Binary Compounds and Alloys

Several structural types, corresponding to about 5500 binary compounds and alloys, were considered 147 structure types were classified as 97 coordination types. The applications of these maps, which, in the most favourable cases make it possible to predict not only the CN and polyhedron but also the structure type or a limited number of possibilities, were discussed. The possible extension to ternary and quaternary phases was also considered. 

Crystalline electric field (CEF) 5.4. Binary compounds and alloys (other ... 

In addition to the binary compounds and alloys discussed above, there exist a large number of molecular compounds in which tin is bonded to the elements nitrogen, phos-... 

RfLl phases The existence of these phases (cubic AuCu3 type) had been reported for R = La, Ce, Pr, Nd and Sm. Subsequently, however, Buschow and van Vucht (1967) found that many of the R3A1 phases do not form, unless some carbon is present. C atoms occupy the body-centred site, which in the AuCu3 type structure is normally vacant, while the Au atoms occupy the corners, and the Cu atoms the face-centred positions. When the face-centred position is completely filled, the structure is known as the anti-perovskite structure. This occurs for R = Nd, Sm, Gd, Tb, Dy Ho and Er. They also noted that neither N nor O would stabilize these compounds. Notice that Ce3Al and Pr3Al are truly binary compounds and C is not required for these two phases to form. Independently, Nowotny (1968) found that the anti-perovskite structure could be formed by C and N additions to R3M alloys, where M = Al, Ga, In, Tl, Sn and Pb. 

A complete solution for a binary compound or alloy can be given in the approximation of the AERDF if one disposes of three different diffraction patterns of the same material taken in conditions under which the two types of atoms have as different scattering factors fi and as possible for the incident radiations. This can be done by using alternatively X-rays of different wave lengths, electrons, and neutrons and/or by changing the isotopic composition of the sample. If one admits that the partial interference functions (see Eq. 2.8) do not depend on composition (cj and Ca), which seems to be true to a first approximation in some alloys, the three measurements can be done with the same radiation, but on three different compositions. 

Figure 5 displays the Sc-U phase diagram established by Terekhov and Sinyakova (1992). No binary compounds and an immiscibility gap in the liquid alloys occur in... 

There is a great number of mostly covalent and tetraliedral binary IV-IV, III-V, II-VI and I-VII semiconductors. Most crystallize in tire zincblende stmcture, but some prefer tire wairtzite stmcture, notably GaN [H, 12]. Wlrile tire bonding in all of tliese compounds (and tlieir alloys) is mostly covalent, some ionic character is always present because of tire difference in electron affinity of tire constituent atoms. 

III-V compound semiconductors with precisely controlled compositions and gaps can be prepared from several material systems. Representative III-V compounds are shown in tire gap-lattice constant plots of figure C2.16.3. The points representing binary semiconductors such as GaAs or InP are joined by lines indicating ternary and quaternary alloys. The special nature of tire binary compounds arises from tlieir availability as tire substrate material needed for epitaxial growtli of device stmctures. 

Temary and quaternary semiconductors are theoretically described by the virtual crystal approximation (VGA) [7], Within the VGA, ternary alloys with the composition AB are considered to contain two sublattices. One of them is occupied only by atoms A, the other is occupied by atoms B or G. The second sublattice consists of virtual atoms, represented by a weighted average of atoms B and G. Many physical properties of ternary alloys are then expressed as weighted linear combinations of the corresponding properties of the two binary compounds. For example, the lattice constant d dependence on composition is written as ... 

Heterostructures and Superlattices. Although useful devices can be made from binary compound semiconductors, such as GaAs, InP, or InSb, the explosive interest in techniques such as MOCVD and MBE came about from their growth of ternary or quaternary alloy heterostmctures and supedattices. Eor the successful growth of alloys and heterostmctures the composition and interfaces must be accurately controlled. The composition of alloys can be predicted from thermodynamics if the flow in the reactor is optimised. Otherwise, composition and growth rate variations are observed... 

Solid solutions are very common among structurally related compounds. Just as metallic elements of similar structure and atomic properties form alloys, certain chemical compounds can be combined to produce derivative solid solutions, which may permit realization of properties not found in either of the precursors. The combinations of binary compounds with common anion or common cation element, such as the isovalent alloys of IV-VI, III-V, II-VI, or I-VII members, are of considerable scientific and technological interest as their solid-state properties (e.g., electric and optical such as type of conductivity, current carrier density, band gap) modulate regularly over a wide range through variations in composition. A general descriptive scheme for such alloys is as follows [41]. 

Of particular interest is the fundamental science and technology of the solid solutions between II-VI binary compounds. These isovalent alloys may be classified according to the scheme introduced previously (see Sect. 1.2.3) - a convenient matrix diagram comprising their observed structures can be found in a publication of Wei and Zunger [102]. 

Figure 2.22. Compound formation capability in binary systems. The different element combinations are mapped on Mendeleev number coordinates and those systems are indicated in which the formation of intermediate phases has been observed (either from the liquid or in the solid state). Blank boxes indicate systems for which no certain data are available. Notice that the compound-forming alloys are crowded in a region corresponding to a large difference in the Mendeleev numbers of the elements involved (for instance, basic metals with semi-metals).

The situation in the solid state is generally more complex. Several examples of binary systems were seen in which, in the solid state, a number of phases (intermediate and terminal) are formed. See for instance Figs 2.18-2.21. Both stoichiometric phases (compounds) and variable composition phases (solid solutions) may be considered and, as for their structures, both fully ordered or more or less completely disordered phases. This variety of types is characteristic for the solid alloys. After a few comments on liquid alloys, particular attention will therefore be dedicated in the following paragraphs to the description and classification of solid intermetallic phases. 

Thermochemistry of cluster compounds. In this short summary of cluster structures and their bonding, a few remarks on their thermochemical behaviour are given, in view of a possible relationship with the intermetallic alloy properties. To this end we remember that for molecular compounds, as for several organic compounds, concepts such as bond energies and their relation to atomization energies and thermodynamic formation functions play an important role in the description of these compounds and their properties. A classical example is given by some binary hydrocarbon compounds. 

Selenides, tellurides andpolonides. Se, Te and Po react easily with most metals and non-metals to form binary compounds (selenides and tellurides are common mineral forms of these elements). Non-stoichiometry is frequently observed in the compounds with the transition elements many of these compounds may be described as metallic alloys. The compounds of the metals of the first two groups may be considered the salts of the acids H2Se, H2Te, etc. The alkali metal selenides... 

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