We review the discovery of a new phase BN (named Q-BN) which has been created by nanosecond laser melting in the super undercooled state and quenching rapidly with rates exceeding several billion degrees per second. This phase, sequel to our earlier discovery of Q-Carbon, has amorphous structure from which phase-pure c-BN is formed in the form of nanodots, microcrystals, nanoneedles, and microneedles. Large-area single c-BN are formed by providing a template for epitaxial growth during quenching of super undercooled liquid BN. Since there is a rapid crystal growth from liquid, both n- and p-type dopants can be incorporated into electrically active substitutional sites with concentrations exceeding solubility limits through the phenomenon of solute trapping. We have grown diamond on c-BN by pulsed laser deposition of carbon at 500°C without the presence of hydrogen, and created c-BN and diamond epitaxial composites. We discuss the mechanism of epitaxial c-BN and diamond growth on lattice matching c-BN template under pulsed laser evaporation of amorphous carbon. This discovery on direct conversion of h-BN into phase-pure c-BN at ambient temperatures and pressures in air, represents a seminal contribution to the field of boron nitride, which is quite complementary to our discovery of graphite to diamond conversion. We have bypassed thermodynamics with the help of kinetics and time control. This research represents a major breakthrough for c-BN and diamond based high-power electronic and photonic devices, and host of other applications related to high-speed machining, deep-sea drilling, field-emission displays and biomedical applications.

Group 6 transition metal oxide thin films are in large demand for photocatalysis, heterogeneous catalysis, fuel cell, battery and electronic applications. Pulsed laser deposition offers an inexpensive method for the preparation of nanostructured thin films that may be suitable for heterogeneous catalysis. We have synthesized molybdenum oxide thin films using two types of pulsed laser deposition (PLD). The first method utilizes femtosecond laser-based PLD (f-PLD) while the second method uses an excimer (nanosecond) laser-based PLD (n-PLD). The PLD films have been deposited using f-PLD and, separately, n-PLD on glass and silicon substrates and subsequently annealed to 450 °C for up to 20 hours in air using a Linkam stage. SEM, XRD and Raman spectroscopic characterization shows that the f-PLD films are substantially more textured and partially crystalline prior to annealing whereas the n-PLD-grown thin films are much smoother and predominantly amorphous. A 3-dimensional nano-crystalline structure is evident in the post-annealed f-PLD synthesized thin films, which is desirable for catalytic applications. XPS elemental analysis shows that the stoichiometry of the f-PLD and n-PLD thin films is consistent with the presence of MoO2 and MoO3. Our results are discussed in terms of thin film growth models suitable for f-PLD vs n-PLD.

Insulating silicon dioxide (SiO2) films can be produced by hydrolysis of metal alkoxide tetraethylorthosilicate (TEOS) in the presence of an acid catalyst in supercritical fluid CO2 (sc-CO2). In this study, SiO2 films are formed on different substrates using TEOS as a source of silicon, and acetic acid (HAc) as a catalyst. Water required for the hydrolysis reaction is from in situ generation of esterification and condensation reactions involving HAc and the alcohol produced. The acid catalyzed deposition reaction actually starts at room temperature but produces decent films in sc-CO2 at moderately high temperatures (e.g. 50 °C). Supercritical fluid CO2 is known to have near zero surface tension and provides an ideal medium for fabrication of SiO2 films. Formation of SiO2 films via hydrolysis reaction in sc-CO2 is more rapid compared to the traditional hydrolysis reaction at room temperature. In general, metal alkoxide hydrolysis reactions carried out in a closed sc-CO2 system is not affected by moisture in air compared with traditional open-air hydrolysis systems. Using sc-CO2 as a reaction medium can eliminate undesirable organic solvents utilized in traditional alkoxide hydrolysis reactions.

X-ray diffraction (XRD) and electron diffraction (ED) measurements demonstrated that the SiO2 films produced are amorphous. Energy dispersive spectroscopy (EDS), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) spectroscopy show elemental compositions of the films formed on the substrate surfaces to be SiO2. Film thickness formation by controlling the amount of the catalyst is discussed.

Sodium bismuth titanate (Na0.5Bi0.5TiO3: NBT) a lead free piezoelectric; exhibits promising features such that it could be an alternate to lead based piezoelectrics. In this work, we report the microstructural influence on piezoelectric and leakage current behavior of NBT thin films grown by pulsed laser ablation (PLD). Various microstructural features like coarse faceted grains and fine spherical grains was achieved by effective optimization of substrate temperature and oxygen partial pressures. The studies reveals that, leakage current of NBT thin films were dominated by interface limited modified Schottky emission type of conduction. The piezoelectric domain studies reveal that for NBT thin films with fine spherical grain the domain pattern was highly dominated by the morphology and in the case of coarse faceted grains the domains were relatively large and the domains were extending beyond the grain boundaries.

This study focuses on understanding the influence of incorporating Ammonium Acetate into the chemical bath used for the deposition of CdS thin films, on its optical, morphology, and microstructural properties. Thus, CdS thin films were deposited on 1” × 2” microscopic glass substrates using chemical bath deposition (CBD) technique. The deposition process was carried out in a double jacket beaker with fixed chemical bath temperature of 90°C for a deposition time of 40 min. The chemical bath solution consisted of fixed concentrations of Cadmium Acetate, Thiourea, and Ammonium Hydroxide; with corresponding values of 4.8×10-4M; 0.97×10-4M; and 0.2M, respectively. However, Ammonium Acetate was incorporated into the deposition bath with concentrations that were varied from 3.0 mM to 12.2 mM. Meanwhile, for comparison purposes associated to the initial physical and chemical properties of the CdS films; reference CdS films were deposited under the same above chemical bath conditions, but in the absence of Ammonium Acetate. The pH of the chemical bath was measured during the deposition process. The films’ morphology and the chemical composition were examined by Field Emission Scanning Electron Microscopy (FE-SEM), and the Energy Dispersive spectrometer (EDS), respectively. The X-Ray Diffraction (XRD) θ/2θ technique was applied to study the structure of the films, including the lattice parameters. Atomic Force Microscopy (AFM) was used to examine the films topography and to determine the root-mean-square (RMS) surface roughness of the films as well as the grain size. Dektak Surface Profilometer was used to determine the CdS films’ thickness, where the films’ optical properties were measured using UV-Vis-NIR spectrometer. Optical energy band gap (Eg), and absorption coefficient (α) were calculated from the transmission spectral data.

Density Functional Theory calculations of electronic and optical properties of NiO, with and without O vacancies, are the focus of this work. Two bands, one fully occupied and the other unoccupied, induced by an O vacancy, are found in the gap. These energy levels are identified and analyzed by means of a local density of states (LDOS) calculation, and notable crystal field splitting can be seen. The real and imaginary parts of the dielectric function are calculated, and an additional optical transition can be seen at lower energy, which can be attributed to the O vacancy induced state in the band gap.

The deposition of PbS thin films by the chemical bath deposition method using sodium citrate as non-toxic complexing agent is presented. As-deposited PbS films and those annealed at 200 and 300 °C in argon atmosphere were formed by tightly compact spherical particles homogeneously distributed along the substrates. The XRD analysis shows that all the films had a galena type cubic crystalline structure. The crystallite size of the as-deposited film was 17 nm which decreased to 14 nm when the film was annealed to 300 °C. Thermal treatments to the films produced a shift of the optical band gap from 1.34 to 1.49 eV. Furthermore, the as-deposited PbS films were photosensitive showing a conductivity of 10-2 Ω-1 cm-1 under illumination. Such a conductivity increased to 10-1 Ω-1 cm-1 with the thermal treatment at 200 °C. The evaluation of the PbS film using a CdS thin film partner as window in the solar cell configuration showed an open circuit voltage of 88 mV and a short current density of 3.5 mA/cm2.

In this study, we provide a novel approach to the epitaxial integration of TiO2 with Si(100) and investigate the defect mediated ferromagnetism in TiO2 structure. Epitaxial TiO2 thin films were grown on a TiN/Si(100) epitaxial heterostructure through oxidation of TiN where a single crystalline rutile-TiO2 (r-TiO2) with a [110] out-of-plane orientation was obtained. The epitaxial relationship is determined to be TiO2(1 $\bar 1$ 0)||TiN(100) and TiO2(110)||TiN(110). We rationalized this epitaxy using the domain matching epitaxy paradigm. First TiN is grown epitaxially on Si(100). Subsequently, TiN/Si(100) samples are oxidized to create r-TiO2/TiN/Si(100) epitaxial heterostructures. The details of the mechanism behind the oxidation of single crystalline TiN to TiO2 was investigated using atomic scale high resolution electron microscopy techniques. Defects introduced to the heterostructure during oxidation caused ferromagnetism in TiO2 thin film which is reversible and can be tuned by controlling oxygen partial pressure. The source of magnetization is correlated with the presence of oxygen vacancy leading to introduction of two localized states; hybrid and polaron among neighboring Ti atoms, and titanium vacancy providing four holes to form molecular oxygen. We present structure property correlations and its impact on the next generation solid state devices.

Bi-epitaxial VO2 thin films with [011] out-of-plane orientation were integrated with Si(100) substrates through TiO2/TiN buffer layers. At the first step, TiN is grown epitaxially on Si(100), where a cube-on-cube epitaxy is achieved. Then, TiN was oxidized in-situ ending up having epitaxial r-TiO2. Finally, VO2 was deposited on top of TiO2. The alignment across the interfaces was stablished as VO2(011)║TiO2(110)║TiN(100)║Si(100) and VO2(110) /VO2(010)║TiO2(011)║TiN(112)║Si(112). The inter-planar spacing of VO2(010) and TiO2(011) equal to 2.26 and 2.50 Å, respectively. This results in a 9.78% tensile misfit strain in VO2(010) lattice which relaxes through 9/10 alteration domains with a frequency factor of 0.5, according to the domain matching epitaxy paradigm. Also, the inter-planar spacing of VO2(011) and TiO2(011) equals to 3.19 and 2.50 Å, respectively. This results in a 27.6% compressive misfit strain in VO2(011) lattice which relaxes through 3/4 alteration domains with a frequency factor of 0.57. We studied semiconductor to metal transition characteristics of VO2/TiO2/TiN/Si heterostructures and established a correlation between intrinsic defects and magnetic properties.