Antimonide

The supplanting of germanium-based semiconductor devices by shicon devices has almost eliminated the use of indium in the related ahoy junction (see Semiconductors). Indium, however, is finding increased use in III—V compound semiconductors such as indium phosphide [22398-80-7] for laser diodes used in fiber optic communication systems (see Electronic materials Fiber optics Light generation). Other important indium-containing semiconductors include indium arsenide [1303-11-3] indium antimonide [1312-41 -0] and copper—indium—diselenide [12018-95-0]. 

Indium also combines with nonmetaUic elements and with metalloids such as N, P, Sb, As, Te, and Se. Many of the latter compounds ate semiconducting as ate the oxide and sulfide. Indium antimonide [1312-41 -0], InSb indium arsenide [1303-11-3], In As and indium phosphide [22398-80-7], InP, ate the principal semiconducting compounds. These ate all prepared by direct combination of the highly purified elements at elevated temperature under controlled conditions. 

If antimony and arsenic are present ia the feed, copper and iron react to form the respective antimonides and arsenides known as speiss (specific gravity 6.0). If it is preferred to remove copper ia a speiss layer, the sulfur ia the siater must be reduced and the addition of scrap iron may be necessary to encourage speiss formation. Matte and speiss are usually sent to a copper smelter for recovery of the metals. 

Lead—antimony or lead—arsenic ahoys must not be mixed with lead—calcium (aluminum) ahoys in the molten state. Addition of lead—calcium—aluminum ahoys to lead—antimony ahoys results in reaction of calcium or aluminum with the antimony and arsenic to form arsenides and antimonides. The dross containing the arsenides and antimonides floats to the surface of the molten lead ahoy and may generate poisonous arsine or stibine if it becomes wet. Care must be taken to prevent mixing of calcium and antimony ahoys and to ensure proper handling of drosses. 

Antimony is also used as a dopant in n-ty e semiconductors. It is a common additive in dopants for siHcon crystals with impurities, to alter the electrical conductivity. Interesting semiconductor properties have been reported for cadmium antimonide [12050-27-0] CdSb, and zinc antimonide [12039-35-9] ZnSb. The latter has good thermoelectric properties. Antimony with a purity as low as 99.9+% is an important alloying ingredient in the bismuth teUuride [1304-82-17, Bi Te, class of alloys which are used for thermoelectric cooling. 

Stibiae may be prepared by the treatment of metal antimonides with acid, chemical reduction of antimony compounds, and the electrolysis of acid or alkaline solutions usiag a metallic antimony cathode ... 

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. 

Cadmium Arsenides, Antimonides, and Phosphides. Cadmium arsenide [12511 -93-2] CdAs, cadmium diarsenide [12044 0-5] ... 

Antimonides of formulas CdSb and Cd2Sb2 have been reported. Both are usually prepared by direct union of the elements, the former is a hole-type semiconductor (9), with properties shown in Table 1, and finds use as a thermoelectric generator. Reagent-grade material costs 2.00/g in small lots. The band gap energy is 0.46 eV (2.70 J.m) (31) is 138 kj/mol (33.0 kcal/mol). Dicadmium triantimonideCd2Sb2, is a metastable, white... 

Figure 7.6. A filled. skutterudite antimonide crystal structure. A transition niclal atom (Fc or Co) at the centre of each octahedron is bonded to antimony atoms at each corner. The rare earth atoms (small spheres) are located in cages made by eight octahedra. The large thermal motion of rattling of the rare earth atoms in their cages is believed be responsible for the strikingly low thermal conductivity of these materials (Sales 1997).

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. 

Figure 3. The lattice parameter for the family of rock-salt structure actinide-antimonide compounds is shown where the line is for the corresponding lanthanide compounds. The metallic radii for the light actinide elements are plotted. The smooth line simply connects Ac to the heavy actinides. In both cases the smooth line represents the ideal tri-valent behavior.

Antimonide-actinide compounds, lattice parameter for rock-salt... 

Indium antimonide Indium sulphate Indium oxide... 

Examples of the anionic structures in polyphosphides, polyarsenides and poly antimonides. For comparison, recall the structures of red and black phosphorus and of arsenic (pp. 108, 109 and 110). Stereo image for NaPs... 

Even smaller c/a ratios are observed for the more electron-rich arsenides and antimonides (e.g. 1.39 for NiAs). Since the ideal c/a ratio of hexagonal closest-packing is 1.633, there is a considerable compression in the c direction, i.e. in the direction of the closest contacts among the metal atoms. 

The structure of MnP is a distorted variant of the NiAs type the metal atoms also have close contacts with each other in zigzag lines parallel to the a-b plane, which amounts to a total of four close metal atoms (Fig. 17.5). Simultaneously, the P atoms have moved up to a zigzag line this can be interpreted as a (P-) chain in the same manner as in Zintl phases. In NiP the distortion is different, allowing for the presence of P2 pairs (P ). These distortions are to be taken as Peierls distortions. Calculations of the electronic band structures can be summarized in short 9-10 valence electrons per metal atom favor the NiAs structure, 11-14 the MnP structure, and more than 14 the NiP structure (phosphorus contributes 5 valence electrons per metal atom) this is valid for phosphides. Arsenides and especially antimonides prefer the NiAs structure also for the larger electron counts. 

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