of SnO2 thin films without producing corrosive or toxic by-products remains challenging. One appealing deposition technique, particularly well-adapted to films presenting nanometric thickness is atomic layer deposition (ALD). In this work, several metalorganic tin-based complexes, namely, tin(IV) tert-butoxide, bis[bis(trimethylsilyl)amino] tin(II), dibutyltin diacetate, tin(II) acetylacetonate, tetrakis(dimethylamino) tin(IV), and dibutyltin bis(acetylacetonate), were explored thanks to DFT calculations. Our theoretical calculations suggest that the three last precursors are very appealing for ALD of SnO2 thin films. The potential use of these precursors for atmospheric-pressure spatial atomic layer deposition (AP-SALD) is also discussed. For the first time, we experimentally demonstrate the AP-SALD growth of SnO2 thin films using tin(II) acetylacetonate (Sn(acac)2) and water. We observe that Sn(acac)2 exhibits efficient ALD activity with a relatively large ALD temperature window (140-200 °C), resulting in a growth rate of 0.85 ± 0.03 Å per cyc. XPS analyses show a single Sn 3d5/2 characteristic peak for Sn4+ at 486.8 ± 0.3 eV, indicating that a pure SnO2 phase is obtained within the ALD temperature window. The as-deposited SnO2 thin films are in all cases amorphous, and film conductivity increases with the deposition temperature. Hall effect measurements confirm the n-type nature of SnO2 with a free electron density of about 8 × 1019 cm-3, electron mobility up to 11.2 cm2 V-1 s-1, and resistivity of 7 × 10-3 Ω cm for samples deposited at 270 °C.

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.

Effects of non-homogeneity and oxide coating on silver nanowire networks under electrical stress: comparison between experiment and modeling.

Silver nanowire (AgNW) networks are among the most promising indium-free, flexible transparent electrodes for energy, lighting and heating devices. However, the lack of stability of such networks is a key factor that limits their industrial application. While applications require homogeneous networks, non-homogeneous AgNW networks are intentionally prepared in the present work to probe the mechanisms leading to failure under electrical stress. We show that induced non-homogeneities have a strong impact both on the spatial distribution of temperature (measured by IR imaging) and the current density throughout the electrode (as deduced from modeling). Regions with higher current density under elevated electrical stress are correlated to the origin of degradation. Furthermore, the influence of a zinc oxide (ZnO) layer on electrical performances of non-homogeneous specimens is studied. Thanks to ZnO coating, the tortuosity of electrical potential lines measured by the one-probe mapping technique is much lower than for bare networks. Additionally, coated network electrical failure occurs at 40% higher voltage compared to bare network, over 18 V, while reaching superior power-induced heating of 360 °C. The results presented here will contribute to the design and fabrication of more robust nanowire networks, particularly for application in transparent heaters.

Planar and Transparent Memristive Devices Based on Titanium Oxide Coated Silver Nanowire Networks with Tunable Switching Voltage.

Threshold switching devices are fundamental active elements in more than Moore approaches, integrating the new generation of non-volatile memory devices. Here, the authors report an in-plane threshold resistive switching device with an on/off ratio above 106 , a low resistance state of 10 to 100 kΩ and a high resistance state of 10 to 100 GΩ. Our devices are based on nanocomposites of silver nanowire networks and titanium oxide, where volatile unipolar threshold switching takes place across the gap left by partially spheroidized nanowires. Device reversibility depends on the titanium oxide thickness, while nanowire network density determines the threshold voltage, which can reach as low as 0.16 V. The switching mechanism is explained through percolation between metal-semiconductor islands, in a combined tunneling conduction mechanism, followed by a Schottky emission generated via Joule heating. The devices are prepared by low-cost, atmospheric pressure, and scalable techniques, enabling their application in printable, flexible, and transparent electronics.