Chalcogenide principles

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... 

In the following, selected results will be presented on the conventional electrochemical synthesis of metal chalcogenide binary and ternary systems, conducted by employing variants of the methods outlined in the previous sections. A brief account of chemical bath deposition principles exemplified will be addressed at the end of this chapter, as being closely related to electrochemical deposition of thin films. 

On account of the fact that the electrode potential of molybdenum is more negative than the discharge potential of hydrogen, principle difficulties arise to cathodically electrodeposit molybdenum chalcogenide films from aqueous solutions. Theoretically, the deposition of pure molybdenum by electrolytic reduction of molybdates in acidic aqueous solutions is possible according to the reaction... 

Thus far, only metal-oxide nanotubes have been synthesized by this process. Whereas crystalline nanotubes were obtained from 2D (layered) oxides, various 3D oxide compounds resulted in semicrystalline or amorphous nanotubes, only. In principle, this kind of process could be extended to the synthesis of nanotubes from chalcogenide and halide compounds in the future. 

Solid-state metathesis reactions. For a number of compounds, solid-state metathesis (exchange) reactions have the advantages of a rapid high-yield method that starts from room-temperature solids and needs little equipment. The principle behind these reactions is to use the exothermicity of formation of a salt to rapidly produce a compound. We may say that for instance a metal halide is combined with an alkali (or alkaline earth) compound of a /7-block element to produce the wanted product together with a salt which is then washed away with water or alcohol. Metathesis reactions have been used successfully in the preparation of several crystalline refractory materials such as borides, chalcogenides, nitrides. 

Abstract This review highlights how molecular Zintl compounds can be used to create new materials with a variety of novel opto-electronic and gas absorption properties. The generality of the synthetic approach described in this chapter on coupling various group-IV Zintl clusters provides an important tool for the design of new kinds of periodically ordered mesoporous semiconductors with tunable chemical and physical properties. We illustrate the potential of Zintl compounds to produce highly porous non-oxidic semiconductors, and we also cover the recent advances in the development of mesoporous elemental-based, metal-chalcogenide, and binary intermetallic alloy materials. The principles behind this approach and some perspectives for application of the derived materials are discussed. 

Probably the least-known aspect of the CD process is what determines the nucle-ation on the substrate and the subsequent film growth. In considering this aspect, we will treat the ion-by-ion and hydroxide cluster mechanisms separately, although there will be many features in common. The principles discussed should be the same for both the free chalcogenide and the complex-decomposition mechanisms. 

In principle, a Cu(In,Ga)Se2 thin-film solar cell should be possible without the use of so-called buffer layers like CdS. The necessary p-n junction might be provided by the p-type Cu(In,Ca)Se2 absorber and the n-type TCO. Such a cell structure is also advantageous as it requires less production steps. Consequently, there has been considerable effort to prepare Cu(In,Ca)Se2 thin-film solar cells without a chalcogenide buffer layer (see Chap. 9 of this book and [120]). Conversion efficiencies above 16% have yet been achieved [121]. 

The crystal structures of ternary and quaternary rare earth chalcogenides of Si, Ge, Sn, Pb, and In can be formed according fo fhe following principles ... 

McHale JM, Auroux A, Perrotta AJ, Navrotsky A (1997) Surface energies and thermodynamic phase stability in nanocrystalline aluminas. Science 277 788-791 Molteni C, Martonak R, Parrinello M (2001) First principles molecular dynamics simulations of pressure-induced stiuctural transformations in silicon clusters. J Chem Phys 114 5358-5365 Murray CB, Norris DJ, Bawendi MG (1993) Synthesis and characterization of nearly monodisperse CdE (E = S, Se, Te) semiconductor nanocrystallites. J Am Chem Soc 115 8706-8715 Onodera A (1972) Kinetics of polymorphic transitions of cadmium chalcogenides under high pressure. Rev Phys Chem Japan 41 1... 

Xerography The high electrical resistivities and optical absorptivities of chalcogenides have lead to many important applications. One of the most remarkable applications is in xerography (dry writing). The principle involved is simply as follows (i) Se film coated on an aluminium substrate is exposed to corona discharge in order to charge the selenium... 

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