Zinc sulfide, crystal

From the relative intensities of the two diffracted waves one can deduce the absolute direction of the vector W —> Y with respect to the b axis. This type of reasoning was exploited by Nishikawa and Matsukawa (14) in 1928 and independently by Coster, Knol, and Prins (15) in 1930 to determine the absolute polarity of successive layers of zinc and sulfur in a polar crystal of zinc sulfide. In the zinc sulfide crystal, planes of zinc and sulfur alternate parallel to the face (111), as shown in Scheme 3 the distance between the close pairs of zinc and sulfur planes is one-quarter of the whole 111 spacing. 

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 ... 

The sulfide ion then reacts with the lead ion in the gel to precipitate lead sulfide. Crystals up to a millimeter in length can be produced in 2 weeks. Temperatures range from room temperature to 35°, with best results reported at the higher temperature. The same sulfide source is used for the growth of zinc sulfide crystals.25,27 The crystals grow to a size of 3-4 mm in 2 months. It should be mentioned that a modified U-tube system has been used to produce this size crystal and it is expected that smaller crystals will be produced if a simple U-tube is employed. 

Zinc sulfide, with its wide band gap of 3.66 eV, has been considered as an excellent electroluminescent (EL) material. The electroluminescence of ZnS has been used as a probe for unraveling the energetics at the ZnS/electrolyte interface and for possible application to display devices. Fan and Bard [127] examined the effect of temperature on EL of Al-doped self-activated ZnS single crystals in a persulfate-butyronitrile solution, as well as the time-resolved photoluminescence (PL) of the compound. Further [128], they investigated the PL and EL from single-crystal Mn-doped ZnS (ZnS Mn) centered at 580 nm. The PL was quenched by surface modification with U-treated poly(vinylferrocene). The effect of pH and temperature on the EL of ZnS Mn in aqueous and butyronitrile solutions upon reduction of per-oxydisulfate ion was also studied. EL of polycrystalline chemical vapor deposited (CVD) ZnS doped with Al, Cu-Al, and Mn was also observed with peaks at 430, 475, and 565 nm, respectively. High EL efficiency, comparable to that of singlecrystal ZnS, was found for the doped CVD polycrystalline ZnS. In all cases, the EL efficiency was about 0.2-0.3%. 

The platinum asbestos is filtered off. The product which has deposited on the catalyst is washed off with a minimum amount of water and the washings are combined with the filtrate. To avoid contamination of the final product with zinc, the zinc is removed from the solution by addition of about 55 ml. of a 20% ammonium sulfide solution (or ammonium sulfide is added until precipitation is complete). The zinc sulfide is removed by filtration, the solid is washed, and the washings are added to the solution. Alcohol is added to the filtrate and washings until some cloudiness appears, then the mixture is cooled to precipitate the product. Additional product may be obtained by concentrating the solution under vacuum, adding hydrochloric acid to obtain a pH below 1, and cooling. The crystals are washed with alcohol. 

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... 

The reaction finished within 1 h at 26°C.. They used seed crystals of CdS to promote the uniformity of the final product, and analyzed the growth kinetics using Nielsen s chronomal. The isoelectric point in terms of pH was determined to be 3.7 by electrokinetic measurement. They also prepared zinc sulfide (ZnS polycrystalline spheres), whose isoelectric point in pH was 3.0 (2), lead sulfide (PbS monocrystalline cubic galena) (3), cadmium zinc sulfide (CdS/ZnS amorphous and crystalline spheres) (3), and cadmium lead sulfide (CdS/PbS crystalline polyhedra) (3), in a similar manner. 

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. 

ZnO Zn is a typical example of a self-activated phosphor. In the case of zinc oxide, it is an excess of zinc which enables the phosphor to luminesce. The production is carried out by thermal oxidation of crystallized zinc sulfide in air at ca. 400 °C. The green luminescence, with a broad maximum at 505 nm, has a very short decay time of 10-6 s. As a phosphor for cathode-ray tubes, ZnO.Zn is classified in the TEPAC list as P 24 and in the WTDS system as GE. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

ELECTROLUMINESCENCE. Luminescence generated in crystals by electric fields or currents in the absence of bombardment or other means of excitation. It is a solid-state phenomenon involving />- and n-type semiconductors, and is observed in many crystalline substances, especially silicon carbide, zinc sulfide, and gallium arsenide, as well as in silicon, germanium, and diamond. 

SPHALERITE BLENDE. Also known as zinc blende, this mineral is zinc sulfide, tZn, Fc)S, practically always containing some iron, crystallizing in the isometric system frequently as tetrahedrons, sometimes as cubes or dodecahedrons, but usually massive with easy cleavage, which is dodecahedral. It is a brittle mineral with a conchoidal fracture hardness, 2.5-4 specific gravity, 3.9-4.1 luster, adamantine to resinous, commonly the latter. It is usually some shade of yellow brown or brownish-black, less often red, green, whitish, or colorless streak, yellowish or brownish, sometimes white transparent to translucent. Certain varieties... 

WURTZITE. A mineral zinc sulfide, (Zn, Fe),S. similar to sphalerite. Crystallizes in the hexagonal system. Hardness, 3.5-4 specific gravity, 3.98 color, brownish-black with resinous luster. Named after Adolphe Wiirtz. Fiance. 

Zinc sulfide, or sphalerite, crystallizes in the following cubic unit cell ... 

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... 

It should not be supposed that crystal defects enter into the picture only as nuisances which the chemist seeks to avoid or eliminate. Actually, certain optical and electrical properties of oxides, sulfides, and halides have been found to depend strongly on the nature and extent of crystal defects. Indeed, semiconductivity, fluorescence (absorption of radiation and emission of less energetic radiation), and phosphorescence (delayed fluorescence) of some salts may be spectacularly increased, not only by a small stoichiometric excess of one of the constituents, but also by addition of very tiny quantities of a foreign ion. Perhaps the best known example is the case of zinc sulfide which, when precipitated from aqueous solution and dried at low temperatures, shows negligible fluorescence upon exposure to ultraviolet light. When the sulfide is heated to... 

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 stracture 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. Consequently, a mineral coating of irregular ferrihydrite particles grew on the surface to a thickness of 2 nm. 

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