Chemisorption, sensors

In Chapter 1 we consider the physical and diemical basis of the method of semiconductor chemical sensors. The items dealing with mechanisms of interaction of gaseous phase with the surface of solids are considered in substantial detail. We also consider in this part the various forms of adsorption and adsorption kinetics processes as well as adsorption equilibria existing in real gas-semiconductor oxide adsorbent systems. We analyze the role of electron theory of chemisorption on... 

Thus, sensor effect deals with the change of various electrophysical characteristics of semiconductor adsorbent when detected particles occur on its surface irrespective of the mechanism of their creation. This happens because the surface chemical compounds obtained as a result of chemisorption are substantially stable and capable on numerous occasions of exchanging charge with the volume bands of adsorbent or directly interact with electrically active defects of a semiconductor, which leads to direct change in concentration of free carriers and, in several cases, the charge state of the surface. 

Thus, the major conclusions of tiie early studies by Volkenshtein and his colleagues applicable to the theory of the method of semiconductor gas sensors are the following a) chemisorption of particles on a semiconductor surface can be accompanied by a charge transfer between adsorption-induced surface levels and volume bands of adsorbent and b) only a certain fraction of absorbed particles is charged, the fraction being dependent on adsorbate and adsorbent. 

This radicals do not escape from the surface (this is indicated by a semiconductor microdetector located near the adsorbent surface) undergoing chemisorption on the same semiconductor adsorbent Him. Thus, they caused a decrease in the electric conductivity of the adsorbent sensor, similarly to the case where free radicals arrived to the film surface from the outside (for example, from the gas phase). Note that in these cases, the role of semiconductor oxide films is twofold. First, they play a part of adsorbents, and photoprocesses occur on their surfaces. Second, they are used as sensors of the active particles produced on the same surface through photolysis of the adsorbed molecular layer. 

Figure 4.8. displays oscillograms of evolution of the electric conductivity of the ZnO film in the process of catalytic dehydration of isopropyl alcohol at various temperatures of the catalyzer and equal portions of alcohol (5-10-2 Torr) admitted into the reaction cell. Experimental curves 1-4 are bell-shaped. We suppose that this fact is associated with two circumstances. On one hand, alcohol vapors dissociate on the oxide film producing hydrogen atoms. The jump in electric conductivity is caused by chemisorption of these hydrogen atoms on the film which plays a part of the sensor in this case. Chi the other hand, the drop in electric conductivity is caused by complete dissociation of the admitted portion of alcohol ( depletion of the source of hydrogen atoms) and by... 

Therefore, the interaction of the EEPs with the surface of sensors is a complex process that, being dependent on the nature of the surface and the nature of the active particle, results either in chemical transformation (chemisorption, for instance), or in transfer of excitation energy to a solid body, the processes that proceed at different velocities. 

VEM excitation energy relaxati( i. Such ways (channels) be probably chemisorption with charge transfer, production of phonons, ejection of electrons from surface states and traps, and the like. The further studies in this field will, obviously, make it possible to give a more complete characteristic of the VEM interaction with the surface of solid bodies and the possibilities of VEM detecting with the aid of semiconductor sensors. 

Self assembly of monolayers on gold electrodes provided a viable approach to sensor construction (see below), as well as permitted electrochemical characterization of the mechanism involved in chemisorption [233,236-239]. Electrochemical investigation of the spontaneous adsorption of n-alkanethiols onto a gold electrode and the subsequent desorption of the monolayer were rationalized in terms of oxidation and reduction of the sulfur atom [233]. More intimate details concerning the chemical fate of all species involved in the chemisorption process have not yet been elucidated. 

Since the pioneering work of Lane and Hubbard, there have been numerous examples of using chemisorption to modify electrode surfaces. For example, Anson and his coworkers have investigated chemisorption of various aromatic systems onto carbon electrodes [12]. In this case, n-electron density is shared between the electrode and the adsorbate molecule. Examples of electroactive molecules that have been used to modify electrode surfaces via this approach are shown in Table 13.1 [8]. It is of interest to note that from the very beginning, there was considerable interest in modifying electrode surfaces with biochemical substances (Table 13.1). This is because such modified electrodes seemed to be likely candidates for use in electrocatalytic processes and biochemical sensors (see Section V). 

Liess, M. and Steffes, H. (2000) The modulation of thermoelectric power by chemisorption a new detection principle for microchip chemical sensors. /. Electrochem. Soc. 147, 3151-3153. Tran-Minh, C. and Vallin, D. (1978) Anal. Chem. 50, 1874. 

The sensing mechanisms of the tin oxide based sensors have been discussed in many publications (9,10,11). The most widely accepted model for tin oxide based sensors operated at temperatures <400°C is based on the modulation of the depletion layer width in the semiconductor (sensor) due to chemisorption as illustrated schematically in Figure 6. For C2H 0H and Sn0x (or PdAu/Sn0x) interaction, the possible reaction steps may be expressed by the following equations ... 

In this part we will describe recent achievements in the development of biosensors based on DNA/RNA aptamers. These biosensors are usually prepared by immobilization of aptamer onto a solid support by various methods using chemisorption (aptamer is modified by thiol group) or by avidin-biotin technology (aptamer is modified by biotin) or by covalent attachment of amino group-labeled aptamer to a surface of self-assembly monolayer of 11-mercaptoundecanoic acid (11-MUA). Apart from the method of aptamer immobilization, the biosensors differ in the signal generation. To date, most extensively studied were the biosensors based on optical methods (fluorescence, SPR) and acoustic sensors based mostly on thickness shear mode (TSM) method. However, recently several investigators reported electrochemical sensors based on enzyme-labeled aptamers, electrochemical indicators and impedance spectroscopy methods of detection. 

Experimental data relating to the conductivity of composite films with M/SC nanoparticles are described by the classical percolation model in terms of tunnel processes. Chemisorption of chemical compounds on the surface of M/SC nanoparticles in films and the subsequent reactions with participation of chemisorbed molecules change the concentration of conducting electrons and/or barriers for their tunnel transfer between the nanoparticles with the result of strong influence on the film conductivity. Such films are used as conductometric sensors for detecting various substances in an atmosphere. 

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