Chemically modified ISFETs

Ever since an ISFET that was chemically modified by a valinomycin-containing PVC membrane was reported [141], there has been general consensus on the advantages of this type of microsensor over conventional ISEs. Some serious problems have also been acknowledged, though e.g. the low mechanical stability of the membranes, the interference of COj in the potentiometric response, the lack of a stable micro-reference electrode and the relatively high drift rate of ISFETs). Attachment of the membrane can... 

Another approach to the solution of this problem is the development of the REFET or reference FET (Fig. 8). Two ISFETs are manufactured on the same sensor chip and the response of both measured and compared. One of the ISFETs is chemically modified to render it less sensitive (or preferably totally insensitive) to ions present in the sample solution. The signal here is actually the difference between the two ISFETs, thereby meaning that effects due to temperature changes and other external effects tend to cancel out and be minimised. 

On-wafer membrane deposition and patterning is an important aspect of the fabrication of planar, silicon based (bio)chemical sensors. Three examples are presented in this paper amperometric glucose and free chlorine sensors and a potentiometric ISRET based calcium sensitive device. For the membrane modified ISFET, photolithographic definition of both inner hydrogel-type membrane (polyHEMA) and outer siloxane-based ion sensitive membrane, of total thickness of 80 pm, has been performed. An identical approach has been used for the polyHEMA deposition on the free chlorine sensor. On the other hand, the enzymatic membrane deposition for a glucose electrode has been performed by either a lift-off technique or by an on-chip casting. 

The first example of chemically modified field-effect transistors (CHEMFETs) was reported by Janata et al. [15] in 1978 for ion-sensitive field-effect transistors (ISFETs) in which the gate oxide was covered with a PVC membrane containing... 

Typical profiles for the potential response of Na -ISFETs based on the sol-gel-derived membranes modified chemically by alkoxysilylated 16-crown-5 (7) and bis(12-crown-4) (11), together with anion excluder (9) show that both of the Na -ISFETs have high sensitivity with a Nernstian response to Na activity changes in wide activity ranges of 3 x 10 to 1 M (Fig. 12). The potential response is quite fast in the Na -ISFETs in spite of the covalent bonding of the neutral carriers to the ion-sensing membranes, as exemplified in the membrane system of the bis(12-crown-4) (11). Some mobility of the chemically bonded neutral carriers can probably be maintained in the present sol-gel-derived membranes. The response time ( 9o) is several seconds for both of the Na -... 

FIG. 12 Potential response to Na activity changes of Na -ISFETs based on sol-gel-derived membranes modified chemically by alkoxysilyl-substituted neutral carriers (7) (O) and (8) ( ), together with anion excluder (9). (From Ref. 49). 

FIG. 15 Potential response of anion ISFETs based on sol-gel-derived membranes encapsulating trioctylmethylammonium chloride ( ) and modified chemically by alkoxysilylated quaternary ammonium salt (12) (O) to CC-activity changes. (From Ref 50.)... 

Successful operation of potentiometric chemosensors opened up the possibility for the fabrication of chemical field-effect transistors (chemFETs) and ion-selective field-effect transistors (ISFETs). A sensing element in these devices, i.e. the MIP film loaded with the molecular, neutral or ionic, respectively, imprinted substance is used to modify surface of the transistor gate area. Apparently, any change in the potential of the film due to its interactions with the analyte alters the current flowing between the source and drain. 

The reference ISFET can be modified by chemically reacting the SiOH groups with trimethoxysilanes [7]. An alternative method involves deposition of a hydrophobic polymer on the surface, for example by thermal deposition of parylene [85]. These layers tend to be chemically bound to the SiOH surface, leading to enhanced stability and long lifetimes. Also the layers are very thin, which is essential because of decreased electrical sensitivity as the insulator thickness increases [9]. For ion-blocking layers, a stable attachment has been realized by plasma deposition [86,87]. 

The scope of ion-selective electrodes (ISEs) has been greatly enhanced by employing a poly(vinyl chloride) matrix to entangle sensor cocktail materials. Fbr ISFET devices an in situ photopolymerisation of monobutyl methacrylate provides a viable poly(butyl methacrylate) calcium sensor film with good gate adhesion properties. One or more enzymes can be chemically immobilized on modified nylon mesh. The resultant matrices are suitable for the amperometric assay of carbohydrates in blood and food products. 

A new type of (bio)chemical sensor, the redox-sensitive field-effect transistor is described It consists of a conventional ISFET with a noble metal added on top of the gate insulator The gate electrode is modified with a redox polymer containing osmium complexes The potentiostatic multi-puls method is introduced which allows the adjustment of the redox potential of the gate to a desired value in a stepwise way It is shown that the open circuit potential after switching off the potentiostat is a good measurement of the presence of the redox active species NADH... 

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