Louis C. P. M. de Smet

Silicon Nanowire-Based Devices for Gas-Phase Sensing

Since their introduction in 2001, SiNW-based sensor devices have attracted considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species. Most studies focus on detecting, sensing and monitoring analytes in aqueous solution, but the number of studies on sensing gases and vapors using SiNW-based devices is increasing. This review gives an overview of selected research papers related to the application of electrical SiNW-based devices in the gas phase that have been reported over the past 10 years. Special attention is given to surface modification strategies and the sensing principles involved. In addition, future steps and technological challenges in this field are addressed.

Polymer‐Induced Surface Modifications of Pd‐based Thin Films Leading to Improved Kinetics in Hydrogen Sensing and Energy Storage Applications

The catalytic properties of Pd alloy thin films are enhanced by a thin sputtered PTFE coating, resulting in profound improvements in hydrogen adsorption and desorption in Pd-based and Pd-catalyzed hydrogen sensors and hydrogen storage materials. The remarkably enhanced catalytic performance is attributed to chemical modifications of the catalyst surface by the sputtered PTFE leading to a possible change in the binding strength of the intermediate species involved in the hydrogen sorption process.

Ionophore-containing siloprene membranes: direct comparison between conventional ion-selective electrodes and silicon nanowire-based field-effect transistors.

Siloprene-based, ion-selective membranes (ISMs) were drop-casted onto a field-effect transistor device that consisted of a single-chip array of top-down prepared silicon nanowires (SiNWs). Within one array, two sets of SiNWs were covered with ISMs, each containing two different ionophores, allowing the simultaneous sensing of K and Na ions using a flow cell. It is shown that both ions can be effectively detected in the same solution over a wide concentration range from 10(-4) to 10(-1) M without interference. The ISMs were also analyzed in a conventional ISE configuration, allowing a direct comparison. While the responses for K(+) were similar for both sensor configurations, remarkably, the Na(+) response of the ISM-covered SiNW device was found to be higher than the one of the ISE configuration. The addition of a Na(+) buffering hydrogel layer between the SiO2 of the SiNW and the ISM reduced the response, showing the importance of keeping the boundary potential at the SiO2/ISM interface constant. The responses of the siloprene-covered SiNW devices were found to be stable over a period of at least 6 weeks, showing their potential as a multichannel sensor device.

Diffusion in porous silicon: effects on the reactivity of alkenes and electrochemistry of alkylated porous silicon

Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent SiC bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)–undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current–distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore–pore interconnections exist in the porous silicon.

Organic Surface Modification of Silicon Nanowire-Based Sensor Devices

The year 2011 marks the 10th anniversary of silicon nanowire (SiNW)-based electronic devices. Since their introduction (Cui & Lieber, 2001) SiNW-based sensor devices have gained considerable interest as a general platform for ultra-sensitive, electrical detection of biological and chemical species (Figure 1). Although SiOx coatings can be used for the detection of protons (Cui, 2001), and gases (Wan, 2009), the specific detection of other analytes, including ions and biomolecules requires the presence of an affinity layer that interacts with the analyte of interest. Such a layer can be added on top of the nanowire by the modification of the nanowire surface. In this chapter we review the surface modification strategies that have been explored on SiNW-based devices over the past decade.

Metal-Organic Polyhedra-Coated Si Nanowires for the Sensitive Detection of Trace Explosives

Surface-modified silicon nanowire-based field-effect transistors (SiNW-FETs) have proven to be a promising platform for molecular recognition in miniature sensors. In this work, we present a novel nanoFET device for the sensitive and selective detection of explosives based on affinity layers of metal-organic polyhedra (MOPs). The judicious selection of the geometric and electronic characteristics of the assembly units (organic ligands and unsaturated metal site) embedded within the MOP cage allowed for the formation of multiple charge-transfer (CT) interactions to facilitate the selective explosive inclusion. Meanwhile, the host-stabilized CT complex inside the cage acted as an effective molecular gating element to strongly modulate the electrical conductance of the silicon nanowires. By grafting the MOP cages onto a SiNW-FET device, the resulting sensor showed a good electrical sensing capability to various explosives, especially 2,4,6-trinitrotoluene (TNT), with a detection limit below the nanomolar level. Importantly, coupling MOPs-which have tunable structures and properties-to SiNW-based devices may open up new avenues for a wide range of sensing applications, addressing various target analytes.

Influence of Conductivity and Dielectric Constant of Water–Dioxane Mixtures on the Electrical Response of SiNW-Based FETs

In this study, we report on the electrical response of top-down, p-type silicon nanowire field-effect transistors exposed to water and mixtures of water and dioxane. First, the capacitive coupling of the back gate and the liquid gate via an Ag/AgCl electrode were compared in water. It was found that for liquid gating smaller potentials are needed to obtain similar responses of the nanowire compared to back gating. In the case of back gating, the applied potential couples through the buried oxide layer, indicating that the associated capacitance dominates all other capacitances involved during this mode of operation. Next, the devices were exposed to mixtures of water and dioxane to study the effect of these mixtures on the device characteristics, including the threshold voltage (VT). The VT dependency on the mixture composition was found to be related to the decreased dissociation of the surface silanol groups and the conductivity of the mixture used. This latter was confirmed by experiments with constant conductivity and varying water–dioxane mixtures.

Gas phase sensing of alcohols by Metal Organic Framework – polymer composite materials

Affinity layers play a crucial role in chemical sensors for the selective and sensitive detection of analytes. Here, we report the use of composite affinity layers containing Metal Organic Frameworks (MOFs) in a polymeric matrix for sensing purposes. Nanoparticles of NH2-MIL-53(Al) were dispersed in a Matrimid polymer matrix with different weight ratios (0–100 wt %) and drop-casted on planar capacitive transducer devices. These coated devices were electrically analyzed using impedance spectroscopy and investigated for their sensing properties toward the detection of a series of alcohols and water in the gas phase. The measurements indicated a reversible and reproducible response in all devices. Sensor devices containing 40 wt % NH2-MIL-53(Al) in Matrimid showed a maximum response for methanol and water. The sensor response time slowed down with increasing MOF concentration until 40 wt %. The half time of saturation response (τ0.5) increased by ∼1.75 times for the 40 wt % composition compared to devices coated with Matrimid only. This is attributed to polymer rigidification near the MOF/polymer interface. Higher MOF loadings (≥50 wt %) resulted in brittle coatings with a response similar to the 100 wt % MOF coating. Cross-sensitivity studies showed the ability to kinetically distinguish between the different alcohols with a faster response for methanol and water compared to ethanol and 2-propanol. The observed higher affinity of the pure Matrimid polymer toward methanol compared to water allows also for a higher uptake of methanol in the composite matrices. Also, as indicated by the sensing studies with a mixture of water and methanol, the methanol uptake is independent of the presence of water up to 6000 ppm of water. The NH2-MIL-53(Al) MOFs dispersed in the Matrimid matrix show a sensitive and reversible capacitive response, even in the presence of water. By tuning the precise compositions, the affinity kinetics and overall affinity can be tuned, showing the promise of this type of chemical sensors.

Control of interpenetration of copper-based MOFs on supported surfaces by electrochemical synthesis

A study of a copper-based metal–organic framework (MOF) synthesized by an electrochemical route is presented. Morphological and adsorption properties of the MOF synthesized as bulk powder and on supported copper surfaces were investigated. Differences in these properties and structural refinement studies indicate that when 4,4′,4′′-s-triazine-2,4,6-triyl-tribenzoic acid (H3TATB) is used as linker interpenetration can be prevented when the structure is grown on a surface.

Fluorescent polyelectrolyte for the visualization of fingermarks

A fluorescent polyelectrolyte, poly(allylamine hydrochloride) (PAH) functionalised with the 7-amino-quinolinium chromophore, has been synthesized for the visualization of latent fingerprints. Exposing fingerprints to pH neutral, dilute aqueous solutions of this polymer results in bright green fluorescent images, which are clearly visible to the naked eye.