Binary selenium oxides

Zhang-Presse, M., Oppermann, H., Thermochemical investigation of RE203-Se02 Systems. III. Yttrium selenium oxides in the pseudo-binary system, J. Therm. Anal. Calorim., 69, (2002), 301-316. Cited on pages 356,585. 

The chalcogenides are binary compounds of a chalcogen (i.e., the elements of Group Ilb zinc, cadmium, mercury) with a less electropositive element, such as those of Group VIb (oxygen, sulfur, selenium, and tellurium). This section covers the sulfides, selenides, andtellurides. Oxides are reviewed above in Ch. 11. Most of the chalcogenides have useful optical characteristics and their applications are usually found in optics. 

Hydrides of variable composition are not only formed with pure metals as solvents. A large number of the binary metal hydrides are non-stoichiometric compounds. Non-stoichiometric compounds are in general common for d,f and some p block metals in combination with soft anions such as sulfur, selenium and hydrogen, and also for somewhat harder anions like oxygen. Hard anions such as the halides, sulfates and nitrides form few non-stoichiometric compounds. Two factors are important the crystal structures must allow changes in composition, and the transition metal must have accessible oxidation states. These factors are partly related. FeO,... 

The chemical properties of selenium fall between sulfur and tellurium. Thus, selenium reacts with oxygen similarly to sulfur, forming two oxides, selenium dioxide, Se02 and trioxide, SeOs. The metal combines with halogens forming their halides. With nonmetals, selenium forms binary compounds exhibiting oxidation states +4 and -i-6. 

Binary Selenides. Most binary selenides are formed by heating selenium in the presence of the element, reduction of selenites or selenates with carbon or hydrogen, and double decomposition of heavy-metal salts in aqueous solution or suspension with a soluble selenide salt, eg, Na2Se or (NH Se [66455-76-3]. Atmospheric oxygen oxidizes the selenides more rapidly than the corresponding sulfides and more slowly than the tellurides. Selenides of the alkali, alkaline-earth metals, and lanthanum elements are water soluble and readily hydrolyzed. Heavy-metal selenides are insoluble in water. Polyselenides form when selenium reacts with alkali metals dissolved in liquid ammonia. Metal (M) hydrogen selenides of the M HSe type are known. Some heavy-metal selenides show important and useful electric, photoelectric, photo-optical, and semiconductor properties. Ferroselenium and nickel selenide are made by sintering a mixture of selenium and metal powder. 

The next five chapters deal with deposition of specific groups of semiconductors. In Chapter 4, II-VI Semiconductors, all the sulphides, selenides, and (what little there is on) tellurides of cadmium (most of the chapter), zinc (a substantial part), and mercury (a small part). (Oxides are left to a later chapter.) This chapter is, understandably, a large one, due mainly to the large amount of work carried out on CdS and to a lesser extent on CdSe. Chapter 5, PbS and PbSe, provides a separate forum for PbS and PbSe, which provided much of the focus for CD in earlier years. The remaining sulphides and selenides are covered in Chapter 6, Other Sulphides and Selenides. There are many of these compounds, thus, this is a correspondingly large chapter. Chapter 7, Oxides and Other Semiconductors, is devoted mainly to oxides and some hydroxides, as well as to miscellaneous semiconductors that have only been scantily studied (elemental selenium and silver halides). These previous chapters have been limited to binary semiconductors, made up of two elements (with the exception of elemental Se). Chapter 8, Ternary Semiconductors, extends this list to semiconductors composed of three elements, whether two different metals (most of the studies) or two different chalcogens. 

Binary compounds can be made with uranium. Such solids state compounds have been investigated because they have interesting magnetic properties. They are made by direct interaction with uranium metal. Oxides mainly form with the general formula UO2, UjOg, UO2. The metal also reacts with other elements such as boron, carbon, nitrogen, phosphorus, and arsenic to make semi-metallic solids. Compounds can also be made using silicon, sulfur, selenium, and tellurium. Urinates can be formed by the addition of uranium with alkali and alkaline Earth metals. 

The copper atoms in the vast majority of the clusters can be assigned a formal charge of +1, while the chalcogen ligands are formally viewed as E or RE groups. Some of the selenium-bridged species, however - and nearly all copper telluride clusters - form nonstoichiometric compounds that display mixed valence metal centers in the formal oxidation states 0 and +I or +I and +11. These observations correlate with those made for the binary phases CU2S, Cu2 xSe, and Cu2- Te [38-40]. 

U, Np, and Pu selenide and oxide-selenide molecular and cluster cations were synthesized by LA of dilute mixtures of An oxides in a selenium matrix (Gibson, 1999d) binary ions, AnSe +, and ternary cluster ions, An OmSe +, were observed, with the compositions of the mixed 0/Se clusters suggesting the aggregation of AnOm with Se , the presence of Se ions in analogy with 0 , or the presence of structures involving O—Se bonding. 

---