The transition metal dichalcogenides are about 60 in number. Two-thirds of these assume layer structures. Crystals of such materials can be cleaved down to less than 1000 A and are then transparent in the region of direct band-to-band transitions. The transmission spectra of the family have been correlated group by group with the wide range of electrical and structural data available to yield useful working band models that are in accord with a molecular orbital approach. Several special topics have arisen; these include exciton screening, d-band formation, and the metal/insulator transition; also magnetism and superconductivity in such compounds. High pressure work seems to offer the possibility for testing the recent theory of excitonic insulators.

The transition metal dichalcogenides discussion and interpretation of the observed optical, electrical and structural properties

Phase-change materials are some of the most promising materials for data-storage applications. They are already used in rewriteable optical data storage and offer great potential as an emerging non-volatile electronic memory. This review looks at the unique property combination that characterizes phase-change materials. The crystalline state often shows an octahedral-like atomic arrangement, frequently accompanied by pronounced lattice distortions and huge vacancy concentrations. This can be attributed to the chemical bonding in phase-change alloys, which is promoted by p-orbitals. From this insight, phase-change alloys with desired properties can be designed. This is demonstrated for the optical properties of phase-change alloys, in particular the contrast between the amorphous and crystalline states. The origin of the fast crystallization kinetics is also discussed.

Phase-change materials for rewriteable data storage

The various origins of a frequency-dependent conductivity in amorphous semiconductors are reviewed, stressing particularly recent advances and the influences that factors such as correlation and non-random spatial distributions of electrically active centres can have on the a.c. conductivity. A comprehensive survey is given of the experimental a.c. data for two types of amorphous semiconductor, namely chalcogenide and pnictide materials. It is concluded that the a.c. behaviour at intermediate to high temperatures is well accounted for by the correlated-barrier-hopping model, whereas the low-temperature behaviour is probably due to atomic tunnelling.

A.c. conduction in amorphous chalcogenide and pnictide semiconductors

High-performance gas sensors prepared using p-type oxide semiconductors such as NiO, CuO, Cr2O3, Co3O4, and Mn3O4 were reviewed. The ionized adsorption of oxygen on p-type oxide semiconductors leads to the formation of hole-accumulation layers (HALs), and conduction occurs mainly along the near-surface HAL. Thus, the chemoresistive variations of undoped p-type oxide semiconductors are lower than those induced at the electron-depletion layers of n-type oxide semiconductors. However, highly sensitive and selective p-type oxide-semiconductor-based gas sensors can be designed either by controlling the carrier concentration through aliovalent doping or by promoting the sensing reaction of a specific gas through doping/loading the sensor material with oxide or noble metal catalysts. The junction between p- and n-type oxide semiconductors fabricated with different contact configurations can provide new strategies for designing gas sensors. p-Type oxide semiconductors with distinctive surface reactivity and oxygen adsorption are also advantageous for enhancing gas selectivity, decreasing the humidity dependence of sensor signals to negligible levels, and improving recovery speed. Accordingly, p-type oxide semiconductors are excellent materials not only for fabricating highly sensitive and selective gas sensors but also valuable additives that provide new functionality in gas sensors, which will enable the development of high-performance gas sensors.

Highly sensitive and selective gas sensors using p-type oxide semiconductors: Overview

In this paper, recent progress of phase change memory (PCM) is reviewed. The electrical and thermal properties of phase change materials are surveyed with a focus on the scalability of the materials and their impact on device design. Innovations in the device structure, memory cell selector, and strategies for achieving multibit operation and 3-D, multilayer high-density memory arrays are described. The scaling properties of PCM are illustrated with recent experimental results using special device test structures and novel material synthesis. Factors affecting the reliability of PCM are discussed.

Phase Change Memory

A model is presented for the structure and properties of active centers in lone-pair semiconductors, based on the possibility of unique bonding configurations which can arise from the presence of nonbonding orbitals. It is shown that the lowest-energy neutral center is unstable towards the creation of different positively and negatively charged centers, thus resulting in a negative effective correlation energy. These centers yield gap states which explain the unusual properties of lone-pair semiconductors.

Valence-Alternation Model for Localized Gap States in Lone-Pair Semiconductors

The electrical and optical properties of materials which are characterized by narrow bands in the vicinity of the Fermi energy are discussed. For such materials, electronic correlations and the electron-phonon coupling must be considered explicitly. Correlations in $f$ bands and in extremely narrow $d$ bands can be handled in the ionic limit of the Hubbard Hamiltonian. It is shown that free carriers in such bands form small polarons which contribute to conduction only by means of thermally activated hopping. Wider bands may also exist near the Fermi energy. Carriers in these bands may form large polarons and give a bandlike contribution to conductivity. A model is proposed for determining the density of states of pure stoichiometric crystals, beginning with the free-ion energy levels, and taking into account the Madelung potential, screening and covalency effects, crystalline-field stabilizations, and overlap effects. Exciton states are considered explicitly. The Franck-Condon principle necessitates the construction of different densities of states for electrical conductivity and optical absorption. Because of the bulk of experimental data presently available, the model is applied primarily to NiO. The many-particle density of states of pure stoichiometric NiO is calculated and is shown to be in agreement with the available experimental data. When impurities are present or nonstoichiometry exists, additional transitions must be discussed from first principles. The case of Li-doped NiO is discussed in detail. The calculations are consistent with the large mass of experimental information on this material. It is concluded that the predominant mechanism for conduction between 200 and 1000 \ifmmode^\circ\else\textdegree\fi{}K is the transport of hole-like large polarons in the oxygen $2p$ band. A method for representing the many-particle density of states on an effective one-electron diagram is discussed. It is shown that if correlations are important, donor or acceptor levels cannot be drawn as localized levels in the energy gap when multiple conduction or valence bands are present. This result comes about because extrinsic ionization energies of two correlated bands differ by an energy which bears no simple relation to the difference in energies of the intrinsic excitations, which are conventionally used to determine the relative positions of the bands.

Electrical and Optical Properties of Narrow-Band Materials

The application of sufficiently high electric fields to any material eventually results in deviations from linearity in the observed current-voltage I(V) characteristic. There are two general classes of explanations for such non-Ohmic effects— thermal and electronic. Thermal effects arise because the electrons accelerated by the field always emit phonons in an attempt to return to equilibrium. Electronic effects are due to changes in the response of the charged carriers to high applied fields. In general, both effects must be considered in any quantitative analysis, and the two can produce a coupled response ofter called “electrothermal.” The use of the terminology electrothermal encompasses predominantly thermal and predominantly electronic processes as well as all intermediate cases, and therefore should not prejudice the casual observer into concluding that both effects are necessarily important. In a discussion of the physical mechanism in a particular sample, the major parameters controlling its operation must be identified and separated out from the less significant features.

Threshold switching in chalcogenide-glass thin films

This paper surveys the characteristics of threshold switching systems and examines the evidence for threshold switching as an electronic process. A semiquantitative model is proposed for the nature of the ON---state. The OFF---ON transition is also discussed in the light of recent experimentation, as are the principal aspects of the problem still in need of furthur clarification.

David Adler

Papers

Valence-Alternation Model for Localized Gap States in Lone-Pair Semiconductors

Electrical and Optical Properties of Narrow-Band Materials

Threshold switching in chalcogenide-glass thin films

The mechanism of threshold switching in amorphous alloys

Tetrahedrally bonded amorphous semiconductors