Binary antimonides

Table 1 Selected physical properties of binary antimonides MSb...

Crystallographic data of the binary antimonides of rare earth are listed in table 1. 

The structures of Eu containing binary antimonides are isotypic with binary antimonides of alkaline earth metals (Ca, Ba, Sr) and do not have the analogues, except for EusSbs, in other... 

The structure types of binary antimonides have been described by Hulliger (1984) in chapter 33 of the Handbook. 

Metallic Antimonides. Numerous binary compounds of antimony with metallic elements are known. The most important of these are indium antimonide [1312-41 -0] InSb, gallium antimonide [12064-03-8] GaSb, and aluminum antimonide [25152-52-7] AlSb, which find extensive use as semiconductors. The alkali metal antimonides, such as lithium antimonide [12057-30-6] and sodium antimonide [12058-86-5] do not consist of simple ions. Rather, there is appreciable covalent bonding between the alkali metal and the Sb as well as between pairs of Na atoms. These compounds are useful for the preparation of organoantimony compounds, such as trimethylstibine [594-10-5] (CH2)2Sb, by reaction with an organohalogen compound. 

Other binary compounds include MAs3 (M = Rh, Ir), which has the skutterudite (CoAs3) structure [33] containing As4 rectangular units and octahedrally coordinated M. The corresponding antimonides are similar. M2P (M = Rh, Ir) has the anti-fluorite structure while MP3 has the CoAs3 structure. In another compound of this stoichiometry, IrSi3, 9-coordination exists for iridium. 

Among binary transition-metal pnictides, only the first-row transition-metal phosphides have been analysed by XPS extensively, whereas arsenides and antimonides have been barely studied [51-61]. Table 2 reveals some general trends in the P 2p3/2 BEs for various first-row transition-metal monophosphides, as well as some metaland phosphorus-rich members forming for a given transition metal. Deviations of as much as a few tenths of an electron volt are seen in the BEs for some compounds measured multiple times by different investigators (e.g., MnP), but these... 

The transition-metal monopnictides MPn with the MnP-type structure discussed above contain strong M-M and weak Pn-Pn bonds. Compounds richer in Pn can also be examined by XPS, such as the binary skutterudites MPn , (M = Co, Rh, Ir Pn = P, As, Sb), which contain strong Pn-Pn bonds but no M-M bonds [79,80], The cubic crystal structure consists of a network of comer-sharing M-centred octa-hedra, which are tilted to form nearly square Pnn rings creating large dodecahedral voids [81]. These voids can be filled with rare-earth atoms to form ternary variants REM Pnn (RE = rare earth M = Fe, Ru, Os Pn = P, As, Sb) (Fig. 26) [81,82], the antimonides being of interest as thermoelectric materials [83]. 

A. Binary Group 13-Antimonide Material Films—Introduction. 298... 

In the last decade, numerous compounds of these types have been the subject of detailed CVD studies, demonstrating their potential for the deposition of the corresponding binary materials. Most of the work has concentrated on binary nitrides and phosphides, while the deposition of binary MSb films has been studied to a far lesser extent. The lack of potential precursors has been the major problem for the deposition of group 13-antimonide films for many years. Only a very few group 13-Sb compounds have been known until we and Wells established general synthetic pathways as was shown in Sections 2 and 3. Consequently, detailed investigations concerning their potential to serve for the deposition of the desired materials... 

Arsenides, antimonides and bismuthides. A number of salt-like related binary compounds formed with these semi-metals pertain to the following structure types NaCl, NiAs, ZnS, Na3As, FeS2, etc. 

A number of binary phosphides and polyphosphides (compounds containing P—P bonds), for instance those of Mn, Tc, Re, Fe, Ru, Os can be prepared, often in well crystallized form, by the tin-flux technique. The mixture generally containing an excess of P (red P) and a high excess of tin is heated, possibly at a slow rate, to the required temperature (600°-1000°C) and maintained at that temperature for several days and then slowly cooled. In several cases the products may be recovered by dissolving the tin-rich residue in hydrochloric acid. The preparation of several ternary phosphides and of arsenides and antimonides has also been described (see 6.11.3). 

Stibine. Sbl h, is formed by hydrolysis of some metal antimonides or reduction (with hydrogen produced by addition of zinc and HC1) of antimony compounds, as in the Gutzeit test. It is decomposed by aqueous bases, in contrast with arsine. It reacts with metals at higher temperatures to give the antimonides. The antimonides of elements of group la. 2a, and 3a usually are stoichiometric, with antimony trivalent. With other metals, the binary compounds are essentially intermetallic. with such exceptions as the nickel series, Ni. Sb.. NiSb, Ni5Sb2 and Ni4Sb. 

Interconnection of the ternary antimonides with the binary structure types 140... 

This chapter presents a review of the current data on phase diagrams and crystal structures of binary, ternary and quaternary metal antimonides with the R elements (R = Sc, Y and the lanthanides). 

Sections 2-4 give the overview of the literature published on these systems, i.e., the isothermal sections and crystallographic characteristics of the binary, ternary and quaternary compounds, as well as, outlines of the experimental methods that have been utilized. A description of the structure types of ternary antimonides is the subject of sect. 5. The physical properties are only briefly presented for the most common isotypic series of compounds (sect. 6). The general features and trends in the 7 -Sb and R-(s-, p-, d-, f- element)-Sb systems are discussed in sect. 7. 

Similar to other binary /(-p-clcment systems, the formation of binary rare earth - antimonides with a simple stoichiometry is a characteristic feature of these systems. The largest number of structure types formed was encountered for the group of RSb2 compounds (4 members). The polymorphic modifications were observed for GdSb2 and TbSb2 as well as the RSb (R = La, Ce) and RsSb (R = Yb, Y and Sc) compounds were noted to undergo the solid state transformations. 

Several families of ternary antimonides crystallize with structure types derived from those of binary types by an insertion of third component in the structure of binary compounds, i.e., LaFe4Pi2 from C0AS3, Y3Au3Sb4 from TI14P3, UsCrSbs fromMnsSis. 

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