Chalcogenide structure

Numerous ternary systems are known for II-VI structures incorporating elements from other groups of the Periodic Table. One example is the Zn-Fe-S system Zn(II) and Fe(II) may substimte each other in chalcogenide structures as both are divalent and have similar radii. The cubic polymorphs of ZnS and FeS have almost identical lattice constant a = 5.3 A) and form solid solutions in the entire range of composition. The optical band gap of these alloys varies (rather anomalously) within the limits of the ZnS (3.6 eV) and FeS (0.95 eV) values. The properties of Zn Fei-xS are well suited for thin film heterojunction-based solar cells as well as for photoluminescent and electroluminescent devices. 

A table of ionic conductors that behave in a similar way to a-Agl is given in Table 5.4. Some of these structures are based on a close-packed array of anions and this is noted in the table the conducting mechanism in these compounds is similar to that in a-Agl. The chalcogenide structures, such as silver sulfide and selenide, tend to demonstrate electronic conductivity as well as ionic, although this can be quite useful in an electrode material as opposed to an electrolyte. 

Betyllium, because of its small size, almost invariably has a coordination number of 4. This is important in analytical chemistry since it ensures that edta, which coordinates strongly to Mg, Ca (and Al), does not chelate Be appreciably. BeO has the wurtzite (ZnS, p. 1209) structure whilst the other Be chalcogenides adopt the zinc blende modification. BeF2 has the cristobalite (SiOi, p. 342) structure and has only a vety low electrical conductivity when fused. Be2C and Be2B have extended lattices of the antifluorite type with 4-coordinate Be and 8-coordinate C or B. Be2Si04 has the phenacite structure (p. 347) in which both Be and Si... 

The chalcogenides of Ga, In and T1 are much more numerous and at least a dozen different structure types have been established by X-ray... 

Of the more complex chalcogenide derivatives of the Group 15 elements two examples must suffiee to indicate the great structural versatility of these elements, particularly... 

All three metals form a wide variety of binary chalcogenides which frequently differ both in stoichiometry and in structure from the oxides. Many have complex structures which are not easily described, and detailed discussion is therefore inappropriate. The various sulfide phases are listed in Table 22.4 phases approximating to the stoichiometry MS have the NiAs-type structure (p. 556) whereas MS2 have layer lattices related to M0S2 (p. 1018), Cdl2, or CdCl2 (p. 1212). Sometimes complex layer-sequences occur in which the 6-coordinate metal atom is alternatively octahedral and trigonal prismatic. Most of the phases exhibit... 

Lower formal oxidation states are stabilized, however, by M-M bonding in ternary chalcogenides such as M MeQn, M4M6Q13 (M = alkali metal M = Re, Tc Q = S, Se) and the recently reported M gMeS. Their structures are all based on the face-capped, octahedral MeXg cluster unit found in Chevrel phases (p. 1018) and in the dihalides of Mo and W... 

Chalcogenides of Cd are similar to those of Zn and display the same duality in their structures. The sulfide and selenide are more stable in the hexagonal form whereas the telluride is more stable in the cubic form. CdS is the most important compound of cadmium and, by addition of CdSe, ZnS, HgS, etc., it yields thermally stable pigments of brilliant colours from pale yellow to deep red, while colloidal dispersions are used to colour transparent glasses. 

The most important mercury chalcogenide halides are of the type HgaYjXj (Y = S, Se, Te X = Cl, Br, I). The corresponding sulfide halides have been known for over 150 years (326). Quite a lot of work has been performed concerning the preparation, structures, electronic and optical properties, and phototropic behavior of these compounds. Mercury chalcogenide halides of other compositions have been mentioned in the literature (141). As most of these compounds are not well established, they will not be treated in detail, with the exception of the latest contributions (see Table V). 

Table VI summarizes the structural data on mercury chalcogenide halides.

Just as, in Group VB, niobium, so, in this Group, molybdenum provides most of the examples of the chalcogenide halides. The occurrence and preparation of such compounds are described in numerous publications. In most cases, they have been obtained as powders, with the composition based on chemical analyses only. The presence of defined, homogeneous phases is, therefore, in many cases doubtful. In addition, some published results are contradictory. A decision is possible where a complete structure analysis has been made. As will be shown later, the formation of metal-metal bonds (so-called clusters), as in the case of niobium, is the most characteristic building-principle. Such clusters... 

The structures of the rhenium chalcogenide halides have not been studied. X-Ray powder data were collected, in order to prove the homogeneity of the compounds 140, 263, 264, 353). 

Fig. 33. Structure relationships and coordinations of lead chalcogenide halides a, Pb4SeBr, b, PbjSjI c, PbvSjBrio. (Redrawn from B. Krebs,. Z. Anorg. Allg. Chem. 396, 137 (1973), Figs. 1 2, and 3, pp. 141, 147, and 148.)...

In the early 1950s, in a systematic study, Donges (106-108) discovered most of the chalcogenide halides of antimony and bismuth that are known today, and then solved their structures. 

---