Formation of crystalline diamond from amorphous diamond-like carbon films by pulsed laser irradiation

The formation of crystalline diamond films from amorphous diamond-like carbon films by pulsed laser irradiation with a 300 μs non-Q-switched Nd:YAG laser has been established by a combined study of transmission electron microscopy, x-ray photoelectron spectroscopy, and electrical resistivity. The films have been prepared by glow discharge decomposition of a mixture of propane, n-butane, and hydrogen in a rf plasma operating at a frequency of 13.56 MHz. Prior to laser irradiation, the films have been found to be amorphous by transmission electron microscope studies. After irradiation, the electron diffraction patterns clearly point out the formation of cubic diamond structure with a lattice spacing of 3.555 Å. However, the close similarity between diamond and graphite electron diffraction patterns could sometimes be misleading regarding the formation of a diamond structure, and hence, x-ray photoelectron spectroscopic studies have been carried out to confirm the results. A chemical shift in the C 1s core level binding energies towards higher values, viz., from 286.5 to 287.8 eV after laser irradiation, and a high electrical resistivity >1013 Ω cm are consistent with the growth of diamond structure. This novel "low-temperature, low-pressure" synthesis of diamond films offers enormous potential in terms of device compatibility with other solid-state devices.

Synthesis and structural aspects of quasicrystals in Mg-Al-Ag system: Mg4Al6Ag

The existence of an icosahedral phase in Mg−Al−Ag is better understood on a crystallographic basis rather than on a quantum structural diagram basis. The quasicrystalline structure is delineated in terms of quasiperiodic arrangement of Pauling triacontahedra, which can be identified in the equilibrium structure. Subtle differences in the electron diffraction patterns have been recorded compared to the ideal quasicrystalline pattern. The misalignment of spots and distortions are better attributed to higher order rational approximate structure than anisotropic phason strain. Ares of diffuse intensity have been related to the ordering among the atoms in the clusters.

Rapidly solidified Al–Cr alloys: Crystalline and quasicrystalline phases

Rapidly solidified Al–Cr alloys up to 20 at. % Cr were studied to delineate the extent of crystalline and quasicrystalline phase formation in these alloys in comparison with as-cast alloys by using transmission electron microscopy and x-ray diffraction technique. The icosahedral quasicrystals are observed from 7 to 15 at. % Cr alloys, while equilibrium ?–Al11Cr2 phase is completely absent. Both rapid solidification and subsequent thermal decomposition studies indicate that the main competing phase is ?–Al2Cr up to 15 at. % Cr. Beyond this composition ?–Al4Cr is the dominant phase together with a small amount of ?4–Al7Cr3. We have shown that the electron diffraction patterns of Al–Cr quasicrystals are often associated with a diffuse intensity distribution, indicative of short-range order. The change in quasilattice constant with composition suggests the existence of structural vacancies. Further, a sudden change from coarse to ultrafine quasicrystalline grain structure in Al-7 at. % Cr alloy points to a change in nucleation mechanism from heterogeneous to homogeneous mode during the rapid solidification.

Investigations on Bi2CuO4: a quasi-one-dimensional oxide system

The potential of Bi2CuO4 as the first oxide system to show a linear-chain magnetic behaviour is examined. Electron diffraction studies do not resolve the previously reported ambiguity regarding its space group. The magnetic susceptibility data at high temperatures are best fitted to a uniform antiferromagnetic spin-1/2 Heisenberg chain. At low temperatures, however, neither the uniform nor the alternating Heisenberg antiferromagnetic model fits the data. Magnetic susceptibility data over the entire temperature range can be fitted if one assumes dimeric units with a nearly degenerate second singlet state close to the ground state, these states being separated from an excited triplet state by an energy gap. A simple heuristic model of a dimer that gives such an energy level spectrum is examined.

Quasicrystals and their crystalline homologues in the Al-Mn-Cu ternary alloys

Electron diffraction and high-resolution electron microscopy have been employed to differentiate among icosahedral, decagonal and crystalline particles that occur in as-cast and rapidly solidified Al-Mn-Cu alloys. The resemblance between decagonal quasicrystals and crystals in their electron diffraction patterns is striking. The crystalline structure is based on the orthorhombic 'Al3Mn' structure, but also a new monoclinic phase called 'X' has been discovered and described here. The present observations are also closely related to the orthorhombic structures in Al60Mn11Ni4. The occurrence of fine-scale twinning and fragmentation into domains explains the complex diffraction effects.

Deffect Structure of LAMNO3

LaMnO3 compositions possessing orthorhombic, rhombohedral and cubic structures and containing 12, 24 and 33% Mn4+ respectively have been investigated by X-ray diffraction, electron diffraction and high resolution electron microscopy. The study shows that the defect structure of LaMnO3 is best described in terms of the random distribution of La and Mn vacancies, rather than by anion excess. Density measurements confirm the cation vacancy model involving an equal number of La and Mn vacancies.

Preparation and dielectric properties of zinc and cadmium doped barium tantalates, Ba3Zn1?xCdxTa2O9

Members of the Ba2Zn1-xCdxTa2O9 (0 less than or equal to x less than or equal to 1) series have been synthesized by solid state reactions at 1473K. Powder x-ray diffraction studies show a cubic perovskite cell with a similar to 4.1 Angstrom which increases with increase in x. Electron diffraction studies show the presence of hexagonal ordered perovskite structure in addition to the cubic structure seen by x-rays, the x = 0.5 composition showing more ordered crystallites. These samples show high dielectric constants with a maximum (epsilon(r) = 30 at 1 kHz) for the x = 0.5 member. The dielectric loss increases with increase in x at all the frequencies under study.

Icosahedral quasicrystalline and hexagonal approximant phases in the Al-Mn-Be alloy system

We report the formation of a primitive icosahedral quasicrystal with increased stability in Al Mn-Be alloys close to the compound Al15Mn13Be2, by melt spinning and injection casting. The crystal structure of this compound was unknown. We show that in as-cast as well as heat treated condition the intermetallic phase H1 has a hexagonal structure with lattice parameters a = 1.2295 run and c = 2.4634 nm. The space group is P6(3)/mmc In the injection-cast samples, the quasicrystal coexists with another closely related hexagonal phase H2 with a = 1.2295 nm and c = 1.2317 nm with a possible space group of P6/mmm. This phase exhibits specific orientation relationships with the icosahedral quasicrystal given by [0001](hex)//2f(QC) and [01 (1) over bar0](hex)//5f(QC) where 2f(QC) and 5f(QC) represent twofold and fivefold axes respectively. Electron diffraction patterns from both phases exhibit a close resemblance to the quasicrystalline phase. It is shown that the H1 phase is closely related to mu-Al4Mn with the same e parameter while the a parameter is reduced by tau. Following Kreiner and Franzen, it is postulated that both structures (H1 and H2) can be understood by a simple hexagonal packing of I13 clusters.

A Study of Nanostructures of Thin Films in B–C–N System Produced by Pulsed Laser Deposition and Nitrogen Ion-Beam-Assisted Pulsed Laser Deposition

We report the synthesis of thin films of B–C–N and C–N deposited by N+ ion-beam-assisted pulsed laser deposition (IBPLD) technique on glass substrates at different temperatures. We compare these films with the thin films of boron carbide synthesized by pulsed laser deposition without the assistance of ion-beam. Electron diffraction experiments in the transmission electron microscope shows that the vapor quenched regions of all films deposited at room temperature are amorphous. In addition, shown for the first time is the evidence of laser melting and subsequent rapid solidification of B4C melt in the form of micrometer- and submicrometer-size round particulates on the respective films. It is possible to amorphize B4C melt droplets of submicrometer sizes. Solidification morphologies of micrometer-size droplets show dispersion of nanocrystallites of B4C in amorphous matrix within the droplets. We were unable to synthesize cubic carbon nitride using the current technique. However, the formation of nanocrystalline turbostratic carbo- and boron carbo-nitrides were possible by IBPLD on substrate at elevated temperature and not at room temperature. Turbostraticity relaxes the lattice spacings locally in the nanometric hexagonal graphite in C–N film deposited at 600 °C leading to large broadening of diffraction rings.

Structural, optical, and electrical properties of bulk single crystals of InAsxSb(1-x) grown by rotatory Bridgman method

Radially-homogeneous and single-phase InAsxSb(1−x) crystals, up to 5.0 at. % As concentration, have been grown using the rotatory Bridgman method. Single crystallinity has been confirmed by x-ray and electron diffraction studies. Infrared transmission spectra show a continuous decrease in optical energy gap with the increase of arsenic content in InSb. The measured values of mobility and carrier density at room temperature (for x = .05) are 5.6×104 cm2/V s and 2.04×1016 cm−3, respectively.

Relaxor behavior of K0.5La0.5Bi2Nb2O9 ceramics

K0.5La0.5Bi2Nb2O9, a relaxor, was synthesized and the structural studies confirmed it to be an n = 2 member of the Aurivillius oxides. The ½{h00} and ½{hk0} types of superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak with frequency dependent dielectric maximum temperature was observed. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein Ea = 0.04 eV, Tf = 428 K,and ωo = 1010 Hz. The diffuseness parameter γ = 2.003 established the relaxor nature and it was attributed to the A-site cationic disorder. The piezoelectric d31 coefficient was 0.5 pC/N at 300 K and 2 pC/N at 480 K.

Quasicrystals and their crystalline homologues in the Al–Mn–Cu ternary alloys

Electron diffraction and high-resolution electron microscopy have been employed to differentiate among icosahedral, decagonal and crystalline particles that occur in as-cast and rapidly solidified Al-Mn-Cu alloys. The resemblance between decagonal quasicrystals and crystals in their electron diffraction patterns is striking. The crystalline structure is based on the orthorhombic ‘Al3Mn’ structure, but also a new monoclinic phase called ‘X’ has been discovered and described here. The present observations are also closely related to the orthorhombic structures in Al60Mn11Ni4. The occurrence of fine-scale twinning and fragmentation into domains explains the complex diffraction effects.

Studies towards synthesis, evolution and alignment characteristics of dense, millimeter long multiwalled carbon nanotube arrays

We report the synthesis of aligned arrays of millimeter long carbon nanotubes (CNTs), from benzene and ferrocene as the molecular precursor and catalyst respectively, by a one-step chemical vapor deposition technique. The length of the grown CNTs depends on the reaction temperature and increases from similar to 85 mu m to similar to 1.4 mm when the synthesis temperature is raised from 650 to 1100 degrees C, while the tube diameter is almost independent of the preparation temperature and is similar to 80 nm. The parallel arrangement of the CNTs, as well as their tube diameter can be verified spectroscopically by small angle X-ray scattering (SAXS) studies. Based on electron diffraction scattering (EDS) studies of the top and the base of the CNT films, a root growth process can be deduced.

Complex structural phase transitions in slightly Ca modified Na0.5Bi0.5TiO3

A temperature dependent neutron powder diffraction study, in conjunction with dielectric and ferroelectric characterization, of slightly Ca modified Na0.5Bi0.5TiO3 (NBT) revealed an instability with regard to a non-polar orthorhombic (Pbnm) distortion above room temperature. This intermediate orthorhombic phase has earlier been reported for unmodified NBT by electron diffraction studies, but has never been captured by global (x-ray/neutron) diffraction techniques. Calcium substitution seems to amplify the magnitude of this intermediate orthorhombic distortion thereby making the corresponding superlattice reflections become visible in the neutron diffraction pattern. The study revealed the following sequence of very complex structural evolution with temperature: Cc -> Cc + Pbnm -> Pbnm + P4/mbm -> P4/mbm -> Pm (3) over barm.

Metastable morphotropic phase boundary state in the multiferroic BiFeO3-PbTiO3

Temperature-time study of the magnetoelectric multiferroic (1-x)BiFeO3-(x)PbTiO3 by x-ray and electron diffraction on the reported morphotropic phase boundary (MPB) compositions revealed that this MPB does not correspond to the equilibrium state. The MPB like state is rather of metastable nature and arise due to kinetic arrest of metastable rhombohedral (R3c) phase, along with the equilibrium tetragonal (P4mm) phase. The life time of the metastable R3c nuclei is very sensitive to composition and temperature, and nearly diverges at x -> 0.27. The MPB like state appears only if the system is cooled before the metastable R3c nuclei could vanish. These findings resolve the long standing controversy with regard to seemingly erratic phase formation behaviour reported by different groups and provides a rational basis for developing genuine equilibrium MPB compositions in this system for better piezoelectric properties. (C) 2013 AIP Publishing LLC.