Analytical characteristics and sensitivity mechanisms of electrolyte-insulator-semiconductor system-based chemical sensors—a critical review

Recent trends in research and development of electrolyte-insulator-semiconductor (EIS) field-effect chemical sensors (ion-selective field-effect transistors, light-addressable potentiometric sensors, capacitive EIS-sensors) with inorganic gate insulators (oxide, nitride and chalcogenide films) are reviewed. Physical properties of EIS systems and basic mechanisms of their chemical sensitivity are examined. Analytical characteristics and sensing mechanisms of EIS pH sensors with oxide and nitride films, as well as metal ions sensors with chalcogenide films, are critically discussed. Prospects of future research on EIS field-effect biosensors are briefly outlined.     

Chemical sensors for determination of thallium ions with membranes based on TlI–Ag<Subscript>2</Subscript>S–As<Subscript>2</Subscript>S<Subscript>3</Subscript>: Radiotracer,solid-state,and analytical studies

A series of chalcogenide glasses of various compositions, based on the TlI–Ag₂S–As₂S₃ system, were prepared. The conductivity parameters and diffusion coefficients of silver and thallium radiotracers in the glass samples were determined. Chemical sensors with membranes of four glass compositions were prepared, and their analytical characteristics (sensitivity, selectivity, detection limit) were studied. Correlation between the ionic conductivity parameters of the ion-sensitive membranes and the analytical characteristics of chemical sensors for thallium ions in solutions was found.     

Copper ion-selective chalcogenide glass electrodes: Analytical characteristics and sensing mechanism

New copper ion-selective electrodes based on chalcogenide glasses, Cu_xAg_25?xAs_37.5Se_37.5, display high copper(II) ion sensitivity with Nernstian response in the range pCu 1–6, short response time, high selectivity, potential stability and reproducibility. These electrodes are 10–30 times more sensitive in strongly acidic media than crystalline copper ion-selective sensors and are superior to the copper(I) selenide electrode in selectivity and resistance to acids and oxidation. A model is proposed to explain the ion sensitivity of these chalcogenide glass sensors. The sensitivity depends on direct exchange of copper(II) ions between solution and the modified surface layer of the glass. The modified surface layer is formed as a result of partial destruction of the glass network on soaking in solution; its atomic density is 2.0–2.5 times less than that of the original glass. The structural defects and hollows make fast copper(II) ion migration within the modified surface layer possible. Exchange sites in this layer can be formed by both disproportionation and oxidation of copper(I) in the glass network, as well as by diffusion of copper(II) ion from solution in the case of glasses with low copper content. Experimental confirmation of this model is provided by x-ray, photo-electron and scanning Auger electron spectroscopy.     

New solid-state ion-selective electrodes — Sensors for chemical analysis of solutions

Summary From the historic point of view one can consider chalcogenide glass ion-selective electrodes (CGISEs) and ion-selective field effect transistors (ISFETs) as new solid-state sensors for chemical analysis. The paper describes the development of the sensors, the methods of investigation, analytical properties and the sensing mechanism of CGISEs and ISFETs.

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Neue ionen-selektive Festkörperelektroden — Sensoren für die chemische Analyse von Lösungen

     

Inverse opal photonic crystal of chalcogenide glass by solution processing

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors.     

人工智能味觉系统：概念、结构与方法

本文将传统的味觉传感器、人工味觉、电子舌等研究统一纳入人工智能味觉的框架中，提出了人工智能味觉的概念、结构及方法学问题。在传统分析科学中，非特异性感应是一个极力避免的现象，而交互感应传感器阵列则是将其作为基本出发点，设计构建成一个优化的组合，使得人工智能化学感受在技术上得以实现，交互感应理论和技术也因此成为其核心概念。作为一种仿生感觉技术，人工智能味觉系统是由交互感应电极及阵列、自学习专家数据库和智能模式识别三部分构成；电位法和伏安法是两类主要的传感方法；传感器材料包括贵金属及稀土金属、类脂/聚合物、硫属玻璃、导电聚合物以及其它如碳糊、酞菁、普鲁士蓝等；主成分分析和人工神经网络是智能识别过程中主要的模式识别工具。导电聚合物修饰电化学传感器和多技术联用分析方法目前已成为人工智能味觉系统研究的两个重要发展方向。     

Chemical sensors with chalcogenide glassy membranes

The present review is emphasized on the recent achievements in the application of chalcogenide glasses (ChG) as membrane materials in chemical sensors, microsensors and multisensor systems. The questions concerning material synthesis, sensor designs and the concepts for the potential-generating mechanisms have briefly discussed. Most of the chalcogenide glass-forming systems and compositions investigated as membrane active materials have been summarized, and their analytical characteristics have been considered. The efficiency of chalcogenide-based chemical sensors in the real system analyses, as well as the advantages and disadvantages in their analytical performance have been evaluated and compared with the corresponding polycrystalline analogous.     

Flattened infrared fiber-optic sensors for the analysis of micrograms of insoluble solid particles in solution or in a dry state

Highly sensitive absorption measurements on various samples may be carried out by Fiber-optic Evanescent Wave Spectroscopy (FEWS) in the mid-IR. Such measurements have already been done on solids, liquids and gases, using chalcogenide glass fibers or crystalline fibers. Segments of crystalline AgClBr fibers may be used as sensors of much higher sensitivity if their middle sections are pressed to form flat waveguides. We carried out measurements on micrograms of insoluble or slightly soluble particles in water, when they sedimented on the flattened parts of such sensors. Measurements were also carried out on few micrograms of dry particles that had been pressed onto the flattened parts. Flattened fiber sensors may therefore be used for measurements on micrograms of particles and they can be used for identifying the chemical nature of particles of organic, inorganic or biological materials and for studying their properties. The FEWS method, based on flattened mid-IR fiber sensors, is simple, inexpensive and does not require sample processing. It would be useful for measurements on very small quantities of particles for biomedical applications, for environmental protection, for drug enforcement agencies and for homeland security.     

Sodium Ion-Selective Chalcogenide Glass Electrodes

Abstract

Analytical characteristics and sensing mechanism of sodium ion-selective electrodes based on NaCl-Ga₂S₃-GeS₂ glasses have been investigated. Chalcogenide glass electrodes containing 10 mol.% NaCl in the membrane showed near-Nernstian response in the concentration range from 10-³ to 1 M sodium nitrate solution. These sensors were superior to the conventional pNa oxide glass electrodes in selectivity in the presence of hydrogen ions and in Na⁺ ion sensitivity in fluoride media. Prolonged solution treatment for several days reduces, however, the detection limit of the sensors and the slope of the electrode response. Ionic processes at the membrane surface have been investigated using XPS technique and ²²Na tracer measurements. It was shown that sodium ion-exchange governed Na⁺ ion response of chalcogenide     

A small angle neutron scattering and electrochemical impedance spectroscopy study of the nanostructure of the iron chalcogenide glass ion-selective electrode

This paper presents a preliminary structural and interfacial study of the iron chalcogenide glass [i.e., Fe_x(Ge₂₈Sb₁₂Se₆₀)_100−x] ion-selective electrode (ISE) using small angle neutron scattering (SANS) and electrochemical impedance spectroscopy (EIS). SANS detected variations in the neutron scattering as a function of iron content in the chalcogenide glass. Furthermore, a change in the chalcogenide glass structure was observed at elevated iron dopant levels. Conversely, EIS was used to show that the iron chalcogenide membrane comprises various time constants, and the interfacial charge transfer reaction depends on the membrane iron content. Equivalent circuit modeling revealed that the charge transfer resistance decreases at elevated iron levels, and this may be related to the presence of iron defects in the glass. It is proposed that the iron chalcogenide membrane comprises an iron nanostructural network embedded in the amorphous matrix, and this directly influences the electrical conductivity and concomitant electrochemical reactivity of the glass.     

超四面体硫簇结构调控与电化学发光研究进展

电化学发光(ECL)因其独特的性能特点在生物分析等领域展现出广阔的应用前景,高效ECL试剂的开发则为性能优异的传感器件的发展和临床应用提供了重要工具. 开放骨架超四面体硫簇由于同时具有分子筛的多孔结构和半导体的优异光电性能,在ECL分析中受到了越来越多的关注. 超四面体硫簇的结构组成可以实现原子级别的精确调控,并且其本身还可以作为结构单元来构筑多孔结构半导体材料. 这些特点使通过原子级别的结构组成调节来调控超四面体硫簇的性能成为可能,为发展性能优异的电化学发光材料,拓展其在生化传感、免疫分析和生物成像等方面的应用提供有效工具. 本综述总结了超四面体硫簇的合成、缺陷掺杂、功能调控及ECL生化分析等方面的研究进展,为推进高效ECL新材料的发展和新应用的拓展提供了借鉴.     

Charged particle activation analysis of oxygen in fluoride and chalcogenide glasses used for fiber amplifiers

The proton activation analysis of oxygen was studied in fluoride and chalcogenide glasses used for fiber amplifiers. First, we studied the interfering nuclear reactions from glass matrices to determine the oxygen concentration in these glasses. By using substoichiometric separation for ¹⁸F after irradiation, we found that the oxygen concentration was 12 to 204 ppm in InF₃-based fluoride glass and 0.04% to 0.7% in chalcogenide glass containing sodium. We also discuss the relation between oxygen concentration and optical properties such as the infrared absorption spectrum and fluorescence lifetime.     

Iodide determination with chalcogenide glass electrodes

Journal of Solid State Electrochemistry - The fabrication and characterisation of potentiometric chalcogenide glass electrodes with selectivity for iodide in aqueous media are reported. While such...     

Glass transition kinetics and fragility index of chalcogenides from Ag–As–S–Se system

Journal of Thermal Analysis and Calorimetry - The glass transition temperature dependence on a heating rate was investigated by differential scanning calorimetry for chalcogenide glasses from the...     

Correlation between glass transition and crystallization phenomena in context of Meyer–Neldel rule

The physical origin of the glass transition and its possible connection with crystallization is still an unresolved problem of glass science. Recent publications demonstrate the strong evidence of intrinsic relation between glass transition and crystallization phenomena. Here, we study this problem by using Meyer–Neldel rule (MNR) as a tool. The observation of MNR in thermally activated non-isothermal crystallization was verified by us in past. The objective of the present work is to check the applicability of MNR for thermally activated non-isothermal glass transition and crystallization in some chalcogenide glasses. We found that like crystallization, the glass transition phenomenon also obeys the MNR.     

Solid-State Thin-Film Sensors Based on Chalcogenide Materials Obtained by Planar Technology and Pulsed Laser Deposition

Methods of silicon planar technology and pulsed laser deposition were applied to fabricate fully solid-state chemical sensors for determining ions of copper, lead, cadmium, thallium, and also sulfide and chloride ions on the basis of thin chalcogenide films as ion-sensitive membranes.     

Structural Characterization of Non-Oxide Chalcogenide Glasses using Solid State NMR

In spite of the long-standing importance of non-oxide chalcogenide glasses in infrared optics and semiconductor technology, concepts describing the structural principles governing glass formation in these systems are just emerging. Most recently, modern quantitative solid state NMR techniques have offered new unique insights into the structural organization of these systems. In this review, we discuss the basic principles of various experimental approaches and their application to boron-silicon, -and phosphorus chalcogenide glasses.     

Thermal investigation of GeSb2Se4 chalcogenide alloy glass

Differential thermal analysis measurements were performed between 115 and 550° on glass samples of GeSb₂Se₄ chalcogenide alloy, and the latent heats of structural transformations were obtained. Heat treatment was found to result in the appearance of an endothermic peak associated with the glass transition.     

Near‐Infrared Active Lead Chalcogenide Quantum Dots: Preparation,Post‐Synthesis Ligand Exchange,and Applications in Solar Cells

Quantum dots (QDs) of lead chalcogenides (e.g. PbS, PbSe, and PbTe) are attractive near‐infrared (NIR) active materials that show great potential in a wide range of applications, such as, photovoltaics (PV), optoelectronics, sensors, and bio‐electronics. The surface ligand plays an essential role in the production of QDs, post‐synthesis modification, and their integration to practical applications. Therefore, it is critically important that the influence of surface ligands on the synthesis and properties of QDs is well understood for their applications in various devices. In this Review we elaborate the application of colloidal synthesis techniques for the preparation of lead chalcogenide based QDs. We specifically focus on the influence of surface ligands on the synthesis of QDs and their solution‐phase ligand exchange. Given the importance of lead chalcogenide QDs as potential light harvesters, we also pay particular attention to the current progress of these QDs in photovoltaic applications.     

Large-scale CdX (X=S, Se) microtube arrays on glass substrate: transformation of CdOHCl microrod arrays by a simple template-sacrificing solution method

Large-scale arrayed CdX (X=S, Se) microtubes have been successfully prepared on glass substrate by a simple solution route. In this process, cadmium hydroxyl chloride (CdOHCl) microrod arrays, which could be directly grown on glass surface in solution of CdCl₂ and methenamine, were used not only as a source of cadmium but also as a new reactive template to fabricate these highly ordered cadmium chalcogenide tube arrays, and the orientation of CdOHCl microrods on glass substrate could be easily achieved by pretreating the glass surface with appropriate concentration of NaOH aqueous solution. The transformation from arrayed CdOHCl rods to CdS and CdSe microtube arrays were conducted in thioacetamide and Na₂SeSO₃ solution, respectively. The conversion was convenient, and no CdOHCl crystallites were detected in the final products measured by X-ray powder diffraction. The hexagonal prismatic morphology and orientation of CdOHCl rods were perfectly maintained in the as-prepared cadmium chalcogenide films according to scanning electron microscopy. Transmission electron microscopy was used to further characterize these microtube structures. The effect of NaOH pretreatment on CdOHCl orientation and the formation of tubular structures were also discussed.