Effect of different oxygen precursors on alumina deposited using a spatial atomic layer deposition system for thin-film encapsulation of perovskite solar cells.

An atmospheric-pressure spatial atomic layer deposition system operated in atmospheric-pressure spatial chemical vapor deposition conditions is employed to deposit alumina (AlOx) thin films using trimethylaluminum and different oxidants, including water (H2O), hydrogen peroxide (H2O2), and ozone (O3). The impact of the oxygen precursor on the structural properties of the films and their moisture-barrier performance is investigated. The O3-AlOxfilms, followed by H2O2-AlOx, exhibit higher refractive indexes, lower concentrations of OH- groups, and lower water-vapor-transmission rates compared to the films deposited using water (H2O-AlOx). The AlOxfilms are then rapidly deposited as thin-film-encapsulation layers on perovskite solar cells at 130 °C without damaging the temperature-sensitive perovskite and organic materials. The stability of thep-i-nformamidinium methylammonium lead iodide solar cells under standard ISOS-D-3 testing conditions (65 °C and 85% relative humidity) is significantly enhanced by the encapsulation layers. Specifically, the O3-AlOxand H2O2-AlOxlayers result in a six-fold increase in the time required for the cells to degrade to 80% of their original efficiency compared to un-encapsulated cells.

Silver nanowire electrodes for transparent light emitting devices based on WS2monolayers.

Transition metal dichalcogenide (TMDC) monolayers with their direct band gap in the visible to near-infrared spectral range have emerged over the past years as highly promising semiconducting materials for optoelectronic applications. Progress in scalable fabrication methods for TMDCs like metal-organic chemical vapor deposition (MOCVD) and the ambition to exploit specific material properties, such as mechanical flexibility or high transparency, highlight the importance of suitable device concepts and processing techniques. In this work, we make use of the high transparency of TMDC monolayers to fabricate transparent light-emitting devices (LEDs). MOCVD-grown WS2is embedded as the active material in a scalable vertical device architecture and combined with a silver nanowire (AgNW) network as a transparent top electrode. The AgNW network was deposited onto the device by a spin-coating process, providing contacts with a sheet resistance below 10 Ω sq-1and a transmittance of nearly 80%. As an electron transport layer we employed a continuous 40 nm thick zinc oxide (ZnO) layer, which was grown by atmospheric pressure spatial atomic layer deposition (AP-SALD), a precise tool for scalable deposition of oxides with defined thickness. With this, LEDs with an average transmittance over 60% in the visible spectral range, emissive areas of several mm2and a turn-on voltage of around 3 V are obtained.

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.

Electrochemical removal of anodic aluminium oxide templates for the production of phase-pure cuprous oxide nanorods for antimicrobial surfaces.

Antimicrobial surfaces are ones that incapacitate or kill pathogens landing on them, which could allow for self-sanitising surfaces for hospitals or implants, ensuring healthier stays and procedures. Cuprous compounds such as Cu2O are especially effective at incapacitating both viruses and bacteria, and nanorod arrays have been shown to prevent the adhesion of pathogens and mechanically deform bacteria to the point that their cell walls rupture. A Cu2O nanorod array should therefore allow for the exploitation of both of these effects. In the present work, an electrochemical method is introduced, where Cu2O nanorods formed in a substrate-supported anodic aluminium oxide (AAO) template are held at a stable electrochemical potential throughout the removal of the AAO template. This avoids the partial reduction of the nanorods from Cu2O to Cu that was observed during chemical removal of the template, which was attributed to the presence of residual aluminium from the template fabrication process that reacts with the etchant and lowers the electrochemical potential of the nanorods to a value that favours reduction. Using the electrochemical removal method, the reliable production of phase-pure, free-standing, crystalline Cu2O nanorod arrays on ITO/glass substrates is demonstrated. This simple method is compatible with nanorod arrays of any size.

Laser-Directed Assembly of Nanorods of 2D Materials.

Herein, the previously unrealized ability to grow nanorods and nanotubes of 2D materials using femtosecond laser irradiation is demonstrated. In as short as 20 min, nanorods of tungsten disulfide, molybdenum disulfide, graphene, and boron nitride are grown in solutions. The technique fragments nanoparticles of the 2D materials from bulk flakes and leverages molecular scale alignment by nonresonant intense laser pulses to direct their assembly into nanorods up to several micrometers in length. The laser treatment process is found to induce phase transformations in some of the materials, and also results in the modification of the nanorods with functional groups from the solvent atoms. Notably, the WS2 nanoparticles, which are ablated from semiconducting 2H WS2 crystallographic phase flakes, reassemble into nanorods consisting of the 1T metallic phase. Due to this transition, and the 1D nature of the fabricated nanorods, the WS2 nanorods display substantial improvements in electrical conductivity and optical transparency when employed as transparent conductors.

Resonant energy transfer of triplet excitons from pentacene to PbSe nanocrystals.

The efficient transfer of energy between organic and inorganic semiconductors is a widely sought after property, but has so far been limited to the transfer of spin-singlet excitons. Here we report efficient resonant-energy transfer of molecular spin-triplet excitons from organic semiconductors to inorganic semiconductors. We use ultrafast optical absorption spectroscopy to track the dynamics of triplets, generated in pentacene through singlet exciton fission, at the interface with lead selenide (PbSe) nanocrystals. We show that triplets transfer to PbSe rapidly (<1 ps) and efficiently, with 1.9 triplets transferred for every photon absorbed in pentacene, but only when the bandgap of the nanocrystals is close to resonance (±0.2 eV) with the triplet energy. Following triplet transfer, the excitation can undergo either charge separation, allowing photovoltaic operation, or radiative recombination in the nanocrystal, enabling luminescent harvesting of triplet exciton energy in light-emitting structures.

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.

Polymer crystallization as a tool to pattern hybrid nanostructures: growth of 12 nm ZnO arrays in poly(3-hexylthiophene).

Well-ordered hybrid materials with a 10 nm length scale are highly desired. We make use of the natural length scale (typically 10-15 nm) of the alternating crystalline and amorphous layers that are generally found in semicrystalline polymers to direct the growth of a semiconducting metal oxide. This approach is exemplified with the growth of ZnO within a carboxylic acid end-functionalized poly(3-hexylthiophene) (P3HT-COOH). The metal-oxide precursor vapors diffuse into the amorphous parts of the semicrystalline polymer so that sheets of ZnO up to 0.5 µm in size can be grown. This P3HT-ZnO nanostructure further functions as a donor-acceptor photovoltaic system, with length scales appropriate for charge photogeneration.

Zinc Aluminum Oxide Encapsulation Layers for Perovskite Solar Cells Deposited Using Spatial Atomic Layer Deposition.

An atmospheric-pressure spatial atomic layer deposition system is used to rapidly deposit 60 nm zinc-aluminum oxide (Zn-AlOx ) thin-film-encapsulation layers directly on perovskite solar cells at 130 °C without damaging the temperature-sensitive perovskite and organic materials. Varying the Zn/Al ratio has a significant impact on the structural properties of the films and their moisture barrier performance. The Zn-AlOx films have higher refractive indexes, lower concentrations of OH─ groups, and lower water-vapor transmission rates (WVTR) than AlOx films without zinc. However, as the Zn/Al ratio increases beyond 0.21, excess Zn atoms segregate, leading to an increase in the number of available hydroxyl groups on the surface of the deposited film and a slight increase in the WVTR. The stability of the p-i-n formamidinium methylammonium lead iodide solar cells under standard ISOS-D-3 testing conditions (65 °C and 85% relative humidity) is significantly enhanced by the thin encapsulation layers. The layers with a Zn/Al ratio of 0.21 result in a seven-fold increase the time required for the cells to degrade to 80% of their original efficiency.

Defect-Rich MoSe2 2H/1T Hybrid Nanoparticles Prepared from Femtosecond Laser Ablation in Liquid and Their Enhanced Photothermal Conversion Efficiencies.

MoSe2 2H/1T hybrid nanoparticles are prepared by femtosecond laser ablation of MoSe2 powder in isopropyl alcohol with different laser powers and ablation times, and their formation mechanisms and photothermal conversion efficiencies (PTCEs) are studied. Two types of spherical nanoparticles are observed. The first type is onion-structured nanoparticles that are formed by nucleation on the surfaces of melted droplets followed by inward growth of {002} planes of MoSe2 . The second type is polycrystalline nanoparticles, formed by coalescence of crystalline nanoclusters fragmented from the powder during the laser ablation. The nanoparticle size in all samples shows a bimodal distribution, corresponding to different fragmentation mechanisms. The 2H-to-1T phase transition in the nanoparticles is likely caused by electron doping from the laser-induced plasma. The PTCEs of the nanoparticles increase with laser power and ablation time; the highest PTCE is around 38%. After examining the bandgaps and the Urbach energies of the nanoparticles, it is found that the high PTCEs are primarily attributed to defects and structural disorder in the laser-synthesized nanoparticles, which allow absorption of photons with energies smaller than the bandgap energy and facilitate non-radiative recombination of photoexcited carriers.

Intelligent matter endows reconfigurable temperature and humidity sensations for in-sensor computing.

Data-centric tactics with in-sensor computing go beyond the conventional computing-centric tactic that is suffering from processing latency and excessive energy consumption. The multifunctional intelligent matter with dynamic smart responses to environmental variations paves the way to implement data-centric tactics with high computing efficiency. However, intelligent matter with humidity and temperature sensitivity has not been reported. In this work, a design is demonstrated based on a single memristive device to achieve reconfigurable temperature and humidity sensations. Opposite temperature sensations at the low resistance state (LRS) and high resistance state (HRS) were observed for low-level sensory data processing. Integrated devices mimicking intelligent electronic skin (e-skin) can work in three modes to adapt to different scenarios. Additionally, the device acts as a humidity-sensory artificial synapse that can implement high-level cognitive in-sensor computing. The intelligent matter with reconfigurable temperature and humidity sensations is promising for energy-efficient artificial intelligence (AI) systems.

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.

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.

Effectiveness of antiviral metal and metal oxide thin-film coatings against human coronavirus 229E.

Virucidal thin-film coatings have the potential to inactivate pathogens on surfaces, preventing or slowing their spread. Six potential nanoscale antiviral coatings, Cu, Cu2O, Ag, ZnO, zinc tin oxide (ZTO), and TiO2, are deposited on glass, and their ability to inactivate the HCoV-229E human coronavirus is assessed using two methods. In one method, droplets containing HCoV-229E are deposited on thin-film coatings and then collected after various stages of desiccation. In the second method, the thin-film coatings are soaked in the virus supernatant for 24 h. The Cu and Cu2O coatings demonstrate clear virucidal behavior, and it is shown that controlled delamination and dissolution of the coating can enhance the virucidal effect. Cu is found to produce a faster and stronger virucidal effect than Cu2O in the droplet tests (3 log reduction in the viral titer after 1 h of exposure), which is attributed, in part, to the differences in film adhesion that result in delamination of the Cu film from the glass and accelerated dissolution in the droplet. Despite Ag, ZnO, and TiO2 being frequently cited antimicrobial materials, exposure to the Ag, ZnO, ZTO, and TiO2 coatings results in no discernible change to the infectivity of the coronavirus under the conditions tested. Thin-film Cu coatings are also applied to the polypropylene fabrics of N95 respirators, and droplet tests are performed. The Cu fabric coating reduces the infectivity of the virus; it results in a 1 order-of-magnitude reduction in the viral titer within 15 min with a 2 order-of-magnitude reduction after 1 h.

In-situ spatial and temporal electrical characterization of ZnO thin films deposited by atmospheric pressure chemical vapour deposition on flexible polymer substrates.

A technique is presented for collecting data on both the spatial and temporal variations in the electrical properties of a film as it is deposited on a flexible substrate. A flexible printed circuit board substrate with parallel electrodes distributed across its surface was designed. Zinc oxide films were then deposited on the flexible substrate at different temperatures via atmospheric pressure chemical vapour deposition (AP-CVD) using a spatial atomic layer deposition system. AP-CVD is a promising high-throughput thin film deposition technique with applications in flexible electronics. Collecting data on the film properties in-situ allows us to directly observe how deposition conditions affect the evolution of those properties in real-time. The spatial uniformity of the growing film was monitored, and the various stages of film nucleation and growth on the polymer substrate were observed. The measured resistance of the films was observed to be very high until a critical amount of material has been deposited, consistent with Volmer-Weber growth. Furthermore, monitoring the film resistance during post-deposition cooling enabled immediate identification of metallic or semiconducting behaviour within the conductive ZnO films. This technique allows for a more complete understanding of metal chalcogen film growth and properties, and the high volume of data generated will be useful for future implementations of machine-learning directed materials science.

Oxygen vacancy migration/diffusion induced synaptic plasticity in a single titanate nanobelt.

Neuromorphic computational systems that emulate biological synapses in the human brain are fundamental in the development of artificial intelligence protocols beyond the standard von Neumann architecture. Such systems require new types of building blocks, such as memristors that access a quasi-continuous and wide range of conductive states, which is still an obstacle for the realization of high-efficiency and large-capacity learning in neuromorphoric simulation. Here, we introduce hydrogen and sodium titanate nanobelts, the intermediate products of hydrothermal synthesis of TiO2 nanobelts, to emulate the synaptic behavior. Devices incorporating a single titanate nanobelt demonstrate robust and reliable synaptic functions, including excitatory postsynaptic current, paired pulse facilitation, short term plasticity, potentiation and depression, as well as learning-forgetting behavior. In particular, the gradual modulation of conductive states in the single nanobelt device can be achieved by a large number of identical pulses. The mechanism for synaptic functionality of the titanate nanobelt device is attributed to the competition between an electric field driven migration of oxygen vacancies and a thermally induced spontaneous diffusion. These results provide insight into the potential use of titanate nanobelts in synaptic applications requiring continuously addressable states coupled with high processing efficiency.

Resistive Switching Memory of TiO2 Nanowire Networks Grown on Ti Foil by a Single Hydrothermal Method.

The resistive switching characteristics of TiO2 nanowire networks directly grown on Ti foil by a single-step hydrothermal technique are discussed in this paper. The Ti foil serves as the supply of Ti atoms for growth of the TiO2 nanowires, making the preparation straightforward. It also acts as a bottom electrode for the device. A top Al electrode was fabricated by e-beam evaporation process. The Al/TiO2 nanowire networks/Ti device fabricated in this way displayed a highly repeatable and electroforming-free bipolar resistive behavior with retention for more than 104 s and an OFF/ON ratio of approximately 70. The switching mechanism of this Al/TiO2 nanowire networks/Ti device is suggested to arise from the migration of oxygen vacancies under applied electric field. This provides a facile way to obtain metal oxide nanowire-based ReRAM device in the future.

Reliable and Low-Power Multilevel Resistive Switching in TiO2 Nanorod Arrays Structured with a TiOx Seed Layer.

The electrical performance of TiO2 nanorod array (NRA)-based resistive switching memory devices is examined in this paper. The formation of a seed layer on the fluorine-doped tin oxide (FTO) glass substrate after treatment in TiCl4 solution, before the growth of TiO2 NRAs on the FTO substrate via a hydrothermal process, is shown to significantly improve the resistive switching performance of the resulting TiO2 NRA-based device. As fabricated, the Al/TiO2 NRA/TiOx layer/FTO device displayed electroforming-free bipolar resistive switching behavior while maintaining a stable ON/OFF ratio for more than 500 direct sweeping cycles over a retention period of 3 × 104 s. Meanwhile, the programming current as low as ∼10-8 A and 10-10 A for low resistance state and high resistance state respectively makes the fabricated devices suitable for low-power memristor applications. The TiOx precursor seed layer not only promotes the uniform and preferred growth of TiO2 nanorods on the FTO substrate but also functions as an additional source layer of trap centers due to its oxygen-deficient composition. Our data suggest that the primary conduction mechanism in these devices arises from trap-mediated space-charge-limited current (SCLC). Multilevel memory performance in this new device is achieved by varying the SET voltage. The origin of this effect is also discussed.

Efficient Triplet Exciton Fusion in Molecularly Doped Polymer Light-Emitting Diodes.

Solution-processed polymer organic light-emitting diodes (OLEDs) doped with triplet-triplet annihilation (TTA)-upconversion molecules, including 9,10-diphenylanthracene, perylene, rubrene and TIPS-pentacene, are reported. The fraction of triplet-generated electroluminescence approaches the theoretical limit. Record-high efficiencies in solution-processed OLEDs based on these materials are achieved. Unprecedented solid-state TTA-upconversion quantum yield of 23% (TTA-upconversion reaction efficiency of 70%) at electrical excitation well below one-sun equivalent is observed.

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO.

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn1-xMgxO thin films onto p-type thermally oxidized Cu2O substrates outside vacuum at low temperature. The performance of photovoltaic devices featuring atmospherically fabricated ZnO/Cu2O heterojunction was dependent on the conditions of AP-SALD film deposition, namely, the substrate temperature and deposition time, as well as on the Cu2O substrate exposure to oxidizing agents prior to and during the ZnO deposition. Superficial Cu2O to CuO oxidation was identified as a limiting factor to heterojunction quality due to recombination at the ZnO/Cu2O interface. Optimization of AP-SALD conditions as well as keeping Cu2O away from air and moisture in order to minimize Cu2O surface oxidation led to improved device performance. A three-fold increase in the open-circuit voltage (up to 0.65 V) and a two-fold increase in the short-circuit current density produced solar cells with a record 2.2% power conversion efficiency (PCE). This PCE is the highest reported for a Zn1-xMgxO/Cu2O heterojunction formed outside vacuum, which highlights atmospheric pressure spatial ALD as a promising technique for inexpensive and scalable fabrication of Cu2O-based photovoltaics.