Structure and features of the surface morphology of <Emphasis Type="Italic">A</Emphasis><Superscript>4</Superscript><Emphasis Type="Italic">B</Emphasis><Superscript>6</Superscript> chalcogenide epitaxial films

The structure and features of the surface morphology of Pb_{1 − x} Mn _x Se (x = 0.03) epitaxial films grown on freshly cleaved BaF₂(111) faces and PbSe_{1 − x} S _x (100) (x = 0.12) single-crystal wafers were investigated by molecular beam condensation and the hot-wall method. It is shown that the epitaxial films, in accordance with the data in the literature for other chalcogenides, grow in the (111) and (100) planes, repeating the substrate orientation. Black aggregates are observed on the film surface of the films grown. The results obtained are compared with the data in the literature and generalized for other chalcogenides: A ⁴ B ⁶:Pb (S, Se, Te); Pb_{1 − x} Sn _x (S, Se, Te); and Pb_{1 − x} Mn (Se, Te). It is established that the formation of black aggregates, which are second-phase inclusions on the surface of epitaxial films obtained by vacuum thermal deposition, is characteristic of narrow-gap A ⁴ B ⁶ chalcogenides.     

MOVPE Growth of Wide Band-Gap II—VI Compounds for Near-UV and Deep-Blue Light Emitting Devices

We report on the growth by metalorganic vapour phase epitaxy of high structural and optical quality ZnS, ZnSe and ZnS/ZnSe multiple quantum well (MQW) based heterostructures for applications to laser diodes operating in the 400 nm spectral region. High purity ^tBuSH, ^tBu₂Se and the adduct Me₂Zn:Et₃N were used as precursors of S, Se and Zn, respectively. The effect of the different MOVPE growth parameters on the growth rates and structural properties of the epilayers is reported, showing that the crystallinity of both ZnS and ZnSe is limited by the kinetics of the incorporation of Zn, S and Se species at the growing surface. Very good structural and optical quality ZnS and ZnSe epilayers are obtained under optimized growth conditions, for which also dominant (excitonic) band-edge emissions are reported. The excellent ZnS and ZnSe obtained by our MOVPE growth matches the stringent requirements needed to achieve high quality ZnS/ZnSe MQWs. Their structural properties under optimized MOVPE conditions are shown to be limited mostly by the formation of microtwins, a result of the intrinsic high lattice mismatch involved into the ZnS/ZnSe heterostructure. Despite the large amount of defects found, the optical quality of the MQWs turned out to be high, which made possible the full characterization of their electronic and lasing properties. In particular, photopumped lasing emission up to 50 K in the 3.0 eV energy region are reported for the present MQWs heterostructures under power excitation density above 100 kW/cm².     

Infrared optical properties of Cu1−xLixSe2 thin films

Infrared absorption spectra of Cu_1−xLi_xInSe₂ thin films are measured at room temperature in the wavenumber range from 100 to 600 cm⁻¹. The spectra exhibit two absorption bands in the wavenumber ranges 200–210 cm⁻¹ and 330–355 cm⁻¹ which are ascribed to vibrational modes due to In Se and Li Se vibrations, respectively. The influence of the phase transition from the chalcopyrite structure to the β-NaFeO₂ structure in the composition range x = 0.5–0.6 on the vibrational characteristics is established and discussed.     

Crystal structure of Ga<Subscript>0.5</Subscript>In<Subscript>1.5</Subscript>Se<Subscript>3</Subscript> solid solution

A solid solution of the GaIn₃Se₆ (2Ga_0.5In_1.5Se₃) composition with a hexagonal lattice (a = 7.051(3) Å, c = 19.148(2) Å, sp. gr. P6₁, z = 6, V = 824.4332(4) ų, ρ = 5.379(2) g/cm³) has been synthesized as a result of alloying Ga, In, and Se elements with a metal ratio of 1: 3. It was established that six out of nine In atoms in the lattice are located in a trigonal bipyramid, while the other three In atoms and three Ga atoms have a tetrahedral coordination.     

Chemistry of organic eutectics: Phenanthrene — benzoic acid and phenanthrene — cinnamic acid systems

Solid-liquid equilibrium data for binary systems of phenanthrene with benzoic acid and cinnamic acid, expressed in the form of temperature-composition curves, show the formation of a simple eutectic in each case. Linear velocity of crystallisation (v), studied by capillary method at different undercoolings (ΔT), suggests the applicability of Hillig-Turnbull equation, v = u(ΔT) ⁿ, where u and n are constants depending on the nature of solidification. Data on heats of fusion of pure components and eutectics, determined by the DTA method, infer appreciable interaction among the components in the eutectic melts. To highlight the nature of interactions among the components forming the eutectic melt, the excess thermodynamic functions such as h^E, s^E, and g^E were computed. Microscopic studies reveal that the structure of eutectic is different from those of the parent components. Infrared spectra, recorded in the region, 4000 —625 cm⁻¹, indicate weak interactions among the components in the eutectic.     

Crystalline structure of Cu<Subscript>4</Subscript>SSe

Ternary compound Cu₄SSe has been first synthesized by alloying the Cu, S, and Se elements taken in stoichiometric ratios. An X-ray diffraction study of polycrystalline samples has revealed the synthesized material to be crystallized into the trigonal system with unit-cell parameters а = 4.021(1) Å, с = 6.838(1) Å, and V = 95.75(4) ų; sp. gr. P\(\bar 3\)m1; Z = 1; D_x = 6.333(3) g/cm³. The crystal structure has been solved and refined to the reliability factor R_Bragg = 0.40%.     

On the morphology of <100>-textured Germanium Crystallites in Zn—Ge Eutectic Alloy

Different geometry parameters for the cross-like germanium crystallites (eutectic dendrites) of the Zn-Ge eutectic alloys unidirectionally solidified have been related to the growth rate R and liquid temperature gradient G using linear regression analysis. It has been found that for eutectic dendrite spacing λ, balk length d and balk thickness b follow the relationship of the type w = C_wR^−rwG^−gw; C_w is a constant. The spacing relationship of eutectic dendrites (r_λ = 0.21; g_λ = 0.48) shows a similarity with published experimental and theoretical results on primary dendrite arm spacing (r_λ = 0.25; g_λ = 0.5). It has been shown in terms of a profile ration λ/d that for geometrical similar morphologies the relationship λ²R = const. is valid.     

The Crystal and Molecular Structure of 11,12‐dibromo‐ 7,8—benzo‐1,5‐di(p—tolylsulphonyl)‐1,5‐diazacyclononan

The crystal structure of the title compound, C₂₅H₂₆Br₂N₂O₄S₂ was determined by single crystal X‐ray diffraction technique. The crystals are monoclinic, space group C 2/c, with a=20.7142(2) Å b=11.7910(2) Å, c= 10.6735(3) Å, β=98.549(2)°, V=2577.94(9) ų, Z=4. The structure was solved by direct methods and refined by least‐squares methods to a final R=0.046 for 1866 observed reflections with I>2sigma(I). The title compound, displays disordered geometry around the C1 atom located almost on twofold axis. The nine‐membered heterocylic ring is close to the half‐chair conformation. The dihedral angle between phenyl rings is 34.2(1)°.     

Spectroscopic study of phosphine selenide complexes of Au(I) and X-ray structure of [(cyclohexyl)3PSeAuBr]

The X-ray structure determination of the complex, [(cyclohexyl)₃PSe-AuBr], revealed a triclinic space group P-1, with a = 9.7654(7), b = 10.9441(9), c = 11.2064(9) Å, = 117.076(6)°, = 99.076(6)° = 95.417(6)°, V = 1034.07(14) ų and Z = 2. The Au(I) atom in this complex has a linear coordination with Se1 atom at 2.3776(9) Å on one side and Br1 at 2.3843(9) Å at the trans position making the Se1-Au1-Br1 angle of 177.97(4)°. The P1 atom in the phosphine has tetrahedral geometry. All three cyclohexyl groups are in their usual boat conformation. The phosphorus atom of the triphenylphosphine is approximately perpendicular to the Se1—Au1—Br1 linkage with P1—Se1—Au1 angle of 99.19(6)°. The in the ³¹P NMR of the free ligands and their corresponding L—Se—Au—Br (L—Se = trialkyl/arylphosphine selenides) complexes, and the changes in the P—Se bond frequencies in the FTIR upon complexation, are indicative of the bonding of the ligand to Au(I) through selenium. There is a strong corelation between the chemical shifts of the ³¹P NMR and the C—P—C angle in the phosphines.     

2-phenyl thiazolidine — its growth and characterisation

The importance of 2-phenyl thiazolidine lies in its being a model for penicillin, as the five-membered thiazolidine ring happens to be the moiety of penicillin. This material is synthesised and crystallised (Tsukerman). The crystals are white in colour, transparent, needle-shaped and of dimensions (0.2 × 0.3 × 0.4 mm³). Employing X-ray diffraction studies, it is found that the crystal belongs to the orthorhombic system with the unit cell parameters a = 8.388(1), b = 18.114(2) and c = 5.625(1) Å. The space group is P 2₁2₁2₁ and Z = 4. The absorption peaks pertaining to NH, NCS, methylene CH₂ and aromatic C₆H₄ have been identified from the infrared absorption spectrum of the sample. The Proton Magnetic Resonance (PMR) spectrum fully accounts for the hydrogens in the sample thereby unambigiously supporting the proposed structure.     

Phase transformation in the system TlBi(Te1‐xSex)2

TlBiTe₂ and TlBiSe₂ ‐ that are ternary analogs of the IV‐VI semiconductors ‐, although they crystallize in the same space group R m (D⁵_3d), exhibit different behaviour during heating. The observed phase transformation depends on Se content (x) in the system TlBi(Te_1‐xSe_x)₂ and the transformation disappears by increasing Se content after a certain value (x = 0.25). This dependence is examined through the analysis of the DSC non‐isothermal measurements and an attempt for the explanation of the observed behaviour is undertaken through the consideration of off‐center atoms. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multimode phonon structure of Be‐containing II ‐ VI mixed crystals determined by IR spectroscopic ellipsometry

Spectroscopic ellipsometry in the infrared spectral range 250‐5000 cm^‐1 is used for analysis of the dielectric response of Zn_1‐x‐yBe_xMg_ySe and Zn_1‐x‐yBe_xMn_ySe crystals grown by a high‐pressure Bridgman method. Ellipsometric spectra display features in the spectral range 390‐500 cm^‐1 associated with BeSe‐type phonon modes. In the optical spectra of Zn_1‐x‐yBe_xMg_ySe crystals both BeSe‐type and MgSe‐type lattice absorption bands are detected. The MgSe‐like modes are located at approximately 300 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three and one or two classical damped oscillators corresponding to the BeSe‐like and the MgSe‐like transverse‐optical phonon modes, respectively. The frequencies of longitudinal‐optical phonons have been derived from the dielectric loss functions. A red‐shift of the BeSe‐like phonons frequencies with a mean rate 0.42 cm^‐1 (0.50 cm^‐1) per mole percent of Mg (Mn) incorporated to the alloy has been found for examined concentration range x, y ≤ 0.25. A noticeable damping the intensities of BeSe‐type modes with increasing fraction of Mg and Mn dopant is observed in comparison to the strengths of BeSe‐type modes in Zn_1‐xBe_xSe crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Mikrohärteuntersuchungen an Einkristallen der Verbindungen Tl3BX4, (B = V,Nb, Ta; X=S,Se)

Vickers microhardness measurements were performed on single crystals of compounds Tl₃BX₄ (B = V, Nb, Ta; X = S, Se). The anisotropy of the hardness on the (111)-plane was beyond the standard deviation. Besides the load-dependent Vickers hardness HV, the corrected, load-independent hardness HV_c was determined. Tl₃VS₄ showed the highest value of hardness (HV = 66 kp/mm² at 15 p load), the othe compounds differ only slightly in hardness.     

Bulk modulus — volume — ionicity relationship in tetrahedrally bonded semiconductors

It is shown that the bulk modulus of all diamond, zincblende and wurtzite structure compounds can be evaluated by means of the simple relation B = b₀a^−m(1 – g₀f_i) where a is the lattice parameter, f_i the spectroscopically defined bond ionicity and b₀, m and g₀ are constants having the same values for all compounds. This bulk modulus relation is used to estimate the bulk moduli for those zincblende and wurtzite structure compounds for which no experimental measurements have been made until now.     

V-ΔT and V-λ relation for the naphthalene—adipic acid system

The mechanism of crystal growth from the undercooled melt is studied experimentally for the naphthalene-adipic ac d system by means of a simple capillary technique. The microscopic observations for the 0.11 molefraction of naphthalene-adipic acid mixture indicated lamellar structure. The relationship between lamellar spacing, λ, and crystallization velocity V was found to be λ²V = constant.     

Dielectric Properties of Superionic System AgBr—PbI2—Ag2O—B2O3

Dielectric properties of the system AgBr—PbI₂—Ag₂O—B₂O₃ has been studied for various temperatures and frequencies. Conductivity of the sample has also been measured and it is found that at 160 °C it attains the value 5.9 × 10^—3 (Ohms cm)^—1 and the activation energy calculated from the Arrhenius is found to be 0.16 eV.     

X‐ray Determination of Lattice Constants of CdXSn1‐XSe Mixed Crystal Systems

Cd_XSn_1‐XSe with x = 0, 0.25, 0.3, 0.5, 0.75 and 1 are synthesized by melt technique and are found to be polycrystalline in nature. The X‐ray powder diffraction data of polycrystalline Cd_XSn_1‐XSe with x = 0, 0.25, 0.3, 0.5, 0.75 and 1 are analysed at room temperature and reported. The XRD peaks are indexed using DICVOL91 and cell constants are refined using the software UNITCELL. The powder diffraction patterns, lattice parameters and other data describing these compounds are presented in this paper.     

Optical and structural properties of Ge–Se bulk glasses and Ag–Ge–Se thin films

The optical and structural properties of Ge₂₀Se₈₀, Ge₂₅Se₇₅ and Ge₃₀Se₇₀ bulk glasses and Ag_x(Ge_0.20Se_0.80)_100−x thin films, where x = 0, 6, 11, 16, 20 and 23 at.% were studied. All samples were confirmed as amorphous according to XRD. The Raman spectra showed increase in 260 cm⁻¹ and 237 cm⁻¹ and decrease in 198 cm⁻¹ and 216 cm⁻¹ bands with different Se content in the bulk samples. The optical bandgap energy of bulk samples decreased (2.17–2.08 eV) and refractive index increased (2.389–2.426 at 1550 nm) with increasing Se content in bulk glasses. The Ge₂₀Se₈₀ thin films were prepared by vacuum thermal evaporation from Ge₃₀Se₇₀ bulk glasses. The Raman spectra of the films showed that peaks at 260 cm⁻¹ and 216 cm⁻¹ decreased their intensities with increasing Ag content in the thin films. The significant red shift of bandgap energy occurred upon different Ag content. The optically induced dissolution and diffusion resulted in graded refractive index profile along the film thickness caused by different Ag concentration. The refractive index increased from the substrate side to the top of thin films. The graded profile was getting more uniform with increasing content of silver in the thin film.     

Investigation of II –VI alloy lattice dynamics by IR spectroscopic ellipsometry

Optical properties related to lattice vibrations of bulk Zn_1‐xBe_xSe, Zn_1‐x‐yBe_xMn_ySe and Cd_1‐xBe_xSe alloys are reported. Optical phonons of the mixed crystals grown by the Bridgman method have been investigated by infrared spectroscopic ellipsometry in the wave‐number range 300‐8000 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three classical damped oscillators corresponding to the BeSe‐like transverse‐optical phonon‐modes and a Drude contribution from the free carriers. The frequencies of longitudinal‐optical phonons have been found from the imaginary parts of the dielectric loss functions. The influence of the alloy composition on the zone‐centre optical phonon frequencies is discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A combined 77Se NMR and Raman spectroscopic study of the structure of GexSe1-x glasses: Towards a self consistent structural model

The short-range structures of stoichiometric and Se-deficient binary Ge_xSe_100 ?x glasses with 42 ≥ x ≥ 33.33 have been investigated using a combination of Raman and ⁷⁷Se Car–Purcell–Meiboom–Gill (CPMG) spikelet nuclear magnetic resonance (NMR) spectroscopy. When taken together, these spectroscopic results allow for self-consistent assignment of average ⁷⁷Se NMR isotropic chemical shifts to Se atoms in various coordination environments in Ge_xSe_100 ?x glasses. Analysis of the compositional variation of the relative concentrations of these Se environments indicates considerable violation of chemical order in the nearest-neighbor coordination environments of the constituent atoms in the stoichiometric Ge_33.33Se_66.67 glass. On the other hand, the presence of a random distribution of Ge―Ge bonds can be inferred in the Se-deficient glasses. Simulations of the previously published ⁷⁷Se NMR line shapes of Se-excess glasses on the basis of the revised structural assignments of ⁷⁷Se NMR chemical shifts obtained in this study conclusively indicate that the structure of these glasses is intermediate between a randomly connected and a fully clustered network of GeSe₄ tetrahedra and Se chains.