Transition semiconductors

Small metal clusters are also of interest because of their importance in catalysis. Despite the fact that small clusters should consist of mostly surface atoms, measurement of the photon ionization threshold for Hg clusters suggest that a transition from van der Waals to metallic properties occurs in the range of 20-70 atoms per cluster [88] and near-bulk magnetic properties are expected for Ni, Pd, and Pt clusters of only 13 atoms [89] Theoretical calculations on Sin and other semiconductors predict that the stmcture reflects the bulk lattice for 1000 atoms but the bulk electronic wave functions are not obtained [90]. Bartell and co-workers [91] study beams of molecular clusters with electron dirfraction and molecular dynamics simulations and find new phases not observed in the bulk. Bulk models appear to be valid for their clusters of several thousand atoms (see Section IX-3). 

Figure Bl.22.4. Differential IR absorption spectra from a metal-oxide silicon field-effect transistor (MOSFET) as a fiinction of gate voltage (or inversion layer density, n, which is the parameter reported in the figure). Clear peaks are seen in these spectra for the 0-1, 0-2 and 0-3 inter-electric-field subband transitions that develop for charge carriers when confined to a narrow (<100 A) region near the oxide-semiconductor interface. The inset shows a schematic representation of the attenuated total reflection (ATR) arrangement used in these experiments. These data provide an example of the use of ATR IR spectroscopy for the probing of electronic states in semiconductor surfaces [44]-...

Wang L S and Wu H 1998 Probing the electronic structure of transition metal clusters from molecular to bulk-like using photoeieotron spectroscopy Cluster Materials, Advances In Metal and Semiconductor Clusters vo 4, ed M A Duncan (Greenwich JAI Press) p 299... 

There are many ways of increasing tlie equilibrium carrier population of a semiconductor. Most often tliis is done by generating electron-hole pairs as, for instance, in tlie process of absorjition of a photon witli h E. Under reasonable levels of illumination and doping, tlie generation of electron-hole pairs affects primarily the minority carrier density. However, tlie excess population of minority carriers is not stable it gradually disappears tlirough a variety of recombination processes in which an electron in tlie CB fills a hole in a VB. The excess energy E is released as a photon or phonons. The foniier case corresponds to a radiative recombination process, tlie latter to a non-radiative one. The radiative processes only rarely involve direct recombination across tlie gap. Usually, tliis type of process is assisted by shallow defects (impurities). Non-radiative recombination involves a defect-related deep level at which a carrier is trapped first, and a second transition is needed to complete tlie process. 

The light emitted in the spontaneous recombination process can leave tire semiconductor, be absorbed or cause additional transitions by stimulating electrons in tire CB to make a transition to tire VB. In tliis stimulated recombination process anotlier photon is emitted. The rate of stimulated emission is governed by a detailed balance between absorjDtion, and spontaneous and stimulated emission rates. Stimulated emission occurs when tire probability of a photon causing a transition of an electron from tire CB to VB witli tire emission of anotlier photon is greater tlian that for tire upward transition of an electron from tire VB to tire CB upon absorjDtion of tire photon. These rates are commonly described in tenns of Einstein s H and 5 coefficients [8, 43]. For semiconductors, tliere is a simple condition describing tire carrier density necessary for stimulated emission, or lasing. This carrier density is known as... 

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). 

Fig. 3. An overview of atomistic mechanisms involved in electroceramic components and the corresponding uses (a) ferroelectric domains capacitors and piezoelectrics, PTC thermistors (b) electronic conduction NTC thermistor (c) insulators and substrates (d) surface conduction humidity sensors (e) ferrimagnetic domains ferrite hard and soft magnets, magnetic tape (f) metal—semiconductor transition critical temperature NTC thermistor (g) ionic conduction gas sensors and batteries and (h) grain boundary phenomena varistors, boundary layer capacitors, PTC thermistors.

Phase transitions are involved in critical temperature thermistors. Vanadium, VO2, and vanadium trioxide [1314-34-7] V2O3, have semiconductors—metal transitions in which the conductivity decreases by several orders of magnitude on cooling. Electronic phase transitions are also observed in superconducting ceramics like YBa2Cu30y but here the conductivity increases sharply on cooling through the phase transition. 

The range of photon energies (160 to 0.12 kJ/mol (38-0.03 kcal/mol)) within the infrared region corresponds to the energies of vibrational and rotational transitions of individual molecules, of electronic transitions in many semiconductors, and of vibrational transitions in crystalline lattices. Semiconductor electronics and crystal lattice transitions are beyond the scope of this article. 

Solid-State Lasers. Sohd-state lasers (37) use glassy or crystalline host materials containing some active species. The term soHd-state as used in connection with lasers does not imply semiconductors rather it appHes to soHd materials containing impurity ions. The impurity ions are typically ions of the transition metals, such as chromium, or ions of the rare-earth series, such as neodymium (see Lanthanides). Most often, the soHd material is in the form of a cylindrical rod with the ends poHshed flat and parallel, but a variety of other forms have been used, including slabs and cylindrical rods with the ends cut at Brewster s angle. 

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. 

Semiconductors can be divided into two groups direct and indirect band gap materials. In direct semiconductors the minimum energy in the conduction band and the maximum in the valence band occur for the same value of the electron momentum. This is not the case in indirect materials. The difference has profound consequences for the transitions of electrons across the band gap in which light is emitted, the radiative transitions, of interest here. 

The uncertainty principle, according to which either the position of a confined microscopic particle or its momentum, but not both, can be precisely measured, requires an increase in the carrier energy. In quantum wells having abmpt barriers (square wells) the carrier energy increases in inverse proportion to its effective mass (the mass of a carrier in a semiconductor is not the same as that of the free carrier) and the square of the well width. The confined carriers are allowed only a few discrete energy levels (confined states), each described by a quantum number, as is illustrated in Eigure 5. Stimulated emission is allowed to occur only as transitions between the confined electron and hole states described by the same quantum number. 

Protein Computers. The membrane protein bacteriorhodopsin holds great promise as a memory component in future computers. This protein has the property of adopting different states in response to varying optical wavelengths. Its transition rates are very rapid. Bacteriorhodopsin could be used both in the processor and storage, making a computer smaller, faster, and more economical than semiconductor devices (34). 

Sihcon is a Group 14 (IV) element of the Periodic Table. This column iacludes C, Si, Ge, Sn, and Pb and displays a remarkable transition from iasulatiag to metallic behavior with increasing atomic weight. Carbon, ia the form of diamond, is a transparent iasulator, whereas tin and lead are metals ia fact, they are superconductors. SiUcon and germanium are semiconductors, ie, they look metaUic, so that a poHshed siUcon wafer is a reasonable gray-toned mirror, but they conduct poorly. Traditionally, semiconductors have been defined as materials whose resistance rises with decreasiag temperature, unlike metals whose resistance falls. 

The equihbtium lever relation, np = can be regarded from a chemical kinetics perspective as the result of a balance between the generation and recombination of electrons and holes (21). In extrinsic semiconductors recombination is assisted by chemical defects, such as transition metals, which introduce new energy levels in the energy gap. The recombination rate in extrinsic semiconductors is limited by the lifetime of minority carriers which, according to the equihbtium lever relation, have much lower concentrations than majority carriers. Thus, for a -type semiconductor where electrons are the minority carrier, the recombination rate is /S n/z. An = n — is the increase of the electron concentration over its value in thermal equihbtium, and... 

Semiconductor devices ate affected by three kinds of noise. Thermal or Johnson noise is a consequence of the equihbtium between a resistance and its surrounding radiation field. It results in a mean-square noise voltage which is proportional to resistance and temperature. Shot noise, which is the principal noise component in most semiconductor devices, is caused by the random passage of individual electrons through a semiconductor junction. Thermal and shot noise ate both called white noise since their noise power is frequency-independent at low and intermediate frequencies. This is unlike flicker or ///noise which is most troublesome at lower frequencies because its noise power is approximately proportional to /// In MOSFETs there is a strong correlation between ///noise and the charging and discharging of surface states or traps. Nevertheless, the universal nature of ///noise in various materials and at phase transitions is not well understood. 

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