The Nature of Semiconductors

Before discussing the preparation of gamma-ray detectors, it is necessary, without delving into solid state physics in any great detail, to understand the basic nature of semiconductor materials. In an absolutely pure semiconductor material, thermal excitation would promote a certain number of electrons from the valence band to the conduction band, leaving behind an equal number of positively charged holes. A material of this kind containing 

On the other hand, five valent impurities, such as arsenic or phosphorus, will have one electron in excess of that required for electronic uniformity. The impurity atom will be a donor atom sitting in a donor site and will introduce donor states just below the conduction band. Germanium with such impurities is n-type germanium ( n for negative donor impurities). 

of course, possible that any particnlar piece of germanium will contain both types of impurity. Each of these impurities will effectively negate one of the opposite type and the net semiconductor character of the material will depend upon the type of impurity in excess. In the unlikely event of an exact cancellation, the material would be called compensated germanium. There is, of course, scope for adjusting the nature of the semiconductor by adding small amounts of impurity of an appropriate type a process known as doping. 

The resistivity, p, is a function of the concentration of dopant atoms in the material, N, and can be calculated as follows (where e is the charge on the electron)  

Not surprisingly, the details of such processes are a closely guarded commercial secret. 

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It is no exaggeration to claim that it was the extensive worldwide body of research on semiconductors from the late 1930s onwards that converted physicists to the recognition that scrupulous control of purity, stoichiometry and crystal perfection, together with characterisation methods that could check on these features, are a precondition of understanding the nature of semiconductors and thus also a precondition of exploiting them successfully - indeed, not only semiconductors but, by extension, many kinds of materials. 

For the influence of the specific surface area of the semiconductor powder on the rate of product formation, two opposite effects are of major importance [81]. One is concerned with the rate of electron-hole recombination which increases linearly with surface area, and accordingly the reaction rate should decrease. The other is a linear increase in the reaction rate of the reactive electron-hole pair with the adsorbed substrates, which should increase product formation. It is therefore expected that, depending on the nature of semiconductor and substrates, the reaction rate, or increasing surface area. This is nicely reflected by the CdS/Pt-catalyzed photoreduction of water by a mixture of sodium sulfide and sulfite. The highest p values are observed with small surface areas and are constant up to 2 m g". From there a linear decrease to almost zero at a specific surface area of 6 m g" takes place. Upon further increase to 100 m g" this low quantum yield stays constant [82]. 

The synthesized doped glasses acquired specific color at the cooling step depending on the nature of semiconductor and its concentration. We have succeed in fabrication of the glasses with dopant concentration up to 0.75 wt% that was quite sufficient for an appropriate optical absorption of samples with thickness of tenths of millimeters. An increase of dopant concentration in the case of tellurides was difficult because of their lower solubility. 

Before discussing the photoelectrochemical cells, a brief review of the nature of semiconductors is perhaps desirable. The electronic properties of solids can be described in terms of a band model which treats the behavior of electrons moving in the field of the atomic nuclei. When a solid is formed, the isolated atoms, which are characterized by filled and vacant atomic orbitals are assembled into a lattice containing about 5 X 10 atoms cm This leads to the formation of new molecular orbitals which are so closely spaced that they form essentially continuous bands. 

Direct and Indirect Energy Gap. The radiative recombination rate is dramatically affected by the nature of the energy gap, E, of the semiconductor. The energy gap is defined as the difference in energy between the minimum of the conduction band and the maximum of the valence band in momentum, k, space. Eor almost all semiconductors, the maximum of the valence band occurs where holes have zero momentum, k = 0. Direct semiconductors possess a conduction band minimum at the same location, k = O T point, where electrons also have zero momentum as shown in Eigure la. Thus radiative transitions that occur in direct semiconductors satisfy the law of conservation of momentum. 

A semiconductor can be described as a material with a Fermi energy, which typically is located within the energy gap region at any temperature. If a semiconductor is brought into electrical contact with a metal, either an ohmic or a rectifying Schouky contact is formed at the interface. The nature of the contact is determined by the workfunction, (the energetic difference between the Fermi level and the vacuum level), of the semiconductor relative to the mclal (if interface effects are neglected - see below) 47J. 

The interest of physicists in the conducting polymers, their properties and applications, has been focused on dry materials 93-94 Most of the discussions center on the conductivity of the polymers and the nature of the carriers. The current knowledge is not clear because the conducting polymers exhibit a number of metallic properties, i.e., temperature-independent behavior of a linear relation between thermopower and temperature, and a free carrier absorption typical of a metal. Nevertheless, the conductivity of these specimens is quite low (about 1 S cm"1), and increases when the temperature rises, as in semiconductors. However, polymers are not semiconductors because in inorganic semiconductors, the dopant substitutes for the host atomic sites. In conducting polymers, the dopants are not substitutional, they are part of a nonstoichiometric compound, the composition of which changes from zero up to 40-50% in... 

In the solid, electrons reside in the valence band but can be excited into the conduction band by absorption of energy. The energy gap of various solids depends upon the nature of the atoms comprising the solid. Semiconductors have a rather narrow energy gap (forbidden zone) whereas that of insulators is wide (metals have little or no gap). Note that energy levels of the atoms "A" are shown in the valence band. These will vary depending upon the nature atoms present. We will not delve further into this aspect here since it is the subject of more advanced studies of electronic and optical materieds. 

In order to have more infoimation on the nature of the oxygen species active in partial and total oxidation we investigated the interaction of the hydrocarbons with the pre-oxidized surfaces of oxides where different types of surface oxygen species are formed. In particular we investigated p-type semiconductors like chromia, chromites and cobalt oxide C03O4. Moreover, we studied n-type metal oxides like FezOs, metal ferrites and CuObased catalysts. 

By the nature of conduction and values of conductivity, materials can be classified as conductors, semiconductors, or insulators (dielectrics). It is a special attribute of conductors that free electric charges are present in them. The migration of these free charges in an applied electric field manifests itself as electric current. 

Electrochemical reactions at semiconductor electrodes have a number of special features relative to reactions at metal electrodes these arise from the electronic structure found in the bulk and at the surface of semiconductors. The electronic structure of metals is mainly a function only of their chemical nature. That of semiconductors is also a function of other factors acceptor- or donor-type impurities present in bulk, the character of surface states (which in turn is determined largely by surface pretreatment), the action of light, and so on. Therefore, the electronic structure of semiconductors having a particular chemical composition can vary widely. This is part of the explanation for the appreciable scatter of experimental data obtained by different workers. For reproducible results one must clearly define all factors that may influence the state of the semiconductor. 

Depending on the nature of the electrode and reaction, the carriers involved in an electrochemical reaction at a semiconductor electrode can be electrons from the conduction band (in the following to be called simply electrons), electrons from the valence band (holes), or both. The concentration of the minority carriers in semiconductors (electrons in p-type, and holes in n-type semiconductors) is always much... 

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