Competing surface reactions limiting the performance of ion-sensitive field-effect transistors

© 2015 Elsevier B.V. All rights reserved.Ion-sensitive field-effect transistors based on silicon nanowires are promising candidates for the detection of chemical and biochemical species. These devices have been established as pH sensors thanks to the large number of surface hydroxyl groups at the gate dielectrics which makes them intrinsically sensitive to protons. To specifically detect species other than protons, the sensor surface needs to be modified. However, the remaining hydroxyl groups after functionalization may still limit the sensor response to the targeted species. Here, we describe the influence of competing reactions on the measured response using a general site-binding model. We investigate the key features of the model with a real sensing example based on gold-coated nanoribbons functionalized with a self-assembled monolayer of calcium-sensitive molecules. We identify the residual pH response as the key parameter limiting the sensor response. The competing effect of pH or any other relevant reaction at the sensor surface has therefore to be included to quantitatively understand the sensor response and prevent misleading interpretations

Plugin for automatic measurement of archeological artifacts with ImageJ software

The Java plugin for ImageJ platform. Plugin allow automatic measurment of flakes supporting a new technique of artifact processing with the aid of image recognition system

Analytical Model To Describe the Effect of Polyethylene Glycol on Ionic Screening of Analyte Charges in Transistor-Based Immunosensing

Recently, the co-immobilization of polyethylene glycol has improved sensor responses of transistor-based immunosensing by approximately three times. However, there is currently no analytical model available to explain this empirical effect. The key parameters thought to affect the potential are the receptor density, the capacitance, the analyte charge, and the dissociation constant. Based on our experimental data, only the analyte charge can account for the signal enhancement. To capture the effect of PEG on the analyte charge, we introduce a prefactor, the detectable charge qdet, which represents the portion of analyte charges effectively detected by the sensor. This parameter can quantitatively describe the PEG-induced signal enhancement and can be used to recommend the choice of PEG size for immuno-field-effect transistors. Additionally, we include the competition between electrolyte ions and the analyte for binding to the recognition molecule to more accurately describe the concentration-dependent sensor responses than the traditional Langmuir binding model does

Enhanced Resonant Tunneling in Symmetric 2D Semiconductor Vertical Heterostructure Transistors

Tunneling transistors with negative differential resistance have widespread appeal for both digital and analog electronics. However, most attempts to demonstrate resonant tunneling devices, including graphene–insulator–graphene structures, have resulted in low peak-to-valley ratios, limiting their application. We theoretically demonstrate that vertical heterostructures consisting of two identical monolayer 2D transition-metal dichalcogenide semiconductor electrodes and a hexagonal boron nitride barrier result in a peak-to-valley ratio several orders of magnitude higher than the best that can be achieved using graphene electrodes. The peak-to-valley ratio is large even at coherence lengths on the order of a few nanometers, making these devices appealing for nanoscale electronics

Graphene Transistors Are Insensitive to pH Changes in Solution

We observe very small gate-voltage shifts in the transfer characteristic of as-prepared graphene field-effect transistors (GFETs) when the pH of the buffer is changed. This observation is in strong contrast to Si-based ion-sensitive FETs. The low gate-shift of a GFET can be further reduced if the graphene surface is covered with a hydrophobic fluorobenzene layer. If a thin Al-oxide layer is applied instead, the opposite happens. This suggests that clean graphene does not sense the chemical potential of protons. A GFET can therefore be used as a reference electrode in an aqueous electrolyte. Our finding sheds light on the large variety of pH-induced gate shifts that have been published for GFETs in the recent literature

Shedding Light on Aging of N‑Doped Titania Photocatalysts

A detailed analysis of nitrogen dopant behavior in nanostructured microspheres of the TiO₂ photocatalyst obtained by the thermally assisted reactions in aqueous sprays method has been performed for the first time using electron paramagnetic resonance, X-ray photoelectron spectroscopy, and UV–vis spectroscopy and is supported by theoretical simulation of possible defect structures. The nitrogen species were found to undergo the N^• to N^– transformation during sample storage under different conditions, with an activation energy of about 0.45 eV. Three main possible evolution pathways for the dopant state were identified and discussed. It was established that the most probable transformation consists of migration of an oxygen vacancy site to an interstitial nitrogen atom followed by the formation of a nonparamagnetic substitution nitrogen center. Possible diffusion routes of oxygen vacancy and corresponding energy barriers were estimated and found to be in agreement with experimental observations

One-Step Microheterogeneous Formation of Rutile@Anatase Core–Shell Nanostructured Microspheres Discovered by Precise Phase Mapping

Nanostructured core–shell microspheres with a rough rutile core and a thin anatase shell are synthesized via a one-step heterogeneous templated hydrolysis process of TiCl₄ vapor on the aerosol water–air interface. The rutile-in-anatase core–shell structure has been evidenced by different electron microscopy techniques, including electron energy-loss spectroscopy and 3D electron tomography. A new mechanism for the formation of a crystalline rutile core inside the anatase shell is proposed based on a statistical evaluation of a large number of electron microscopy data. We found that the control over the TiCl₄ vapor pressure, the ratio between TiCl₄ and H₂O aerosol, and the reaction conditions plays a crucial role in the formation of the core–shell morphology and increases the yield of nanostructured microspheres

Selective sodium sensing with gold-coated silicon nanowire field-effect transistors in a differential setup

Ion-sensitive field-effect transistors based on silicon nanowires with high dielectric constant gate oxide layers (e.g., Al2O3 or HfO2) display hydroxyl groups which are known to be sensitive to pH variations but also to other ions present in the electrolyte at high concentration. This intrinsically nonselective sensitivity of the oxide surface greatly complicates the selective sensing of ionic species other than protons. Here, we modify individual nanowires with thin gold films as a novel approach to surface functionalization for the detection of specific analytes. We demonstrate sodium ion (Na+) sensing by a self-assembled monolayer (SAM) of thiol-modified crown ethers in a differential measurement setup. A selective Na+ response of ≈-44 mV per decade in a NaCl solution is achieved and tested in the presence of protons (H+), potassium (K+), and chloride (Cl-) ions, by measuring the difference between a nanowire with a gold surface functionalized by the SAM (active) and a nanowire with a bare gold surface (control). We find that the functional SAM does not affect the unspecific response of gold to pH and background ionic species. This represents a clear advantage of gold compared to oxide surfaces and makes it an ideal candidate for differential measurements. © 2013 American Chemical Society

Understanding the Electrolyte Background for Biochemical Sensing with Ion-Sensitive Field-Effect Transistors

Silicon nanowire field-effect transistors have attracted substantial interest for various biochemical sensing applications, yet there remains uncertainty concerning their response to changes in the supporting electrolyte concentration. In this study, we use silicon nanowires coated with highly pH-sensitive hafnium oxide (HfO₂) and aluminum oxide (Al₂O₃) to determine their response to variations in KCl concentration at several constant pH values. We observe a nonlinear sensor response as a function of ionic strength, which is independent of the pH value. Our results suggest that the signal is caused by the adsorption of anions (Cl^–) rather than cations (K⁺) on both oxide surfaces. By comparing the data to three well-established models, we have found that none of those can explain the present data set. Finally, we propose a new model which gives excellent quantitative agreement with the data

Selective Sodium Sensing with Gold-Coated Silicon Nanowire Field-Effect Transistors in a Differential Setup

Ion-sensitive field-effect transistors based on silicon nanowires with high dielectric constant gate oxide layers (<i>e.g.</i>, Al₂O₃ or HfO₂) display hydroxyl groups which are known to be sensitive to pH variations but also to other ions present in the electrolyte at high concentration. This intrinsically nonselective sensitivity of the oxide surface greatly complicates the selective sensing of ionic species other than protons. Here, we modify individual nanowires with thin gold films as a novel approach to surface functionalization for the detection of specific analytes. We demonstrate sodium ion (Na⁺) sensing by a self-assembled monolayer (SAM) of thiol-modified crown ethers in a differential measurement setup. A selective Na⁺ response of ≈−44 mV per decade in a NaCl solution is achieved and tested in the presence of protons (H⁺), potassium (K⁺), and chloride (Cl^–) ions, by measuring the difference between a nanowire with a gold surface functionalized by the SAM (active) and a nanowire with a bare gold surface (control). We find that the functional SAM does not affect the unspecific response of gold to pH and background ionic species. This represents a clear advantage of gold compared to oxide surfaces and makes it an ideal candidate for differential measurements