Multifunctional Three-in-One Sensor on t-ZnO for Ultraviolet and VOC Sensing for Bioengineering Applications.

Zinc oxide (ZnO) is considered to be one of the most explored and reliable sensing materials for UV detection due to its excellent properties, like a wide band gap and high exciton energy. Our current study on a photodetector based on tetrapodal ZnO (t-ZnO) reported an extremely high UV response of ~9200 for 394 nm UV illumination at 25 °C. The t-ZnO network structure and morphology were investigated using XRD and SEM. The sensor showed a UV/visible ratio of ~12 at 25 °C for 394 nm UV illumination and 443 nm visible illumination. By increasing the temperature, monotonic decreases in response and recovery time were observed. By increasing the bias voltage, the response time was found to decrease while the recovery time was increased. The maximum responsivity shifted to higher wavelengths from 394 nm to 400 nm by increasing the operating temperature from 25 °C to 100 °C. The t-ZnO networks exhibited gas-sensing performances at temperatures above 250 °C, and a maximum response of ~1.35 was recorded at 350 °C with a good repeatability and fast recovery in 16 s for 100 ppm of n-butanol vapor. This study demonstrated that t-ZnO networks are good biosensors that can be used for diverse biomedical applications like the sensing of VOCs (volatile organic compounds) and ultraviolet detection under a wide range of temperatures, and may find new possibilities in biosensing applications.

Composition and Surface Optical Properties of GaSe:Eu Crystals before and after Heat Treatment.

This work studies the technological preparation conditions, morphology, structural characteristics and elemental composition, and optical and photoluminescent properties of GaSe single crystals and Eu-doped ß-Ga2O3 nanoformations on ε-GaSe:Eu single crystal substrate, obtained by heat treatment at 750-900 °C, with a duration from 30 min to 12 h, in water vapor-enriched atmosphere, of GaSe plates doped with 0.02-3.00 at. % Eu. The defects on the (0001) surface of GaSe:Eu plates serve as nucleation centers of ß-Ga2O3:Eu crystallites. For 0.02 at. % Eu doping, the fundamental absorption edge of GaSe:Eu crystals at room temperature is formed by n = 1 direct excitons, while at 3.00 at. % doping, Eu completely shields the electron-hole bonds. The band gap of nanostructured ß-Ga2O3:Eu layer, determined from diffuse reflectance spectra, depends on the dopant concentration and ranges from 4.64 eV to 4.87 eV, for 3.00 and 0.05 at. % doping, respectively. At 0.02 at. % doping level, the PL spectrum of ε-GaSe:Eu single crystals consists of the n = 1 exciton band, together with the impurity band with a maximum intensity at 800 nm. Fabry-Perrot cavities with a width of 9.3 µm are formed in these single crystals, which determine the interference structure of the impurity PL band. At 1.00-3.00 at. % Eu concentrations, the PL spectra of GaSe:Eu single crystals and ß-Ga2O3:Eu nanowire/nanolamellae layers are determined by electronic transitions of Eu2+ and Eu3+ ions.

Surface Conversion of ZnO Tetrapods Produces Pinhole-Free ZIF-8 Layers for Selective and Sensitive H2 Sensing Even in Pure Methane.

As the necessary transition to a supply of renewable energy moves forward rapidly, hydrogen (H2) becomes increasingly important as a green chemical energy carrier. The manifold applications associated with the use of hydrogen in the energy sector require sensor materials that can efficiently detect H2 in small quantities and in gas mixtures. As a possible candidate, we here present a metal-organic framework (MOF, namely ZIF-8) functionalized metal-oxide gas sensor (MOS, namely ZnO). The gas sensor is based on single-crystalline tetrapodal ZnO (t-ZnO) microparticles, which are coated with a thin layer of ZIF-8 ([Zn(C4H5N2)2]) by a ZnO conversion reaction to obtain t-ZnO@ZIF-8 (core@shell) composites. The vapor-phase synthesis enables ZIF-8 thickness control as shown by powder X-ray diffraction, thermogravimetric analysis, and N2 sorption measurements. Gas-sensing measurements of a single microrod of t-ZnO@ZIF-8 composite demonstrate the synergistic benefits of both MOS sensors and MOFs, resulting in an outstanding high selectivity, sensitivity (S ≅ 546), and response times (1-2 s) to 100 ppm H2 in the air at a low operation temperature of 100 °C. Under these conditions, no response to acetone, n-butanol, methane, ethanol, ammonia, 2-propanol, and carbon dioxide was observed. Thereby, the sensor is able to reliably detect H2 in mixtures with air and even methane, with the latter being highly important for determining the H2 dilution level in natural gas pipelines, which is of great importance to the energy sector.

Preparation, Chemical Composition, and Optical Properties of (ß-Ga2O3 Composite Thin Films)/(GaSxSe1-x Lamellar Solid Solutions) Nanostructures.

GaSxSe1-x solid solutions are layered semiconductors with a band gap between 2.0 and 2.6 eV. Their single crystals are formed by planar packings of S/Se-Ga-Ga-S/Se type, with weak polarization bonds between them, which allows obtaining, by splitting, plan-parallel lamellae with atomically smooth surfaces. By heat treatment in a normal or water vapor-enriched atmosphere, their plates are covered with a layer consisting of ß-Ga2O3 nanowires/nanoribbons. In this work, the elemental and chemical composition, surface morphology, as well as optical, photoluminescent, and photoelectric properties of ß-Ga2O3 layer formed on GaSxSe1-x (0 ≤ x ≤ 1) solid solutions (as substrate) are studied. The correlation is made between the composition (x) of the primary material, technological preparation conditions of the oxide-semiconducting layer, and the optical, photoelectric, and photoluminescent properties of ß-Ga2O3 (nanosized layers)/GaSxSe1-x structures. From the analysis of the fundamental absorption edge, photoluminescence, and photoconductivity, the character of the optical transitions and the optical band gap in the range of 4.5-4.8 eV were determined, as well as the mechanisms behind blue-green photoluminescence and photoconductivity in the fundamental absorption band region. The photoluminescence bands in the blue-green region are characteristic of ß-Ga2O3 nanowires/nanolamellae structures. The photoconductivity of ß-Ga2O3 structures on GaSxSe1-x solid solution substrate is determined by their strong fundamental absorption. As synthesized structures hold promise for potential applications in UV receivers, UV-C sources, gas sensors, as well as photocatalytic decomposition of water and organic pollutants.

Two-in-One Sensor Based on PV4D4-Coated TiO2 Films for Food Spoilage Detection and as a Breath Marker for Several Diseases.

Certain molecules act as biomarkers in exhaled breath or outgassing vapors of biological systems. Specifically, ammonia (NH3) can serve as a tracer for food spoilage as well as a breath marker for several diseases. H2 gas in the exhaled breath can be associated with gastric disorders. This initiates an increasing demand for small and reliable devices with high sensitivity capable of detecting such molecules. Metal-oxide gas sensors present an excellent tradeoff, e.g., compared to expensive and large gas chromatographs for this purpose. However, selective identification of NH3 at the parts-per-million (ppm) level as well as detection of multiple gases in gas mixtures with one sensor remain a challenge. In this work, a new two-in-one sensor for NH3 and H2 detection is presented, which provides stable, precise, and very selective properties for the tracking of these vapors at low concentrations. The fabricated 15 nm TiO2 gas sensors, which were annealed at 610 °C, formed two crystal phases, namely anatase and rutile, and afterwards were covered with a thin 25 nm PV4D4 polymer nanolayer via initiated chemical vapor deposition (iCVD) and showed precise NH3 response at room temperature and exclusive H2 detection at elevated operating temperatures. This enables new possibilities in application fields such as biomedical diagnosis, biosensors, and the development of non-invasive technology.

Development of 2-in-1 Sensors for the Safety Assessment of Lithium-Ion Batteries via Early Detection of Vapors Produced by Electrolyte Solvents.

Batteries play a critical role in achieving zero-emission goals and in the transition toward a more circular economy. Ensuring battery safety is a top priority for manufacturers and consumers alike, and hence is an active topic of research. Metal-oxide nanostructures have unique properties that make them highly promising for gas sensing in battery safety applications. In this study, we investigate the gas-sensing capabilities of semiconducting metal oxides for detecting vapors produced by common battery components, such as solvents, salts, or their degassing products. Our main objective is to develop sensors capable of early detection of common vapors produced by malfunctioning batteries to prevent explosions and further safety hazards. Typical electrolyte components and degassing products for the Li-ion, Li-S, or solid-state batteries that were investigated in this study include 1,3-dioxololane (C3H6O2─DOL), 1,2-dimethoxyethane (C4H10O2─DME), ethylene carbonate (C3H4O3─EC), dimethyl carbonate (C4H10O2─DMC), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3) salts in a mixture of DOL and DME, lithium hexafluorophosphate (LiPF6), nitrogen dioxide (NO2), and phosphorous pentafluoride (PF5). Our sensing platform was based on ternary and binary heterostructures consisting of TiO2(111)/CuO(1̅11)/Cu2O(111) and CuO(1̅11)/Cu2O(111), respectively, with various CuO layer thicknesses (10, 30, and 50 nm). We have analyzed these structures using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), micro-Raman spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy. We found that the sensors reliably detected DME C4H10O2 vapors up to a concentration of 1000 ppm with a gas response of 136%, and concentrations as low as 1, 5, and 10 ppm with response values of approximately 7, 23, and 30%, respectively. Our devices can serve as 2-in-1 sensors, functioning as a temperature sensor at low operating temperatures and as a gas sensor at temperatures above 200 °C. Density functional theory calculations were also employed to study the adsorption of the vapors produced by battery solvents or their degassing products, as well as water, to investigate the impact of humidity. PF5 and C4H10O2 showed the most exothermic molecular interactions, which are consistent with our gas response investigations. Our results indicate that humidity does not impact the performance of the sensors, which is crucial for the early detection of thermal runaway under harsh conditions in Li-ion batteries. We show that our semiconducting metal-oxide sensors can detect the vapors produced by battery solvents and degassing products with high accuracy and can serve as high-performance battery safety sensors to prevent explosions in malfunctioning Li-ion batteries. Despite the fact that the sensors work independently of the type of battery, the work presented here is of particular interest for the monitoring of solid-state batteries, since DOL is a solvent typically used in this type of batteries.

Tuning the Selectivity of Metal Oxide Gas Sensors with Vapor Phase Deposited Ultrathin Polymer Thin Films.

Metal oxide gas sensors are of great interest for applications ranging from lambda sensors to early hazard detection in explosive media and leakage detection due to their superior properties with regard to sensitivity and lifetime, as well as their low cost and portability. However, the influence of ambient gases on the gas response, energy consumption and selectivity still needs to be improved and they are thus the subject of intensive research. In this work, a simple approach is presented to modify and increase the selectivity of gas sensing structures with an ultrathin polymer thin film. The different gas sensing surfaces, CuO, Al2O3/CuO and TiO2 are coated with a conformal < 30 nm Poly(1,3,5,7-tetramethyl-tetravinyl cyclotetrasiloxane) (PV4D4) thin film via solvent-free initiated chemical vapor deposition (iCVD). The obtained structures demonstrate a change in selectivity from ethanol vapor to 2-propanol vapor and an increase in selectivity compared to other vapors of volatile organic compounds. In the case of TiO2 structures coated with a PV4D4 thin film, the increase in selectivity to 2-propanol vapors is observed even at relatively low operating temperatures, starting from >200 °C. The present study demonstrates possibilities for improving the properties of metal oxide gas sensors, which is very important in applications in fields such as medicine, security and food safety.

Nanosensors Based on a Single ZnO:Eu Nanowire for Hydrogen Gas Sensing.

Fast detection of hydrogen gas leakage or its release in different environments, especially in large electric vehicle batteries, is a major challenge for sensing applications. In this study, the morphological, structural, chemical, optical, and electronic characterizations of ZnO:Eu nanowire arrays are reported and discussed in detail. In particular, the influence of different Eu concentrations during electrochemical deposition was investigated together with the sensing properties and mechanism. Surprisingly, by using only 10 µM Eu ions during deposition, the value of the gas response increased by a factor of nearly 130 compared to an undoped ZnO nanowire and we found an H2 gas response of ∼7860 for a single ZnO:Eu nanowire device. Further, the synthesized nanowire sensors were tested with ultraviolet (UV) light and a range of test gases, showing a UV responsiveness of ∼12.8 and a good selectivity to 100 ppm H2 gas. A dual-mode nanosensor is shown to detect UV/H2 gas simultaneously for selective detection of H2 during UV irradiation and its effect on the sensing mechanism. The nanowire sensing approach here demonstrates the feasibility of using such small devices to detect hydrogen leaks in harsh, small-scale environments, for example, stacked battery packs in mobile applications. In addition, the results obtained are supported through density functional theory-based simulations, which highlight the importance of rare earth nanoparticles on the oxide surface for improved sensitivity and selectivity of gas sensors, even at room temperature, thereby allowing, for instance, lower power consumption and denser deployment.

Al2O3/ZnO Heterostructure-Based Sensors for Volatile Organic Compounds in Safety Applications.

Monitoring volatile organic compounds (VOCs) in harsh environments, especially for safety applications, is a growing field that requires specialized sensor structures. In this work, we demonstrate the sensing properties toward the most common VOCs of columnar Al2O3/ZnO heterolayer-based sensors. We have also developed an approach to tune the sensor selectivity by changing the thickness of the exposed amorphous Al2O3 layer from 5 to 18 nm. Columnar ZnO films are prepared by a chemical solution method, where the exposed surface is decorated with an Al2O3 nanolayer via thermal atomic layer deposition at 75 °C. We have investigated the structure and morphology as well as the vibrational, chemical, electronic, and sensor properties of the Al2O3/ZnO heterostructures. Transmission electron microscopy (TEM) studies show that the upper layers consist of amorphous Al2O3 films. The heterostructures showed selectivity to 2-propanol vapors only within the range of 12-15 nm thicknesses of Al2O3, with the highest response value of ∼2000% reported for a thickness of 15 nm at the optimal working temperature of 350 °C. Density functional theory (DFT) calculations of the Al2O3/ZnO(1010) interface and its interaction with 2-propanol (2-C3H7OH), n-butanol (n-C4H9OH), ethanol (C2H5OH), acetone (CH3COCH3), hydrogen (H2), and ammonia (NH3) show that the molecular affinity for the Al2O3/ZnO(1010) interface decreases from 2-propanol (2-C3H7OH) ≈ n-butanol (n-C4H9OH) > ethanol (C2H5OH) > acetone (CH3COCH3) > hydrogen (H2), which is consistent with our gas response experiments for the VOCs. Charge transfers between the surface and the adsorbates, and local densities of states of the interacting atoms, support the calculated strength of the molecular preferences. Our findings are highly important for the development of 2-propanol sensors and to our understanding of the effect of the heterojunction and the thickness of the top nanolayer on the gas response, which thus far have not been reported in the literature.

TiO2/Cu2O/CuO Multi-Nanolayers as Sensors for H2 and Volatile Organic Compounds: An Experimental and Theoretical Investigation.

TiO2/Cu2O/CuO multi-nanolayers highly sensitive toward volatile organic compounds (VOCs) and H2 have been grown in various thicknesses by a cost-effective and reproducible combined spray-sputtering-annealing approach. The ultrathin TiO2 films were deposited by spray pyrolysis on top of sputtered-annealed Cu2O/CuO nanolayers to enhance their gas sensing performance and improve their protection against corrosion at high operating temperatures. The prepared heterostructures were investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), and ultraviolet visible (UV-vis) and micro-Raman spectroscopy. The gas sensing properties were measured at several operating temperatures, where the nanolayered sensors with oxide thicknesses between 20 and 30 nm (Cu2O/CuO nanolayers) exhibited a high response and an excellent selectivity to ethanol vapor after thermal annealing the samples at 420 °C. The results obtained at an operating temperature of 350 °C demonstrate that the CuO/Cu2O nanolayers with thicknesses between 20 and 30 nm are sensitive mainly to ethanol vapor, with a response of ∼150. The response changes from ethanol vapors to hydrogen gas as the thickness of the CuO/Cu2O nanolayers changes from 50 to 20 nm. Density functional theory-based calculations were carried out for the geometries of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) heterostructures and their sensing mechanism toward alcohols of different chain lengths and molecular hydrogen. The reconstructed hexagonal Cu2O(111) surface and the reconstructed monoclinic CuO(1̅11) and TiO2(111) facets, all of which terminate in an O layer, lead to the lowest surface energies for each isolated material. We studied the formation of the binary and ternary heteroepitaxial interfaces for the surface planes with the best-matching lattices. Despite the impact of the Cu2O(111) substrate in lowering the atomic charges of the CuO(1̅11) adlayer in the binary sensor, we found that it is the different surface structures of the CuO(1̅11)/Cu2O(111) and TiO2(111)/CuO(1̅11)/Cu2O(111) devices that are fundamental in driving the change in the sensitivity response observed experimentally. The experimental data, supported by the computational results, are important in understanding the use of the multi-nanolayered films tested in this work as reliable, accurate, and selective sensor structures for the tracking of gases at low concentrations.

Comparison of Thermal Annealing versus Hydrothermal Treatment Effects on the Detection Performances of ZnO Nanowires.

A comparative investigation of the post-electroplating treatment influence on the gas detecting performances of single ZnO nanorod/nanowire (NR/NW), as grown by electrochemical deposition (ECD) and integrated into nanosensor devices, is presented. In this work, hydrothermal treatment (HT) in a H2O steam and conventional thermal annealing (CTA) in a furnace at 150 °C in ambient were used as post-growth treatments to improve the material properties. Herein, the morphological, optical, chemical, structural, vibrational, and gas sensing performances of the as-electrodeposited and treated specimens are investigated and presented in detail. By varying the growth temperature and type of post-growth treatment, the morphology is maintained, whereas the optical and structural properties show increased sample crystallization. It is shown that HT in H2O vapors affects the optical and vibrational properties of the material. After investigation of nanodevices based on single ZnO NR/NWs, it was observed that higher temperature during the synthesis results in a higher gas response to H2 gas within the investigated operating temperature range from 25 to 150 °C. CTA and HT or autoclave treatment showed the capability of a further increase in gas response of the prepared sensors by a factor of ∼8. Density functional theory calculations reveal structural and electronic band changes in ZnO surfaces as a result of strong interaction with H2 gas molecules. Our results demonstrate that high-performance devices can be obtained with high-crystallinity NWs/NRs after HT. The obtained devices could be the key element for flexible nanoelectronics and wearable electronics and have attracted great interest due to their unique specifications.

Single CuO/Cu2O/Cu Microwire Covered by a Nanowire Network as a Gas Sensor for the Detection of Battery Hazards.

In this study, a strategy to prepare CuO/Cu2O/Cu microwires that are fully covered by a nanowire (NW) network using a simple thermal-oxidation process is developed. The CuO/Cu2O/Cu microwires are fixed on Au/Cr pads with Cu microparticles. After thermal annealing at 425 °C, these CuO/Cu2O/Cu microwires are used as room-temperature 2-propanol sensors. These sensors show different dominating gas responses with operating temperatures, e.g., higher sensitivity to ethanol at 175 °C, higher sensitivity to 2-propanol at room temperature and 225 °C, and higher sensitivity to hydrogen gas at ∼300 °C. In this context, we propose the sensing mechanism of this three-in-one sensor based on CuO/Cu2O/Cu. X-ray diffraction (XRD) studies reveal that the annealing time during oxidation affects the chemical appearance of the sensor, while the intensity of reflections proves that for samples oxidized at 425 °C for 1 h the dominating phase is Cu2O, whereas upon further increasing the annealing duration up to 5 h, the CuO phase becomes dominant. The crystal structures of the Cu2O-shell/Cu-core and the CuO NW networks on the surface were confirmed with a transmission electron microscope (TEM), high-resolution TEM (HRTEM), and selected area electron diffraction (SAED), where (HR)TEM micrographs reveal the monoclinic CuO phase. Density functional theory (DFT) calculations bring valuable inputs to the interactions of the different gas molecules with the most stable top surface of CuO, revealing strong binding, electronic band-gap changes, and charge transfer due to the gas molecule interactions with the top surface. This research shows the importance of the nonplanar CuO/Cu2O layered heterostructure as a bright nanomaterial for the detection of various gases, controlled by the working temperature, and the insight presented here will be of significant value in the fabrication of new p-type sensing devices through simple nanotechnology.

Low-Temperature Solution Synthesis of Au-Modified ZnO Nanowires for Highly Efficient Hydrogen Nanosensors.

In this research, the low-temperature single-step electrochemical deposition of arrayed ZnO nanowires (NWs) decorated by Au nanoparticles (NPs) with diameters ranging between 10 and 100 nm is successfully demonstrated for the first time. The AuNPs and ZnO NWs were grown simultaneously in the same growth solution in consideration of the HAuCl4 concentration. Optical, structural, and chemical characterizations were analyzed in detail, proving high crystallinity of the NWs as well as the distribution of Au NPs on the surface of zinc oxide NWs demonstrated by transmission electron microscopy. Individual Au NPs-functionalized ZnO NWs (Au-NP/ZnO-NWs) were incorporated into sensor nanodevices using an focused ion bean/scanning electron microscopy (FIB/SEM) scientific instrument. The gas-sensing investigations demonstrated excellent selectivity to hydrogen gas at room temperature (RT) with a gas response, Igas/Iair, as high as 7.5-100 ppm for Au-NP/ZnO-NWs, possessing a AuNP surface coverage of ∼6.4%. The concentration of HAuCl4 in the electrochemical solution was observed to have no significant impact on the gas-sensing parameters in our experiments. This highlights the significant influence of the total Au/ZnO interfacial area establishing Schottky contacts for the achievement of high performances. The most significant performance of H2 response was observed for gas concentrations higher than 500 ppm of H2 in the environment, which was attributed to the surface metallization of ZnO NWs during exposure to hydrogen. For this case, an ultrahigh response of about 32.9 and 47 to 1000 and 5000 ppm of H2 was obtained, respectively. Spin-polarized periodic density functional theory calculations were realized on Au/ZnO bulk and surface-functionalized models, validating the experimental hypothesis. The combination of H2 gas detection at RT, ultralow power consumption, and reduced dimensions makes these micro-nanodevices excellent candidates for hydrogen gas leakage detection, including hydrogen gas monitoring (less than 1 ppm).

Tuning ZnO Sensors Reactivity toward Volatile Organic Compounds via Ag Doping and Nanoparticle Functionalization.

Nanomaterials for highly selective and sensitive sensors toward specific gas molecules of volatile organic compounds (VOCs) are most important in developing new-generation of detector devices, for example, for biomarkers of diseases as well as for continuous air quality monitoring. Here, we present an innovative preparation approach for engineering sensors, which allow for full control of the dopant concentrations and the nanoparticles functionalization of columnar material surfaces. The main outcome of this powerful design concept lies in fine-tuning the reactivity of the sensor surfaces toward the VOCs of interest. First, nanocolumnar and well-distributed Ag-doped zinc oxide (ZnO:Ag) thin films are synthesized from chemical solution, and, at a second stage, noble nanoparticles of the required size are deposited using a gas aggregation source, ensuring that no percolating paths are formed between them. Typical samples that were investigated are Ag-doped and Ag nanoparticle-functionalized ZnO:Ag nanocolumnar films. The highest responses to VOCs, in particular to (CH3)2CHOH, were obtained at a low operating temperature (250 °C) for the samples synergistically enhanced with dopants and nanoparticles simultaneously. In addition, the response times, particularly the recovery times, are greatly reduced for the fully modified nanocolumnar thin films for a wide range of operating temperatures. The adsorption of propanol, acetone, methane, and hydrogen at various surface sites of the Ag-doped Ag8/ZnO(0001) surface has been examined with the density functional theory (DFT) calculations to understand the preference for organic compounds and to confirm experimental results. The response of the synergistically enhanced sensors to gas molecules containing certain functional groups is in excellent agreement with density functional theory calculations performed in this work too. This new fabrication strategy can underpin the next generation of advanced materials for gas sensing applications and prevent VOC levels that are hazardous to human health and can cause environmental damages.

3D-Printed Chemiresistive Sensor Array on Nanowire CuO/Cu2O/Cu Heterojunction Nets.

In this work, the one-step three-dimensional (3D) printing of 20 nm nanowire (NW)-covered CuO/Cu2O/Cu microparticles (MPs) with diameters of 15-25 µm on the surface of the glass substrate forming an ordered net is successfully reported for the first time. 3D-printed Cu MP-based stripes formed nonplanar CuO/Cu2O/Cu heterojunctions after thermal annealing at 425 °C for 2 h in air and were fully covered with a 20 nm NW net bridging MPs with external Au contacts. The morphological, vibrational, chemical, and structural investigations were performed in detail, showing the high crystallinity of the NWs and 3D-printed CuO/Cu2O/Cu heterojunction lines, as well as the growth of CuO NWs on the surface of MPs. The gas-sensing measurements showed excellent selectivity to acetone vapor at an operating temperature of 350 °C with a high gas response about 150% to 100 ppm. The combination of the possibility of fast acetone vapor detection, low power consumption, and controllable size and geometry makes these 3D-printed devices ideal candidates for fast detection, as well as for acetone vapor monitoring (down to 100 ppm). This 3D-printing approach will pave a new way for many different devices through the simplicity and versatility of the fabrication method for the exact detection of acetone vapors in various atmospheres.

Concept and modelling of memsensors as two terminal devices with enhanced capabilities in neuromorphic engineering.

We report on memsensors, a class of two terminal devices that combines features of memristive and sensor devices. Apart from a pinched hysteresis (memristive property) and stimulus dependent electrical resistance (sensing property) further properties like dynamic adaptation to an external stimulus emerge. We propose a three component equivalent circuit to model the memsensor electrical behaviour. In this model we find stimulus dependent hysteresis, a delayed response to the sensory signal and adaptation. Stimulus dependent IV hysteresis as a fingerprint of a memsensor device is experimentally shown for memristive ZnO microrods. Adaptation in memsensor devices as found in our simulations resembles striking similarities to the biology. Especially the stimulus dependency of the IV hysteresis and the adaptation to external stimuli are superior features for application of memsensors in neuromorphic engineering. Based on the simulations and experimental findings we propose design rules for memsensors that will facilitate further research on memsensitive systems.

Improving gas sensing by CdTe decoration of individual Aerographite microtubes.

Novel gas sensors have been realized by decorating clusters of tubular Aerographite with CdTe using magnetron sputtering techniques. Subsequently, individual microtubes were separated and electrically contacted on a SiO2/Si substrate with pre-patterned electrodes. Cathodoluminescence, electron microscopy and electrical characterization prove the successful formation of a polycrystalline CdTe thin film on Aerographite enabling an excellent gas response to ammonia. Furthermore, the dynamical response to ammonia exposure has been investigated, highlighting the quick response and recovery times of the sensor, which is highly beneficial for extremely short on/off cycles. Therefore, this gas sensor reveals a large potential for cheap, highly selective, reliable and low-power gas sensors, which are especially important for hazardous gases such as ammonia.

PdO/PdO2 functionalized ZnO : Pd films for lower operating temperature H2 gas sensing.

Noble metals and their oxide nano-clusters are considered to be the most promising candidates for fabricating advanced H2 gas sensors. Through this work, we propose a novel strategy to grow and modulate the density of PdO/PdO2 nanoparticles uniformly on nanostructured Pd-doped ZnO (ZnO : Pd) films by a one-step solution approach followed by thermal annealing at 650 °C, and thus to detect ppm-level H2 gas in a selective manner. The gas sensing properties of such hybridized materials showed that the PdO-functionalized ZnO samples offer significantly improved H2 gas sensing properties in an operating temperature range of 25-200 °C. The deposition of ZnO : Pd films via a simple synthesis from chemical solutions (SCS) approach with an aqueous bath (at relatively low temperatures, <95 °C) is reported. Furthermore, the functionalization of palladium oxide nanoclusters by a simple but highly effective approach on ZnO : Pd film surfaces was performed and is reported here for the first time. The morphological, structural, vibrational, optical, chemical, and electronic properties were studied in detail and the mixed phases of palladium oxide nanoclusters on the ZnO surface were found. Sensor studies of the ZnO : Pd samples (in the range of 25-350 °C operating temperature) showed good selectivity to H2 gas, especially in the range of higher temperatures (>150 °C, up to 350 °C); however, the PdO/PdO2 mixed phases of the nanocluster-modified surface ZnO : Pd films showed a much better selectivity to H2 gas, even at a lower operating temperature, in the range of 25-150 °C. For such PdO-functionalized ZnO : Pd films, even at room temperature, a gas response of ∼12.7 to 1000 ppm of H2 gas was obtained, without response to any other reducing gases or tested vapors. The large recovery time of the samples at room temperatures (>500 s) can be drastically reduced by applying higher bias voltages. Furthermore, we propose and discuss the gas sensing mechanism for these structures in detail. Our study demonstrates that surface functionalization with PdO/PdO2 mixed phase nanoclusters-nanoparticles (NPs) is much more effective than only the Pd doping of nanostructured ZnO films for selective sensing applications. This approach will pave a new way for the controlled functionalization of PdO/PdO2 nanoclusters on ZnO : Pd surfaces to the exact detection of highly explosive H2 gas under various atmospheres by using solid state gas sensors.

Buckminsterfullerene hybridized zinc oxide tetrapods: defects and charge transfer induced optical and electrical response.

Buckminster fullerene (C60) based hybrid metal oxide materials are receiving considerable attention because of their excellent fundamental and applied aspects, like semiconducting, electron transfer, luminescent behaviors, etc. and this work briefly discusses the successful fabrication of C60 decorated ZnO tetrapod materials and their detailed structure-property relationships including device sensing applications. The electron microscopy investigations indicate that a quite dense surface coverage of ZnO tetrapods with C60 clusters is achieved. The spectroscopy studies confirmed the identification of the C60 vibrational modes and the C60 induced changes in the absorption and luminescence properties of the ZnO tetrapods. An increased C60 concentration on ZnO results in steeper ZnO bandgap absorption followed by well-defined free exciton and 3.31 eV line emissions. As expected, higher amounts of C60 increase the intensity of C60-related visible absorption bands. Pumping the samples with photons with an energy corresponding to these absorption band maxima leads to additional emission from ZnO showing an effective charge transfer phenomenon from C60 to the ZnO host. The density of states model obtained from DFT studies for pure and C60 coated ZnO surfaces confirms the experimental observations. The fabricated C60-ZnO hybrid tetrapod based micro- and nanodevices showed interesting ethanol gas sensing characteristics.

Sensing performances of pure and hybridized carbon nanotubes-ZnO nanowire networks: A detailed study.

In this work, the influence of carbon nanotube (CNT) hybridization on ultraviolet (UV) and gas sensing properties of individual and networked ZnO nanowires (NWs) is investigated in detail. The CNT concentration was varied to achieve optimal conditions for the hybrid with improved sensing properties. In case of CNT decorated ZnO nanonetworks, the influence of relative humidity (RH) and applied bias voltage on the UV sensing properties was thoroughly studied. By rising the CNT content to about 2.0 wt% (with respect to the entire ZnO network) the UV sensing response is considerably increased from 150 to 7300 (about 50 times). With respect to gas sensing, the ZnO-CNT networks demonstrate an excellent selectivity as well as a high gas response to NH3 vapor. A response of 430 to 50 ppm at room temperature was obtained, with an estimated detection limit of about 0.4 ppm. Based on those results, several devices consisting of individual ZnO NWs covered with CNTs were fabricated using a FIB/SEM system. The highest sensing performance was obtained for the finest NW with diameter (D) of 100 nm,  with a response of about 4 to 10 ppm NH3 vapor at room temperature.