Highly Sensitive Self-Actuated Zinc Oxide Resonant Microcantilever Humidity Sensor.

A resonant microcantilever sensor is fabricated from a zinc oxide (ZnO) thin film, which serves as both the structural and sensing layers. An open-air spatial atomic layer deposition technique is used to deposit the ZnO layer to achieve a ∼200 nm thickness, an order of magnitude lower than the thicknesses of conventional microcantilever sensors. The reduction in the number of layers, in the cantilever dimensions, and its overall lower mass lead to an ultrahigh sensitivity, demonstrated by detection of low humidity levels. A maximum sensitivity of 23649 ppm/% RH at 5.8% RH is observed, which is several orders of magnitude larger than those reported for other resonant humidity sensors. Furthermore, the ZnO cantilever sensor is self-actuated in air, an advantageous detection mode that enables simpler and lower-power-consumption sensors.

Advances in Flexible Metallic Transparent Electrodes.

Transparent electrodes (TEs) are pivotal components in many modern devices such as solar cells, light-emitting diodes, touch screens, wearable electronic devices, smart windows, and transparent heaters. Recently, the high demand for flexibility and low cost in TEs requires a new class of transparent conductive materials (TCMs), serving as substitutes for the conventional indium tin oxide (ITO). So far, ITO has been the most used TCM despite its brittleness and high cost. Among the different emerging alternative materials to ITO, metallic nanomaterials have received much interest due to their remarkable optical-electrical properties, low cost, ease of manufacturing, flexibility, and widespread applicability. These involve metal grids, thin oxide/metal/oxide multilayers, metal nanowire percolating networks, or nanocomposites based on metallic nanostructures. In this review, a comparison between TCMs based on metallic nanomaterials and other TCM technologies is discussed. Next, the different types of metal-based TCMs developed so far and the fabrication technologies used are presented. Then, the challenges that these TCMs face toward integration in functional devices are discussed. Finally, the various fields in which metal-based TCMs have been successfully applied, as well as emerging and potential applications, are summarized.

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.

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.

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.

Oxidation of copper nanowire based transparent electrodes in ambient conditions and their stabilization by encapsulation: application to transparent film heaters.

Whereas the integration of silver nanowires in functional devices has reached a fair level of maturity, the integration of copper nanowires still remains difficult, mainly due to the intrinsic instability of copper nanowires in ambient conditions. In this paper, copper nanowire based transparent electrodes with good performances (33 Ω sq-1 associated with 88% transparency) were obtained, and their degradation in different conditions was monitored, in particular by electrical measurements, transmission electron microscopy, x-ray photoelectron spectrometry and Auger electron spectroscopy. Several routes to stabilize the random networks of copper nanowires were evaluated. Encapsulation through laminated barrier film with optical clear adhesive and atmospheric pressure spatial atomic layer deposition were found to be efficient and were used for the fabrication of transparent film heaters.

Direct Imaging of the Onset of Electrical Conduction in Silver Nanowire Networks by Infrared Thermography: Evidence of Geometrical Quantized Percolation.

Advancement in the science and technology of random metallic nanowire (MNW) networks is crucial for their appropriate integration in many applications including transparent electrodes for optoelectronics and transparent film heaters. We have recently highlighted the discontinuous activation of efficient percolating pathways (EPPs) for networks having densities slightly above the percolation threshold. Such networks exhibit abrupt drops of electrical resistance when thermal or electrical annealing is performed, which gives rise to a "geometrically quantized percolation". In this Letter, lock-in thermography (LiT) is used to provide visual evidence of geometrical quantized percolation: when low voltage is applied to the network, individual "illuminated pathways" can be detected, and new branches get highlighted as the voltage is incrementally increased. This experimental approach has allowed us to validate our original model and map the electrical and thermal distributions in silver nanowire (AgNW) networks. We also study the effects of electrode morphology and wire dimensions on quantized percolation. Furthermore, we demonstrate that the network failure at high temperature can also be governed by a quantized increase of the electrical resistance, which corresponds to the discontinuous destruction of individual pathways (antipercolation). More generally, we demonstrate that LiT is a promising tool for the detection of conductive subclusters as well as hot spots in AgNW networks.

Improved Exciton Dissociation at Semiconducting Polymer:ZnO Donor:Acceptor Interfaces via Nitrogen Doping of ZnO.

Exciton dissociation at the zinc oxide/poly(3-hexylthiophene) (ZnO/P3HT) interface as a function of nitrogen doping of the zinc oxide, which decreases the electron concentration from approximately 1019 cm-3 to 1017 cm-3, is reported. Exciton dissociation and device photocurrent are strongly improved with nitrogen doping. This improved dissociation of excitons in the conjugated polymer is found to result from enhanced light-induced de-trapping of electrons from the surface of the nitrogen-doped ZnO. The ability to improve the surface properties of ZnO by introducing a simple nitrogen dopant has general applicability.

Exploring the degradation of silver nanowire networks under thermal stress by coupling in situ X-ray diffraction and electrical resistance measurements.

The thermal instability of silver nanowires (AgNWs) leads to a significant increase of the electrical resistance of AgNW networks. A better understanding of the relationship between the structural and electrical properties of AgNW networks is primordial for their efficient integration as transparent electrodes (TEs) for next-generation flexible optoelectronics. Herein, we investigate the in situ evolution of the main crystallographic parameters (i.e. integrated intensity, interplanar spacing and peak broadening) of two Ag-specific Bragg peaks, (111) and (200), during a thermal ramp up to 400 °C through in situ X-ray diffraction (XRD) measurements, coupled with in situ electrical resistance measurements on the same AgNW network. First, we assign the (111) and (200) peaks of χ-scans to each five crystallites within AgNWs using a rotation matrix model. Then, we show that the thermal transition of bare AgNW networks occurs within a temperature range of about 25 °C for the electrical properties, while the structural transition spans over 200 °C. The effect of a protective tin oxide coating (SnO2) on AgNW networks is also investigated through this original in situ coupling approach. For SnO2-coated AgNW networks, the key XRD signatures from AgNWs remain constant, since the SnO2 coating prevents Ag atomic surface diffusion, and thus morphological instability (i.e. spheroidization). Moreover, the SnO2 coating does not affect the strain of both (111) and (200) planes. The thermal expansion for bare and SnO2-coated AgNW networks appears very similar to the thermal expansion of bulk Ag. Our findings provide insights into the underlying failure mechanisms of AgNW networks subjected to thermal stress, helping researchers to develop more robust and durable TEs based on metallic nanowire networks.

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.

Silver Nanowire-Based Transparent Electrodes for V2O5 Thin Films with Electrochromic Properties.

The development of electrochromic systems, known for the modulation of their optical properties under an applied voltage, depends on the replacement of the state-of-the-art ITO (In2O3:Sn) transparent electrode (TE) as well as the improvement of electrochromic films. This study presents an innovative ITO-free electrochromic film architecture utilizing oxide-coated silver nanowire (AgNW) networks as a TE and V2O5 as an electrochromic oxide layer. The TE was prepared by simple spray deposition of AgNWs that allowed for tuning different densities of the network and hence the resistance and transparency of the film. The conformal oxide coating (SnO2 or ZnO) on AgNWs was deposited by atmospheric-pressure spatial atomic layer deposition, an open-air fast and scalable process yielding a highly stable electrode. V2O5 thin films were then deposited by radio frequency magnetron sputtering on the AgNW-based TE. Independent of the oxide's nature, a 20 nm protective layer thickness was insufficient to prevent the deterioration of the AgNW network during V2O5 deposition. On the contrary, crystalline V2O5 films were grown on 30 nm thick ZnO or SnO2-coated AgNWs, exhibiting a typical orange color. Electrochromic characterization demonstrated that only V2O5 films deposited on 30 nm thick SnO2-coated AgNW showed characteristic oxidation-reduction peaks in the Li+-based liquid electrolyte associated with a reversible orange-to-blue color switch for at least 500 cycles. The electrochromic key properties of AgNW/SnO2 (30 nm)/V2O5 films are discussed in terms of structural and morphological changes due to the AgNW network and the nature and thickness of the two protective oxide coatings.

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.

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.

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.

Liquid atomic layer deposition as emergent technology for the fabrication of thin films.

Atomic layer deposition (ALD) is widely recognized as a unique chemical vapor deposition technique for the fabrication of thin films with high conformality and precise thickness control down to the Ångstrom level, thereby allowing surface and interface nanoengineering. However, several challenges such as the availability of chemical precursors for ALD and the use of vacuum conditions have hampered its widespread adoption and scalability for mass production. In recent years, the liquid phase homolog of ALD, liquid atomic layer deposition (LALD), has emerged as a much simpler and versatile strategy to overcome some of the current constraints of ALD. This perspective describes the different strategies that have been explored to achieve conformality and sub-nanometer thickness control with LALD, as well as the current challenges it faces to become a part of the thin-film community toolbox, in particular its automation and compatibility with different types of substrates. In this regard, the important role of LALD as complementary technology to ALD is emphasized by comparing the different pathways to deposit the same material and the precursors used to do so.

Dynamic degradation of metallic nanowire networks under electrical stress: a comparison between experiments and simulations.

Metallic nanowire networks represent a promising solution for a new generation of transparent and flexible devices, including touch screens, solar cells and transparent heaters. They, however, lack stability under thermal and electrical stresses, often leading to the degradation of nanowires, which results in the loss of electrical percolation paths. We propose a comprehensive description of the degradation mechanism in a metallic nanowire network subjected to electrical stress. The nanowire network degradation is ascribed, at a very local scale, to the hot-spot formation and the subsequent propagation of a spatially correlated disruptive crack. We compare the behaviour of actual networks under electrical and thermal stresses to dynamic simulations of randomly deposited sticks on a 2D surface, and a thermal phenomenon simulated in a metal thin film. On one hand, such comparison allows us to deduce an average junction resistance between nanowires. On the other hand, we observed that initial flaws in a discrete network result in a local current density increase in the surrounding area, further leading to an amplified Joule effect. This phenomenon promotes the spatial correlation in the damage of the percolating network. Such non-reversible failure of the transparent electrode is in good agreement with experimental observations.

Transparent and Mechanically Resistant Silver-Nanowire-Based Low-Emissivity Coatings.

This article reports on the fabrication and investigation of low-emissivity (low-E) coatings based on random networks of silver nanowires (AgNWs). The transparent layers based on AgNWs do exhibit low emissivity while being still transparent: an overall emissivity as low as 0.21 at 78% total transmittance was obtained. A simple physical model allows to rationalize the emissivity-transparency dependence and a good agreement with experimental data is observed. This model demonstrates the role played by AgNWs which partially reflect IR photons emitted by the substrate, exacerbating then the presence of AgNWs and lowering the total emissivity. The potential use of such layers in functional devices is hampered by the poor intrinsic surface adhesion of the AgNWs, which renders the coating fragile and prone to mechanical damaging. Two very efficient encapsulation processes based on the deposition of a conformal alumina thin film using the spatial atomic layer deposition technique and the solution processed layer deposition of a polysiloxane varnish have been developed to thwart this weakness. Both coatings combine sturdy mechanical resistance relying on a strong interfacial adhesion and excellent optical transmittance properties. The performances for the mechanically resistant low-E coatings achieve an overall emissivity as low as 0.34 at 74% total transparency. The set of optical properties and mechanical resistance of the reported AgNWs based low-E coatings combined with the ease of fabrication and the cost-effective production process make it an excellent candidate for a wide set of applications, including smart windows for energy-saving buildings.

Tuning the band gap and carrier concentration of titania films grown by spatial atomic layer deposition: a precursor comparison.

Spatial atomic layer deposition retains the advantages of conventional atomic layer deposition: conformal, pinhole-free films and excellent control over thickness. Additionally, it allows higher deposition rates and is well-adapted to depositing metal oxide nanofilms for photovoltaic cells and other devices. This study compares the morphological, electrical and optical properties of titania thin films deposited by spatial atomic layer deposition from titanium isopropoxide (TTIP) and titanium tetrachloride (TiCl4) over the temperature range 100-300 °C, using the oxidant H2O. Amorphous films were deposited at temperatures as low as 100 °C from both precursors: the approach is suitable for applying films to temperature-sensitive devices. An amorphous-to-crystalline transition temperature was observed for both precursors resulting in surface roughening, and agglomerates for TiCl4. Both precursors formed conformal anatase films at 300 °C, with growth rates of 0.233 and 0.153 nm s-1 for TiCl4 and TTIP. A drawback of TiCl4 use is the HCl by-product, which was blamed for agglomeration in the films. Cl contamination was the likely cause of band gap narrowing and higher defect densities compared to TTIP-grown films. The carrier concentration of the nanofilms was found to increase with deposition temperature. The films were tested in hybrid bilayer solar cells to demonstrate their appropriateness for photovoltaic devices.

Advanced technologies for the fabrication of MOF thin films.

Metal-organic framework (MOF) thin films represent a milestone in the development of future technological breakthroughs. The processability of MOFs as films on surfaces together with their major features (i.e. tunable porosity, large internal surface area, and high crystallinity) is broadening their range of applications to areas such as gas sensing, microelectronics, photovoltaics, and membrane-based separation technologies. Despite the recent attention that MOF thin films have received, many challenges still need to be addressed for their manufacturing and integrability, especially when an industrial scale-up perspective is envisioned. In this brief review, we introduce several appealing approaches that have been developed in the last few years. First, a summary of liquid phase strategies that comprise microfluidic methods and supersaturation-driven crystallization processes is described. Then, gas phase approaches based on atomic layer deposition (ALD) are also presented.