Semiconductivity

In the past, there have been two main types of interpretations of chemisorption and catalysis on chromia. One is more or less of the type given in this chapter (for example, 39, 56, 63a, 66). The other is based upon theories of semiconductors (for example, 68-70). Chromia is a semiconductor at high temperatures (20). No complete theory of chemisorption on chromia is possible at present one can only use approximate treatments. However, in our opinion, the first type of approximation (which is related to coordination chemistry and cry.stal field theory) is much more useful than the second type for reactions in reducing atmospheres at lower temperatures, say below 300°. Morin (70a) has given an analysis of transition metal oxides which indicates that the 3d band in a-Ci 203 is so narrow as to correspond to 3d charge carriers localized on the cations. 

It is difficult to imagine any band theory for an amorphous chromia activated at 250°. In terms of semiconductor theory, it is difficult to imagine such large surface coverages as we observe at —78°. The close correlations which are developing between homogeneous catalysis and catalysis on chromia cannot be understood at all on the basis of semiconductor theory. 

The electrical conductivity of semiconducting materials is not as high as that of metals nevertheless, they have some unique electrical characteristics that render them especially useful. The electrical properties of these materials are extremely sensitive to the presence of even minute concentrations of impurities. Intrinsic semkonductois are those in which the electrical behavior is based on the electronic structiue inherent in the pure material. When the electrical characteristics are dictated by impurity atoms, the semiconductor is said to be extrinsic. 

---

In contrast to metals, most studies have concentrated on insulators and semiconductors where the optical structure readily lends itself to a straightforward interpretation. Within certain approximations, the imaginary part of the dielectric fiinction for semiconducting or insulating crystals is given by... 

Typical results for a semiconducting liquid are illustrated in figure Al.3.29 where the experunental pair correlation and structure factors for silicon are presented. The radial distribution function shows a sharp first peak followed by oscillations. The structure in the radial distribution fiinction reflects some local ordering. The nature and degree of this order depends on the chemical nature of the liquid state. For example, semiconductor liquids are especially interesting in this sense as they are believed to retain covalent bonding characteristics even in the melt. 

Plenary 14. A K Ramdas et al, e-mail address akr phYsics.purdue.edu (RS). Electronic RS studies of doped diamond as potential semiconducting materials. A Raman active Is (p3 2) ls (Pi/2 transition of a hole... 

Free-electron lasers have long enabled the generation of extremely intense, sub-picosecond TFlz pulses that have been used to characterize a wide variety of materials and ultrafast processes [43]. Due to their massive size and great expense, however, only a few research groups have been able to operate them. Other approaches to the generation of sub-picosecond TFlz pulses have therefore been sought, and one of the earliest and most successfid involved semiconducting materials. In a photoconductive semiconductor, carriers (for n-type material, electrons)... 

The most connnonly used detector in EPR is a semiconducting silicon crystal in contact with a tungsten wire, which acts as an MW rectifier. At microwatt powers, crystal detectors are typically non-linear and render a... 

As outlined above, electron transfer through the passive film can also be cmcial for passivation and thus for the corrosion behaviour of a metal. Therefore, interest has grown in studies of the electronic properties of passive films. Many passive films are of a semiconductive nature [92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102 and 1031 and therefore can be investigated with teclmiques borrowed from semiconductor electrochemistry—most typically photoelectrochemistry and capacitance measurements of the Mott-Schottky type [104]. Generally it is found that many passive films cannot be described as ideal but rather as amorjDhous or highly defective semiconductors which often exlribit doping levels close to degeneracy [105]. 

Stella A ef al 1996 Comparative study of thermodynamic properties of metallic and semiconducting nanoparticles in a dielectric matrix Mater. Res. Soc. Symp. Proc. 400 161... 

Semiconductors may also be made from a maferial which is normally an insulator by infroducing an impurify, a process known as doping. Figure 9.9 shows fwo ways in which an impurify may promote semiconducting properties. In Figure 9.9(a) fhe dopanf has one more valence election per atom fhan fhe hosf and confribufes a band of filled impurify levels 1 close to fhe conduction band of fhe hosf. This characterizes an n-fype semiconductor. An example is silicon (KL3s 3p ) doped wifh phosphoms (KL3s 3p ), which reduces fhe band gap to abouf 0.05 eY Since kT af room femperafure is abouf 0.025 eY the phosphoms... 

The highly conductive class of soHds based on TTF—TCNQ have less than complete charge transfer (- 0.6 electrons/unit for TTF—TCNQ) and display metallic behavior above a certain temperature. However, these soHds undergo a metal-to-insulator transition and behave as organic semiconductors at lower temperatures. The change from a metallic to semiconducting state in these chain-like one-dimensional (ID) systems is a result of a Peieds instabihty. Although for tme one-dimensional systems this transition should take place at 0 Kelvin, interchain interactions lead to effective non-ID behavior and inhibit the onset of the transition (6). 

Charge-Transfer Salts. Most charge-transfer salts can be prepared by direct mixing of donors and acceptors in solution. Semiconducting salts of TCNQ have been prepared with a variety of both organic and inorganic counterions. Simple salts of the type TCNQ can be obtained by direct reaction of a metal such as copper or silver with TCNQ in solution. Solutions of metal iodides can be used in place of the metals, and precipitation of the TCNQ salt occur direcdy (24). 

Polymers. The Tt-conjugated polymers used in semiconducting appHcations are usually insulating, with semiconducting or metallic properties induced by doping (see Flectrically conductive polymers). Most of the polymers of this type can be prepared by standard methods. The increasing use of polymers in devices in the last decade has led to a great deal of study to improve the processabiUty of thin films of commonly used polymers. 

---