Zinc sulfide crystal structure

The zinc blende and wurtzite structures. Zinc sulfide crystallizes in two distinct lattices hexagonal wurtzite (Fig. 4.2a) and cubic zinc blende (Fig. 4.2b). We shall not elaborate upon them now (see page 121), but simply note that in both the coordination number is 4 fbr both cations and anions. The space groups are Ptync and F43m. Can you tell which is which ... 

Virion templates of TMV were also used in combination with different synthetic routes for CdS, PbS, and Fe oxide nanoparticles.Nanoparticle-virion tubules were prepared by reacting a buffered solution of TMV in CdCl2 (pH 7) or TMV in Pb(N03)2 (pH 5) with H2S gas. The formation of metal sulfide nanoparticles occurred over 6 hours as observed by a uniform coating of CdS and PbS nanocrystals on the TMV surface from TEM analysis. Selected area electron diffraction of the mineralized products indicated a zinc blende crystal structure for CdS particles and a rock salt structure for single domain PbS nanocrystals. The iron oxide nanoparticles were mineralized by the TMV templates by the oxidative hydrolysis of an Fe VFe acidic solution with NaOH. Consequendy, a mineral coating of irregular ferrihydrite particles grew on the surface to a thickness of 2 nm. 

Fig. 1.2 Crystal structures of the major sulfides (metal atoms are shown as smaller or black spheres) (A) galena (PbS) structure (rock salt) (B) sphalerite (ZnS) structure (zinc blende) (C) wurtzite (ZnS) strucmre (D) pyrite structure and the linkage of metal-sulfur octahedra along the c-axis direction in (/) pyrite (FeSa) and (//) marcasite (FeSa) (E) niccolite (NiAs) structure (F) coveUite (CuS) structure (layered). (Adapted from Vaughan DJ (2005) Sulphides. In Selley RC, Robin L, Cocks M, Plimer IR (eds.) Encyclopedia of Geology, MINERALS, Elsevier p 574 (doi 10.1016/B0-12-369396-9/00276-8))...

The monosulfides of the alkaline earth metals crystallize in the rock salt (MgS, CaS, SrS, BaS) and zinc blende (BeS) structures. BaS is insoluble in water, while the other monosulfides are sparingly soluble but hydrolyzed on warming (except MgS that is completely hydrolyzed). The monoselenides are isomorphous to the sulfides. The monotellurides CaTe, SrTe, BaTe adopt the rock salt stmcture, while BeTe has the zinc blende and MgTe the wurtzite structure. Alkaline earth polysulfides may be prepared by boiling a solution or suspension of the metal hydroxide with sulfur, e.g.,... 

Zinc sulfide is white to gray-white or pale yellow powder. It exists in two crystalline forms, an alpha (wurtzite) and a beta (sphalerite). The wurtzite form has hexagonal crystal structure refractive index 2.356 density 3.98 g/cm3 melts at 1,700°C practically insoluble in water, about 6.9 mg/L insoluble in alkalis soluble in mineral acids. The sphalerite form arranges in cubic crystalline state refractive index 2.368 density 4.102 g/cm changes to alpha form at 1,020°C practically insoluble in water, 6.5 mg/L soluble in mineral... 

Wurtzite structure. Zinc sulfide can also crystallize in a hexagonal form called wurtzite that is formed slightly less exothermically than the cubic zinc blende (sphalerite) modification (Afff = —192.6 and —206.0 kJ mol-1, respectively) and hence is a high temperature polymorph of ZnS. The relationship between the two structures is best described in terms of close packing (Section 4.3) in zinc blende, the anions (or cations) form a cubic close-packed array, whereas in wurtzite they form hexagonal close-packed arrays. This relationship is illustrated in Fig. 4.13 note, however, that this does not represent the actual unit cell of either form. 

The luminescent properties can be influenced by the nature of the activators and coactivators, their concentrations, the composition of the flux, and the firing conditions. In addition, specific substitution of zinc or sulfur in the host lattice by cadmium or selenium is possible, which also influences the luminescent properties. Zinc sulfide is dimorphic and crystallizes below 1020 °C in the cubic zinc-blende structure and above that temperature in the hexagonal wurtzite lattice. When the zinc is replaced by cadmium, the transition temperature is lowered so that the hexagonal modification predominates. Substitution of sulfur by selenium, on the other hand, stabilizes the zinc-blende lattice. 

Cation holes can also be created by coactivation with trivalent metal ions or by incorporation of oxygen [5.313]. The luminescence band of self-activated zinc sulfide with the zinc-blende structure exhibits a maximum at 470 nm. On transition to the wurtzite structure, the maximum shifts to shorter wavelengths. In the mixed crystals zinc sulfide-cadmium sulfide and zinc sulfide-zinc selenide, the maximum shifts to longer wavelengths with increasing cadmium or selenium concentration. 

The structure of cubic zinc sulfide (zinc blende, sphalerite) may be described as a ccp of S atoms, in which half of the tetrahedral sites are filled with Zn atoms the arrangement of the filled sites is such that the coordination numbers of S and Zn are both four, as shown in Fig. 10.1.7. The crystal belongs to space group 7 2 — / 43m. Note that the roles of the Zn and S atoms can be interchanged by a simple translation of the origin. 

In the crystal structure of hexagonal zinc sulfide (wurtzite), the S atoms are arranged in hep, in which half of the tetrahedral interstices are filled with Zn atoms, and the space group is C v — P6imc. The positions of atoms in the hexagonal unit cell are... 

Aluminum and Gallium Sulfides. The crystal structures of the various forms of A12S3 were studied by Flahaut (2) and those of Ga2S3 by Hahn and his coworkers (13, 15). These crystal structures are similar, and closely related to the wurtzite and zinc blende types. 

Most inorganic chemistry texts list cut-off values for ther+/r ratios corresponding to the various geometries of interstitial sites (Table 2.3). However, it should also be pointed out that deviations in these predictions are found for many crystals due to covalent bonding character. An example for such a deviation is observed for zinc sulfide (ZnS). The ionic radius ratio for this structure is 0.52, which indicates that the cations should occupy octahedral interstitial sites. However, due to partial covalent bonding character, the anions are closer together than would occur from purely electrostatic attraction. This results in an effective radius ratio that is decreased, and a cation preference for tetrahedral sites rather than octahedral. 

The crystal structure for this complex lattice (wurtzite structure) is shown in Figure 2.15. This is best described as an hep lattice of sulfide ions, with zinc ions occupying one-half of the available tetrahedral interstitial sites. For this lattice, there are two units of ZnS per unit cell ... 

Most crystals will emit light when fractured. Because most inorganic phosphors have a crystalline structure, they should emit TL. One phosphor, namely, zinc sulfide doped with manganese (ZnS Mn), has often been noted for its TL. To develop an effective phosphor-based sensor, the relationship between TL intensity and impact velocity for ZnS Mn or any other material must be quantified. 

Silicon carbide occurs in two sUghtly different crystal structures the cubic pSiC, and a large number of hexagonal rhombohcdral varieties known collectively as aSiC.1 11 1 The single cubic form, pSiC, is obtained vdien the carbide is synthesized below 2100"C. It is a fiice-centered cubic (fee) structure of the zincblende type shown in Fig. 7.1. Zincblende is a mineral of zinc sulfide also known as sphalerite. In this illustration, the zincblende structure is represented with the cube diagonals vertical and appears as series of identical (although translated) puckered sheets of atoms widi an AA layer sequence. Another view of the pSiC crystal is shown in Fig. 7.2 (the carbon atoms, all located in the 4/ sites, are omitted for clarity] The pSiC structure has no polytype (see Table 7.3 for crystal structure data). 

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