Ion-sensitive field effect transistors using carbon nanotubes as the transducing layer

We report a new type of ion-sensitive field effect transistor (ISFET). This type of ISFET incorporates a new architecture, containing a network of single-walled carbon nanotubes (SWCNTs) as the transduction layer, making an external reference electrode unnecessary. To show an example of its application, the SWCNT-based ISFET is able to detect at least 10(-8) M of potassium in water using an ion-selective membrane containing valinomycin.     

A novel Urushi matrix chloride ion-selective field effect transistor

A durable chloride ion-selective field effect transistor (ISFET) is proposed with Urushi as the membrane matrix. The chloride ion-sensing material is a quaternary ammonium chloride: trioctylmethylammonium chloride (TOMA-Cl) or tridodecylmethylammonium chloride (TDMA-Cl). The optimum composition of the Urushi membrane was found by use of Urushi ion-selective electrodes. The mixture with the most favourable composition was coated on the gate region of the FET device. The Urushi ISFET with TDMA-Cl proved to be superior to that with TOMA-Cl, in sensitivity, linearity and selectivity. The Urushi ISFET with TDMA-Cl showed a linear response of about -51 mV per decade change of chloride ion activity in the range 10(-4)-1M. The Urushi ISFET showed excellent stability and durability for over two months, because of strong adhesion of the membrane to the Si(3)N(4) gate.     

Towards advanced chemical microsensors-an overview

The paper presents design and performance of miniaturized chemical sensors based on silicon transducers: ion-sensitive field effect transistor (ISFET) and solid-state electrode (SSE). The sensors were fabricated as back-side contact structures, which facilitate their mounting in a flow-cell. The role of an intermediate layer between the transducer and the ion-selective membrane is discussed. Various polymeric matrices were used to manufacture microsensors: polysiloxanes, polyacrylates (polymethacrylates), polyurethanes.     

Ion-selective field effect transistors with polymeric membranes

The construction and operation of ion-selective field effect transistors (ISFET) with polymeric membranes are described, and their electrical and chemical performance are discussed. The H⁺, K⁺, and Ca²⁺ ISFET's all show responses similar to those of the corresponding ion-selective electrodes, with t_95% response times of approximately 40 ms and accurate ion activity measurements for periods up to one month.     

Sodium ion sensors based on dibenzo-16-crown-5 compounds with amide side arms

Abstract

Lipophilic dibenzo-16-crown-5 compounds with amide-containing side arms attached to the central carbon atom of the three-carbon bridge in the polyether ring have been applied as neutral carriers for sodium ion-selective field-effect transistors (Na⁺-ISFET′s). ISFET′s based on these lariat ether amides exhibit excellent Na⁺/K⁺ selectivities (K_Na′K ^Pot = 7 × 10^?3) and Na⁺/H⁺ selectivities (K_Na′H ^Pot = 3 × 10^?3) with good selectivities for Na⁺ over other alkali metal cations and alkaline-earth metal cations. High sensor durability was obtained for these ISFET′s.     

Role of ion-selective membranes in the carbon balance for CO2 electroreduction via gas diffusion electrode reactor designs

In this work, the effect of ion-selective membranes on the detailed carbon balance was systematically analyzed for high-rate CO₂ reduction in GDE-type flow electrolyzers. By using different ion-selective membranes, we show nearly identical catalytic selectivity for CO₂ reduction, which is primarily due to a similar local reaction environment created at the cathode/electrolyte interface via the introduction of a catholyte layer. In addition, based on a systematic exploration of gases released from electrolytes and the dynamic change of electrolyte speciation, we demonstrate the explicit discrepancy in carbon balance paths for the captured CO₂ at the cathode/catholyte interface via reaction with OH⁻ when using different ion-selective membranes: (i) the captured CO₂ could be transported through an anion exchange membrane in the form of CO₃²⁻, subsequently releasing CO₂ along with O₂ in the anolyte, and (ii) with a cation exchange membrane, the captured CO₂ would be accumulated in the catholyte in the form of CO₃²⁻, while (iii) with the use of a bipolar membrane, the captured CO₂ could be released at the catholyte/membrane interface in the form of gaseous CO₂. The unique carbon balance path for each type of membrane is linked to ion species transported through the membranes.

In this work, the effect of ion-selective membranes on the detailed carbon balance was systematically analyzed for high-rate CO₂ reduction in GDE-type flow electrolyzers.     

Application of an ion-selective field effect transistor with a photocured polymer membrane in nephrology for determination of potassium ions in dialysis solutions and in blood plasma

Application of a potassium ion sensor based on an ion sensitive field effect transistor (ISFET) for ion control of a dialysis solution in an artificial kidney and in blood plasma of patients treated by hemodialysis is presented. Sensors and their long-term stability were characterised in constant contact with test solutions. Test results are compared to those obtained with conventional ion-selective electrodes and commercial blood ion analyser. Tested ISFET sensors showed high reliability in potassium ion measurements in the physiologically significant concentration range which, along with low cost of their production, makes them promising for cited application.     

AgI-Ag2O-V2O5 glasses as ion-to-electron transducers for the construction of all-solid-state microelectrodes

A method for the fabrication of ion-selective all-solid-state microelectrodes is presented. The ion-to-electron transduction process takes place into the transducer material. In this approach, AgI-Ag₂O-V₂O₅ glasses, which exhibit ionic and electrical conductivity are applied as ion-to-electron transducers of polymeric membrane microelectrodes. All-solid-state electrodes based on potassium-sensitive poly(vinyl chloride) membranes, deposited directly on the surface of glass composites, exhibited theoretical responses. Their selectivity and durability were comparable to planar microelectrodes containing an internal electrolyte immobilized in the intermediate hydrogel layer. The only disadvantage of the proposed structures was their limited reproducibility. Moreover, it was found that the unmodified AgI-Ag₂O-V₂O₅ glasses can be applied as ion-sensitive membrane of solid-state microelectrodes for the determination of Ag⁺ and I⁻ ions.     

Development of microbiosensors

Semiconductor fabrication technology was used for development of ion sensitive field effect transistor (ISFET) and micro-electrodes which have been utilized as transducers of enzyme-based microbiosensors. A urea sensor consisted of two ISFETs; one ISFET is urease-coated ISFET and the other ISFET is reference ISFET. A linear relationship was obtained between the initial rate of voltage change and the logarithm of urea concentration over the range 1.3 to 16.7 mM. ATP and hypoxanthine sensors were also developed utilizing ISFET as a transducer. Furthermore, microelectrodes such as hydrogen peroxide and oxygen sensors were prepared by the silicone fabrication technology. A glucose sensor consisted of a hydrogen peroxide electrode and immobilized glucose oxidase membrane. A linear relationship was observed between the current increase and the concentration of glucose (1–100 mg dl⁻¹). A microoxygen electrode was constructed from Au electrodes, polymer matrix containing alkaline electrolyte and a photocross-linkable polymer membrane. This electrode was used as a transducer in microglucose sensor. A microglutamic acid sensor is also described.     

Adding Plasticizer Dispersible Conducting Polymer to the Ion-selective Membrane Composition – Revitalizing Single Piece Ion-selective Electrodes Concept

Typically, ion-selective electrodes used in current triggered electrochemical sensing apply a conducting polymer layer covered with an ion-selective membrane. In this work we propose an ion-selective membrane containing a dispersed conducting polymer. Thus obtained system allows elimination of the Achilles hell of heterogeneous ion-selective membranes containing solid particulates dispersed within the ion-selective polymeric membrane. The herein proposed system, even for high conducting polymer loading equal to 5 % w/w, is characterized with insensitivity towards redox interferences, as well as potentiometric detection limits, selectivity well comparable with that for other ion-selective electrodes constructions. Under voltammetric conditions, with increasing loading of the conducting polymer in the membrane cathodic peak potentials are shifted towards more negative values, yet the linear dependence of the peak potential on logarithm of concentration of the analyte in the solution is preserved.     

Micro Ammonia Sensor

Abstract

A micro ammonia sensor, consisting of an ISFET covered with a dry membrane which is made from nonactin and substituted poly-γ-methyl-L-glutamate (PMG) is described. The gate output voltage of the micro ammonia sensor increased with NH₄OH addition. The response time of the sensor was 2 min at 30°C, and the sensor exhibited superior selectivity for NH₄ ⁺ compared to a pH sensitive ISFET.     

Covalent binding of sensor phases--a recipe for stable potentials of solid-state ion-selective sensors

In this work, a new concept of the solid-state sensors free from EMF instabilities is proposed. In order to prevent the formation of an aqueous layer underneath the ion-selective membrane, instead of improving the hydrophobicity of the monolayer, the moieties terminated with acrylate groups were incorporated within the redox-active monolayer structure. It allowed to “sew” all phases of the sensor (i.e., the transducer, the intermediate layer and the ion-selective membrane) and to obtain a stable and durable ion-selective sensor. It is shown that newly designed monolayer containing both the ferrocene- and the acrylate-terminated molecules does not affect the working parameters of the electrode, such as selectivity or the slope of the calibration curve, although the EMF drift of the sensor is significantly reduced to 0.2 mV per day.     

Design and performance of some microflow-cell potentiometric transducers

The paper presents and compares the design of three potentiometric transducers: ion-selective field effect transistor (ISFET), solid-state Ag/AgCl electrode and miniaturized classical Ag/AgCl electrode. The reported transducers were fabricated using different, less or more complicated and expensive, technologies. The transducers were constructed to be compatible with the sensor housing of the flow-cell, designed previously. Moreover, the back-side contact structures of the two planar devices, where electrical connectors and the sensing layer are on the opposite sides, facilitated their application in the flow analysis. Exemplary potassium-selective microsensors based on developed transducers were prepared, applying plasticized PVC and polysiloxane membranes containing valinomycine. The determined microsensor performances allowed comparison of their usefulness for multiparameter flow analysis.     

Silver and lead all-plastic sensors—polyaniline vs. poly(3,4-ethyledioxythiophene) solid contact

Silver and lead selective all-plastic ion-selective electrodes were obtained using poly(vinyl chloride)-based membranes and either poly(3,4-ethylenedioxythiophene) or polyaniline dispersion cast on an insulating plastic support as transducer and electrical lead. The effect of interactions of applied conducting polymer with analyte ions on potentiometric responses was evaluated and correlated with changes in elemental composition and element distribution within the ion-selective membrane and the conducting polymer transducer revealed in course of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) experiments. In the case of silver selective electrodes, potentiometric responses obtained are much dependent on the oxidation state of the polymer placed beneath the ion-selective membrane. For semi-oxidized polymer (poly(3,4-ethylenedioxythiophene)-based electrodes, linear responses with detection limit equal to 10^−5.4 M were obtained. For a more oxidized polyaniline (of higher conductivity), although the electrodes were pretreated exactly in the same way and tested in parallel, super Nernstian potential slope was recorded within the AgNO₃ activities range form 10⁻⁶ to 10⁻⁷ M. These responses were consistent with results of LA-ICP-MS, revealing profoundly higher silver signals intensities for poly(3,4-ethylenedioxythiophene) underlying silver selective membrane. It seems highly probable that silver is accumulated in this polymer layer as Ag⁰ due to spontaneous redox reaction leading to oxidation of the polymer; however, this process requires also the presence of silver ions at the interface. In fact, when reduced (deprotonated) polyaniline was used as transducer, the potentiometric responses of the sensor were, within the range of experimental error, the same as obtained for poly(3,4-ethylenedioxythiophene)-based sensor. On the other hand, for lead(II) selective sensors, the difference in responses of electrodes prepared using poly(3,4-ethylenedioxythiophene) or polyaniline was less pronounced, which is in accordance with the elemental composition of these sensors.     

Comparison of copper(II) ion-selective electrodes for measurements at micromolar concentrations

Four types of copper ion-selective electrodes have been tested for determining copper at concentrations below lO^-6 mol 1^l-1. None of the electrodes has a Nemstian response in dilute copper solutions in this concentration range, though their responses are linear in pCu buffer solutions. The causes of the deviations are a direct redox effect in the case of an electrode with a Cu_1.8,Se single crystal membrane, production of copper ions by oxidation of the membrane itself in Ag₂S—CuS membrane electrodes, and a combination of the two in the case of the R??i?ka Selectrode. The electrode potentials are affected by the oxygen content and pH of the sample solution and the condition of the membrane surface. Precision tests on two types of electrode are described.     

Characteristics of the hydrogen ion-sensitive field effect transistors with sol-gel-derived lead titanate gate

The sol-gel-derived lead titanate (PbTiO₃) membrane has been successfully applied as a pH sensitive layer to form the PbTiO₃ gate ion-sensitive field-effect transistor (ISFET). There exhibit the excellent quasi-Nernstian response of 56-59 mV pH⁻¹, good surface adsorption and anticorrosion characteristics via the C-V measurement of the EIS structure. At a specific pH concentration, the output and transfer characteristics are very similar to the behaviours of MOSFETs, and the ISFET model can be derived by the modified MOSFET model. As it operated in the nonsaturation region, there exhibits a linear pH response of about 56-59 mV pH⁻¹. On the other hand, as it operated in the saturation region, the pH response and linearity can be controlled by adjusting the V_GS values, e.g. the pH responses of −4.2, −24.8 and −31.3 μA pH⁻¹ and the correlation coefficients of 0.9491, 0.9995 and 0.9996 at V_GS=1, 3 and 5 V can be obtained, respectively. Besides, in order to get the best pH response and the minimized leakage current, the heat treatment temperature of the PbTiO₃ membrane must be limited between 350 and 450 °C.     

An all-solid-state polymeric membrane Pb-selective electrode with bimodal pore C60 as solid contact

An all-solid-state polymeric membrane Pb²⁺ ion-selective electrode (Pb²⁺-ISE) based on bimodal pore C₆₀ (BP-C₆₀) as solid contact has been developed. A BP-C₆₀ film can be readily formed on the surface of a glassy carbon electrode by electrochemical deposition. Cyclic voltammetry and electrochemical impedance spectroscopy have been employed to characterize the BP-C₆₀ film. The large double layer capacitance and fast charge-transfer capability make BP-C₆₀ favorable to be used as solid contact for developing all-solid-state ISEs. The all-solid-state BP-C₆₀-based Pb²⁺-ISE shows a Nernstian response in the range from 1.0 × 10⁻⁹ to 1.0 × 10⁻³ M with a detection limit of 5.0 × 10⁻¹⁰ M. The membrane electrode not only displays an excellent potential stability with the absence of a water layer between the ion-selective membrane and the underlying BP-C₆₀ solid contact, but also is insensitive to interferences from O₂, CO₂ and light. The proposed solid-contact Pb²⁺-ISE has been applied to determine Pb²⁺ in real water samples and the results agree well with those obtained by anodic stripping voltammetry.     

Development of an ion-sensitive field effect transistor based on PVC membrane technology with improved long-term stability

An NH -ISFET sensor based on PVC membrane technology with improved long-term stability has been developed. As a new approach, the plasticizer (tetra-n-undecyl) 3,3′,4,4′ -benzhydroltetracarboxylate (ETH2112) was used in membrane preparation. Its lipophilic nature provides a restricted diffusion of the membrane components to the external solution and improves membrane adhesion to the gate area of the ISFET. The good performance of this plasticizer was confirmed by comparison with usual plasticizers applied in standard ISE technology. Moreover, the durability and stability of the sensor were enhanced by the application of a graphite-epoxy layer as an internal reference between the gate area and the PVC membrane. This composite layer permits the reduction of the optical sensitivity and improves the adherence of the PVC membrane to the ISFET surface. Furthermore, this composite layer acts as a plug, preventing the entrance of water upon the encapsulant-chip interface, thus protecting electrical connections from moisture. As a result, an NH -ISFET with a long-term stability of three months and a sensitivity of −58.7 ± 2.3 mV decade⁻¹ in a linear range of 10⁻⁵ −0.1 mol dm⁻³ has been developed. The application of this sensor to a continuous-flow system has confirmed the feasibility of the technological approach proposed.     

Theory and applications of ion-selective electrodes Part III

This review of ion-selective electrodes is arranged in the same way as Parts I and II. The continuous growth of the whole subject should be noted. Theory has particularly progressed through mechanistic studies. Among new types of electrodes, ISFET systems have become important. Among new applications of both solid and liquid membrane electrodes, the fluoride electrode still predominates, closely followed by potassium electrodes. In the field of biological and medical applications, the steady growth is significant. More than 800 papers published between mid-1976 and the end of 1978 are mentioned in the review.     

Alcohol-FET sensor based on a complex cell membrane enzyme system

An alcohol -FET sensor was developed by use of a complex enzyme system in a cell membrane and an ion-sensitive field effect transistor (ISFET). The cell membrane of Gluconobacter suboxydans IFO 12528, which converts ethanol to acetic acid, was immobilized on the gate of an ISFET with calcium alginate gel coated with nitrocellulose. This ISFET (1), a reference ISFET without the cell membrane (ISFET 2) and an Ag/AgCl reference electrode were placed in 5 mM Trismalate buffer (pH 5.5, 25°C), and the differential output between ISFETS 1 and 2 was measured. The output of the sensor was stabilized by adding pyrroloquinoline quinone. The response time was ca. 10 min., and there was a linear relationship between the differential output voltage and the ethanol concentration up to 20 mg l^?1. The output of the sensor was stable for 40 h below 30°C. The sensor responded to ethanol, propan- 1-ol and butan- 1-ol, but not to methanol, propan-2-ol and butan-2-ol. The sensor was used to determine blood ethanol.