ZIF-8-Based Surface Plasmon Resonance and Fabry-Pérot Sensors for Volatile Organic Compounds.

This work explores the use of ZIF-8, a metal-organic framework (MOF) material, for its use in the optical detection of volatile organic compounds (VOCs) in Fabry-Pérot and surface plasmon resonance (SPR)-based sensors. The experiments have been carried out with ethanol (EtOH) and show response times as low as 30 s under VOC-saturated atmospheres, and the estimated limit of detection is below 4000 ppm for both sensor types. The selectivity towards other VOCs is relatively poor, although the dynamics of adsorption/desorption differ for each VOC and could be used for selectivity purposes. Furthermore, the hydrophobicity of ZIF-8 has been confirmed and the fabricated sensors are insensitive to this compound, which is a very attractive result for its practical use in gas sensing devices.

Fabrication, Characterization and Performance of Low Power Gas Sensors Based on (GaxIn1-x)2O3 Nanowires.

Active research in nanostructured materials aims to explore new paths for improving electronic device characteristics. In the field of gas sensors, those based on metal oxide single nanowires exhibit excellent sensitivity and can operate at extremely low power consumption, making them a highly promising candidate for a novel generation of portable devices. The mix of two different metal oxides on the same nanowire can further broaden the response of this kind of gas sensor, thus widening the range of detectable gases, without compromising the properties related to the active region miniaturization. In this paper, a first study on the synthesis, characterization and gas sensing performance of (GaxIn1-x)2O3 nanowires (NWs) is reported. Carbothermal metal-assisted chemical vapor deposition was carried out with different mixtures of Ga2O3, In2O3 and graphite powders. Structural characterization of the NWs revealed that they have a crystalline structure close to that of In2O3 nanowires, with a small amount of Ga incorporation, which highly depends on the mass ratio between the two precursors. Dedicated gas nanosensors based on single NWs were fabricated and tested for both ethanol and nitrogen dioxide, demonstrating an improved performance compared to similar devices based on pure In2O3 or Ga2O3 NWs.

Pursuing the Diffraction Limit with Nano-LED Scanning Transmission Optical Microscopy.

Recent research into miniaturized illumination sources has prompted the development of alternative microscopy techniques. Although they are still being explored, emerging nano-light-emitting-diode (nano-LED) technologies show promise in approaching the optical resolution limit in a more feasible manner. This work presents the exploration of their capabilities with two different prototypes. In the first version, a resolution of less than 1 µm was shown thanks to a prototype based on an optically downscaled LED using an LED scanning transmission optical microscopy (STOM) technique. This research demonstrates how this technique can be used to improve STOM images by oversampling the acquisition. The second STOM-based microscope was fabricated with a 200 nm GaN LED. This demonstrates the possibilities for the miniaturization of on-chip-based microscopes.

Nano illumination microscopy: a technique based on scanning with an array of individually addressable nanoLEDs.

In lensless microscopy, spatial resolution is usually provided by the pixel density of current digital cameras, which are reaching a hard-to-surpass pixel size / resolution limit over 1 µm. As an alternative, the dependence of the resolving power can be moved from the detector to the light sources, offering a new kind of lensless microscopy setups. The use of continuously scaled-down Light-Emitting Diode (LED) arrays to scan the sample allows resolutions on order of the LED size, giving rise to compact and low-cost microscopes without mechanical scanners or optical accessories. In this paper, we present the operation principle of this new approach to lensless microscopy, with simulations that demonstrate the possibility to use it for super-resolution, as well as a first prototype. This proof-of-concept setup integrates an 8 × 8 array of LEDs, each 5 × 5 µm2 pixel size and 10 µm pitch, and an optical detector. We characterize the system using Electron-Beam Lithography (EBL) pattern. Our prototype validates the imaging principle and opens the way to improve resolution by further miniaturizing the light sources.

Strong Cavity-Optomechanical Transduction of Nanopillar Motion.

Nanomechanical resonators can serve as ultrasensitive, miniaturized force probes. While vertical structures such as nanopillars are ideal for this purpose, transducing their motion is challenging. Pillar-based photonic crystals (PhCs) offer a potential solution by integrating optical transduction within the pillars. However, achieving high-quality PhCs is hindered by inefficient vertical light confinement. Here, we present a full-silicon photonic crystal cavity based on nanopillars as a platform for applications in force sensing and biosensing areas. Its unit cell consists of a silicon pillar with a larger diameter at its top portion than at the bottom, which allows vertical light confinement and an energy band gap in the near-infrared range for transverse-magnetic polarization. We experimentally demonstrate optical cavities with Q factors exceeding 103, constructed by inserting a defect within a periodic arrangement of this type of pillars. Each nanopillar naturally behaves as a nanomechanical cantilever, making the fabricated geometries excellent optomechanical (OM) photonic crystal cavities in which the mechanical motion of each nanopillar composing the cavity can be optically transduced. These geometries display enhanced mechanical properties, cost-effectiveness, integration possibilities, and scalability. They also present an alternative in front of the widely used suspended Si beam OM cavities made on silicon-on-insulator substrates.

A Novel Approach for a Chip-Sized Scanning Optical Microscope.

The recent advances in chip-size microscopy based on optical scanning with spatially resolved nano-illumination light sources are presented. This new straightforward technique takes advantage of the currently achieved miniaturization of LEDs in fully addressable arrays. These nano-LEDs are used to scan the sample with a resolution comparable to the LED sizes, giving rise to chip-sized scanning optical microscopes without mechanical parts or optical accessories. The operation principle and the potential of this new kind of microscope are analyzed through three different implementations of decreasing LED dimensions from 20 µm down to 200 nm.

A cyclo olefin polymer microfluidic chip with integrated gold microelectrodes for aqueous and non-aqueous electrochemistry.

This paper presents an entirely polymeric microfluidic system, made of cyclo olefin polymer (COP), with integrated gold microband electrodes for electrochemical applications in organic media. In the present work, we take advantage of the COP's high chemical stability to polar organic solvents in two different ways: (i) to fabricate gold microelectrodes using COP as a substrate by standard lithographic and lift-off techniques; and (ii) to perform electrochemical experiments in organic media. In particular, fourteen parallel gold microelectrodes with a width of 14 microm and separated from their closest neighbour by 16 microm were fabricated by lithographic and lift-off techniques on a 188 microm thick COP sheet. A closed channel configuration was obtained by pressure-assisted thermal bonding between the COP sheet containing the microelectrodes and a microstructured COP sheet, where a 3 cm long, 50 microm wide and 24 microm deep channel was fabricated via hot embossing. Cyclic voltammetric measurements were carried out in aqueous and organic media, using a solution consisting of 5 mM ferrocyanide/ferricyanide in 0.5 M KNO(3) and 5 mM ferrocene in 0.1 M TBAP/acetonitrile, respectively. Experimental currents obtained for different flow rates ranging from 1 to 10 microL min(-1) were compared to the theoretical steady state currents calculated by the Levich equation for a band electrode (R. G. Compton, A. C. Fisher, R. G. Wellington, P. J. Dobson and P. A. Leigh, J. Phys. Chem., 1993, 97, 10410-10415). In both cases, the difference between the experimental and the predicted data is less than 5%, thus validating the behaviour of the fabricated device. This result opens the possibility to use a microfluidic system made entirely from COP with integrated microband electrodes in organic electroanalysis and in electrosynthesis.

Experimental study of the retention properties of a cyclo olefin polymer pillar array column in reversed-phase mode.

Experimental measurements to study the retention capacity and band broadening under retentive conditions using micromachined non-porous pillar array columns fabricated in cyclo olefin polymer are presented. In particular, three columns with different depths but with the same pillar structure have been fabricated via hot embossing and pressure-assisted thermal bonding. Separations of a mixture of four coumarins using varying mobile phase compositions have been monitored to study the relation between the retention factor and the ratio of organic solvent in the aqueous mobile phase. Moreover, the linear relation between the retention and the surface/volume ratio predicted in theory has been observed, achieving retention factors up to k=2.5. Under the same retentive conditions, minimal reduced plate height values of h(min)=0.4 have been obtained at retention factors of k=1.2. These experimental results are compared with the case of non-porous and porous silicon pillars. Similar results for the plate heights are achieved while retention factors are higher than the non-porous silicon column and considerably smaller than the porous pillar column, given the non-porous nature of the used cyclo olefin polymer. The feasibility of using this polymer column as an alternative to the pillar array silicon columns is corroborated.

An array of ordered pillars with retentive properties for pressure-driven liquid chromatography fabricated directly from an unmodified cyclo olefin polymer.

The current paper describes the development and characterization of a pillar array chip that is constructed out of a sandwich of cyclo olefin polymer (COP) sheets. The silicon master of a 5 cm long pillar array was embossed into the COP, yielding 4.3 microm deep pillars of 15.3 microm diameter with an external porosity of 43 % and a well designed sidewall region to avoid side wall induced band broadening. A closed channel configuration was obtained by pressure assisted thermal bonding to a non-processed COP lid. Injection of coumarin dye plugs and detection with a fluorescence microscope showed very close agreement of this channel configuration to theoretical expectations in terms of band broadening. This agreement is due to the low taper, the optimized sidewall region and the excellent bonding quality between the two polymer sheets, even at the pillar area. Under non-retained conditions (pure methanol as mobile phase), plate heights as low as 4 microm were obtained. Under retained conditions, using the native hydrophobic properties of the COP channel (in 70/30 v/v water/methanol mixture as mobile phase), a minimum plate height of 6 microm was obtained. A 4 component separation was successfully achieved, demonstrating that COP is a cheap and efficient alternative for silicon and silica based liquid chromatography formats.

A model for the response towards oxidizing gases of photoactivated sensors based on individual SnO2 nanowires.

The paper presents a quantitative model to elucidate the role of impinging photons on the final response towards oxidizing gases of light-activated metal oxide gas sensors. The model is based on the competition between oxygen molecules in air and oxidizing target gases (such as NO(2)) for the same adsorption sites: the surface oxygen vacancies (OV). The model fairly reproduces the experimental measurements of both the steady-state and the dynamic response of individual SnO(2) nanowires towards oxidizing gases. Quantitative results indicate that: (1) at room temperature NO(2) adsorbs onto OV more avidly than oxygen; (2) the flux of photons and the NO(2) concentration determine the partition of the two gas populations at the surface; and (3) the band-to-band generation of electron-hole pairs plays a significant role in the photodesorption process of gas molecules. The model also offers a methodology to estimate some fundamental parameters, such as the adsorption rates and the photodesorption cross sections of oxidizing molecules interacting with the nanowires' surface. All these results, enabled by the use of individual nanowires, provide deep insight about how to control the response of metal oxide nanowires towards oxidizing gases, paving the way to the development and consolidation of this family of low consumption conductometric sensors operable at room temperature.

Site-Specific Growth and in Situ Integration of Different Nanowire Material Networks on a Single Chip: Toward a Nanowire-Based Electronic Nose for Gas Detection.

A new method for the site-selective synthesis of nanowires has been developed to enable material growth with defined morphology and, at the same time, different composition on the same chip surface. The chemical vapor deposition approach for the growth of these nanowire-based resistive devices using micromembranes can be easily modified and represents a simple, adjustable fabrication process for the direct integration of nanowire meshes in multifunctional devices. This proof-of-concept study includes the deposition of SnO2, WO3, and Ge nanowires on the same chip. The individual resistors exhibit adequate gas sensing responses toward changing gas concentrations of CO, NO2, and humidity diluted in synthetic air. The data have been processed by principal component analysis with cluster responses that can be easily separated, and thus, the devices described herein are in principle suitable for environmental monitoring.

Localized growth and in situ integration of nanowires for device applications.

Simultaneous localized growth and device integration of inorganic nanostructures on heated micromembranes is demonstrated for single crystalline germanium and tin oxide nanowires. Fully operating CO gas sensors prove the potential of the presented approach. With this simple CMOS compatible technique, issues of assembly, transfer and contact formation are addressed.

Experimental study of the depth influence on the band broadening effect in a cyclo-olefin polymer column containing an array of ordered pillars.

An experimental study of a micromachined non-porous pillar array column performance under non-retentive conditions is presented. The same pillar structure has been fabricated in cyclo-olefin polymer (COP) chips with three different depths via hot embossing and pressure-assisted thermal bonding. The influence of the depth on the band broadening along with the already known contribution arising from the top and bottom cover plates has been studied. The experimental results exhibit reduced plate heights as low as 0.2, which are in agreement with the previous experimental work. Moreover, the constant values of the reduced Van Deemter expression are also in accordance with the previous studies. A more exhaustive study of the C-term band broadening is also presented, showing that comparing the space between the pillars with different open tubular rectangular channels offers a good estimation of the C-term band broadening that is obtained experimentally. These experimental results, hence, confirm that micromachined pillar array columns fabricated in COP can achieve the same performance as the ones fabricated in silicon for the presently studied pillar channel design.

On the role of individual metal oxide nanowires in the scaling down of chemical sensors.

Single-crystalline semiconductor metal oxide nanowires exhibit novel structural and electrical properties attributed to their reduced dimensions, well-defined geometry and the negligible presence of grain boundaries and dislocations in their inside. This favours direct chemical transduction mechanisms at their surfaces upon exposure to gas molecules, making them promising active device elements for a new generation of chemical sensors. Furthermore, metal oxide nanowires can be heated up to the optimal operating temperature for gas sensing applications with extremely low power consumption due to their small mass, giving rise to devices more efficient than their nanoparticle-based counterparts. Here, the current status of development of sensors based on individual metal oxide nanowires is surveyed, and the main technological challenges which act as bottleneck to their potential use in real applications are presented.

Mesoporous silica: a suitable adsorbent for amines.

Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices.

Fabrication and electrical characterization of circuits based on individual tin oxide nanowires.

Two- and four-probe electrical measurements on individual tin oxide (SnO(2)) nanowires were performed to evaluate their conductivity and contact resistance. Electrical contacts between the nanowires and the microelectrodes were achieved with the help of an electron- and ion-beam-assisted direct-write nanolithography process. High contact resistance values and the nonlinear current-bias (I-V) characteristics of some of these devices observed in two-probe measurements can be explained by the existence of back-to-back Schottky barriers arising from the platinum-nanowire contacts. The nanoscale devices described herein were characterized using impedance spectroscopy, enabling the development of an equivalent circuit. The proposed methodology of nanocontacting and measurements can be easily applied to other nanowires and nanometre-sized materials.