The ternary transition metal nitrides of general formulation AMN2 (A = alkaline earth metal, M = transition metal) have been systematically studied. These compounds have been synthesised by high temperature solid state reaction from their component binary nitrides in sealed systems. The structures of these materials have been determined by powder X-ray diffraction (PXD) and two layered structure-types (α-NaFeO2-type and KCoO2-type) have been observed, thus far. Intriguingly, magnetic measurements performed on nitride samples indicate they may not be diamagnetic (d = 0, S = 0) as their nominal stoichiometry suggests.

Aluminum nitride whiskers were synthesized by nitridation of commercial aluminum powder at 1623K in a nitrogen atmosphere. The starting materials consisted of aluminum and carbon black. The carbon acted as a barrier between aluminum powders during nitridation and was removed by heating in air at 923K. The whiskers were about 0.5-1μm in diameter and 10-20μm in length. The droplets at the whisker tips showed that the whiskers grew via a vapor-liquid-solid mechanism. The morphologies of the whiskers were studied by means of SEM and TEM. The formation of the whiskers depended on the processing conditions.

Whiskers of silicon nitride were synthesized by heating silicon powder compacts, silicon single crystal and polycrystalline silicon in microwave in the presence of flowing forming gas or nitrogen. Various gas compositions and form of silicon used resulted in different whisker morphologies. Silicon powder as starting material leads to the formation of needle-like whiskers while silicon single crystal and polycrystalline silicon led to the formation of wool-like and web-like structures respectively. Length of the whiskers apparently depends on the holding time at the optimum temperature ~1350°C; whiskers up to 250 micrometers in length may be grown in 30 minutes. Microstructural data suggest that the silicon nitride whiskers form through gas-solid reaction and vapor-solid mechanism.

Solvothermal reactions in ethylenediamine have resulted in two quaternary mercury containing selenoantimonates: RbHgSbSe3 (I) and CsHgSbSe3 (II). Compound I crystallizes in monoclinic system, space group P2l/c (no. 14) with a = 7.758(2)Å, b = 11.234(2)Å, c = 8.849(2) Å, β = 106.60(3)°, V = 739.1(3)Å3, Z = 4. Compound II crystallizes in orthorhombic system, space group Cmcm (no. 63) with a = 4.444(1)Å, b = 15.514(6)Å, c = 11.261(7) Å, V = 776.4(6) Å3, Z = 4. Both compounds are layered materials and their crystal structures are closely related. Both contain layers of 2[HgSbSe3-] separated by alkali-metal cations A+ (Rb, Cs). Diffuse reflectance experiments show that both compounds are semiconductors with estimated band gaps of 1.7 eV for I and 1.6 eV for II, respectively.

The electrical and optical properties of the NiS2-xSex system are interpreted in terms of a band structure diagram that places a Mott-Hubbard, correlation-split Ni 3deg and the S 3pσ* band in the vicinity of the Fermi level. A variety of seemingly problematic experimental findings are resolved by adoption of this hypothesis.

The synthesis and characterisation of several mesostructured thiogermanates are shown. In particular the first supramolecular templated synthesis of mesostructured binary metal chalcogenides in a microwave is presented. The obtained products are characterised by x-ray powder diffraction, transmission electron microscopy, thermal analysis and x-ray absorption spectroscopy.

Studies have shown that complex Zintl phases exhibit a rich diversity of crystal structures. These have also revealed a remarkable success of the Zintl concept in rationalizing stoichiometry, crystal structure and chemical bonding of many main group intermetallics. Still there are unresolved questions about the usefulness of the concept in explaining structure-property relationships in intermetallics near the Zintl border, and as a rational tool in designing new materials. Limitations of the concept are represented by violations often associated with “electron-deficient” phases that contain Group 13 metalloids. Recent investigations on “electron-deficient” Zintl phases containing post transition metals have led to the synthesis of a number of novel inorganic-intermetallic π-systems. Since unique structures and properties are already apparent in normal Zintl phases, it is anticipated that the exploratory synthesis and characterization of conjugated and multiple-bonded inorganic systems will produce not only unusual crystal chemistry but interesting physical properties as well. We report on new complex Zintl phases that include the semiconducting SrCa2In2Ge - which features [In2Ge]6- chains and represents a novel inorganic conjugated π-system analogous to a polyallyl chain with In-In double bonds, and Ca5In9Sn6 - which contains In trimers, [In3]5- analogous and isoelectronic with the aromatic cyclopropenium cation, [C3H3]+. These unusual materials, Zintl π-systems, represent a promising class of electronic materials with a range of potential applications.

The phases K6Sn23Bi2, K6Sn25, NaSn5, BaSn3, BaSn5, and K5Pb24 depict the structural transition from Zintl phases with localized chemical bonds to typical intermetallic compounds which may even have superconducting properties. The question of the nature of the chemical bond in these compounds is studied with the help of quantum mechanical calculations. Tight binding band structure calculations and real space representations using the Electron Localization Function (ELF) show that free electron pairs play a crucial role for the description of the chemical bond in polar intermetallic compounds. Interactions between lone pairs have a dominant influence on the electronic structures. The coincident appearance of quasi-molecular localized states in form of lone pairs and disperse delocalized bands at the Fermi level EF is discussed with respect to a ‘chemical view’ of the superconductivity observed for BaSn3, BaSn5, and K5Pb24.

The synthesis of many targeted ternary compounds using conventional synthesis approaches has been unsuccessful because the ternary compounds are thermodynamically unstable with respect to disproportionation to a mixture of binary compounds. Typically these compounds have been synthetic targets based on predictions of enhanced properties. The ternary skutterudites with formula M'xM4Sbl2 (where M' = La, Lu, Y) are prime examples. Compounds with this structure have been found to be very promising thermoelectric materials having both good electrical properties and low thermal conductivities. Inserting heavy M' atoms into this crystal structure has been predicted to further decrease the thermal conductivity by increased phonon scattering. Attempts to make the title compound using conventional synthesis approaches failed due the formation of binary compounds as reaction products. Using modulated elemental reactants we were able to prepare the title compound at 160°C. Annealing at temperatures above 500°C resulted in exothermic decomposition into binary compounds. The Bi containing compounds are therefore thermodynamically unstable with respect to disproportionation at all temperatures. The amount of Bi can be varied by varying the composition of the starting modulated elemental reactant. Preliminary measurements to determine the variation of electrical conductivity and Seebeck coefficient as a function of bismuth content are presented.

The solid state reaction of YNi2B2C by mechanical alloying of elemental powders has been investigated by X-ray diffraction, transmission electron microscopy and susceptibility measurements. Depending on the ball milling parameters either nanocrystalline YNi2B2C or an amorphous phase can be produced. Crystallization of the amorphous phase by annealing at 893 K produces YNi2B2C as major and Ni2B as minor intermetallic compound. Superconductivity is only observed in the annealed state. However, the transition temperature is much lower than in arc-melted samples. This is discussed with respect to the nanocrystalline and amorphous state as well as deviations from stoichiometry produced by impurities introduced during milling.

The promising hydrogenation properties of oxygen-stabilised qr-phases with filled-Ti2Ni structure type in Zr-M-O systems (M - V, Cr, Mn, Fe, Co, Ni) are shown in this work. Hydrogenation capacity of the representative examples of compounds with 1:1 and 2:1 metal/metal ratio – Zr3V3O and Zr4Fe2Ox – are presented on the dependence of oxygen content in order to discuss its influence on the hydrogen storage capacity of Zr-based η-phases. The hydrogen disproportionation of η-Zr4Fe2Ox as well as oxygenless pseudobinary (Zr0.6Hf0.4)2Fe compounds with the same structure was studied. The reducing of metal matrix stability with the decrease of oxygen content is shown and explained by the increase of the total energy of crystal lattice.

The synthesis and characterization of binary and ternary semiconductor alloys and ordered phases based on C, Si and Ge are described. Thin films of these materials were synthesized using molecular precursors such as (SiH3)4C and (GeH3)4C in which the Si4C and Ge4C tetrahedra are incorporated as building blocks during deposition. Materials systems prepared include a new ordered structure (Si2Ge)1-xCx (x=5%), and Ge1-xCx hybrids of Ge and C-diamond. The (Si2Ge)Cx phase has a P 3ml structure formed by ordering of the [111] lattice planes in a Ge-Si-Si sequence. The Ge-C materials display unusual morphologies ranging from coherent heterostructures to carbide nanorods and quantum dots which are formed by CVD reactions utilizing a new family of (GeH3)4-xCHx (x=0-2) precursors. The morphology and microstructure in the samples is dependent upon the molecular design of the precursor and the carbon concentration.

The low temperature (ca. 300°C) deposition of antimony films by low-pressure chemical vapor deposition (LPCVD) on glass substrates from tribenzylantimony, Bn3Sb, is described. The facile elimination of the benzyl ligands results in preferentially oriented antimony films with low carbon content. The pyrolysis, decomposition mechanism and precursor design strategies are discussed. In addition, the deposition of bismuth from tribenzylbismuth, Bn3Bi, is presented. The potential for alloy growth using these precursors is discussed. Resulting films were characterized by XRD, SEM, and AFM.

Iron(II)-ethylene-bis-(phosphonates), Fe2[O3P-(CH2)2-PO3]·2H2O was synthesized by reaction of [FeSO4]·7H2O and the corresponding ethylene-bis-(phosphonic acid) and it was characterized by X-ray powder diffraction, thermogravimetry, UV-visible and infrared spectroscopy, and the magnetic properties were studied by a SQUID magnetometer. The metal-ion is in the d6 high-spin electronic configuration and it appears to have an octahedral coordination. The thermal variation of the d.c. magnetic susceptibility of Fe2[O3P-(CH2)2-PO3]·2H2O follows the Curie-Weiss law, with a negative Weiss constant of θ =-55K. Below 100K, the susceptibility increases until a peak at TN=24K is observed, and this is associated to the three-dimensional antiferromagnetic order. Below 24K, Fe2[O3P-(CH2)2-PO3]·2H2O behaves as a “weak” ferromagnet and it represents an example of an unusual kind of molecular-based magnetic materials, having a finite zero-field magnetization.

Growth of [(C10H8N2)2CuBr]Cu3Br4(I) crystals was achieved using the hydrothermal synthesis. Single crystal X-ray diffraction analysis shows that this compound crystallizes in monoclinic system, space group P21/c (no. 14) with four formula units in the unit cell. The cell dimensions are the following: a = 16.769(2) Å, b = 23.873(6) Å, c = 6.523(2) Å, β = 98.37(3)°, V = 2584(1) Å3. The title compound represents a new structure type. It consists of one-dimensional ribbons of 1[(Cu3Br4)] extending along the c-axis and discrete [(C10H8N2)2CuBr]+ complexes. The magnetic susceptibility study indicates a paramagnetic behavior due to the Cu(II) in the complex cations. The effective paramagnetic moment was calculated to be 2.20 μB from fitting the χ(T) data.

Formation of nanocomposites in the course of hydrolytic polycondensation processes is investigated. Depending on the order of particle-formation and matrix-formation steps three possible synthetic strategies are studied. The freeze-drying technique is used for dehydration of the gel precursor to avoid the redistribution of a soluble component. Heat treatment or chemical modification of the cryogel yields the desired nanomaterial.

Compacts of composites SiC-diamond were made by infiltration of Si into nanocrystalline diamond powders in a toroid-type press under the pressure of 7.7 GPa at 1300 °C. In-situ high pressure diffraction studies of these processes were performed in MAX80 cubic anvil press at a pressure of 8.5 GPa in temperatures up to 1800°C in HASYLAB at DESY, Hamburg, Germany. Sintering was performed for (i) pure nanocrystalline diamond powders, (ii) a mixture of nanocrystalline powders of diamond and nanocrystalline SiC, (iii) a mixture of nanocrystalline diamond with microcrystalline Si powders and (iv) compacts of nanocrystalline diamond infiltrated by Si. The SiC-diamond composites obtained by infiltration of Si have best physical properties: hardness similar to conventional diamond compacts (approximately 50 GPa), highest density 3.35 g cm-3 and uniform nanocrystalline microstructure.

Retention of the void space upon loss of the solvent template is directly demonstrated using single-crystal X-ray diffraction for molecular frameworks constructed using both hydrogen and co-ordinate bonds. While the co-ordination polymer remains rigid upon desolvation, the extra flexibility in the hydrogen-bonded framework, due both to the large number of redundant hydrogen-bonding donor and acceptor groups and the possibility of significant φ-φ stacking interactions within the framework, lead to a significant structural and symmetry change while retaining significant void volume. Molecular modelling techniques are used to understand and predict the guest uptake chemistry of these host frameworks.

The graphite intercalation compounds CxC8F17SO3 · yF and CxN(SO2CF3)2 are readily prepared under ambient conditions in 48 % hydrofluoric acid, using the oxidant K2MnF6. The product compositions are evaluated by mass uptake, TGA, and elemental analysis. PXRD peak position and peak width analyses indicate that the stable product CxC8F17SO3 · yF is obtained after 50 h. (x ≅ 18, y ≅ 4) and is comprised of a solid solution of stage 2 and 3. This material can be obtained within 1 h. at 50 °C. The addition of up to 83 vol. % conc. HNO3 or 17 % fuming H2SO4 produces a stage 2 intercalation compound within hours. Stage 2 CxN(SO2CF3)2 (x = 37) is obtained within 15 minutes under ambient condition in HF. The anion orientations for these GICs are evaluated by structural refinement. Larger anions containing –SO2CnF2n+1 substitutents can also be intercalated, although the reaction rates are very slow.