Effect of Li substitution on dielectric and ferroelectric properties of ZnO thin films grown by pulsed-laser ablation

Li-doped ZnO thin films (Zn1-xLixO, x=0.05-0.15) were grown by pulsed-laser ablation technique. Highly c-axis-oriented films were obtained at a growth temperature of 500 degrees C. Ferroelectricity in Zn1-xLixO was found from the temperature-dependent dielectric constant and from the polarization hysteresis loop. The transition temperature (T-c) varied from 290 to 330 K as the Li concentration increased from 0.05 to 0.15. It was found that the maximum value of the dielectric constant at T-c is a function of Li concentration. A symmetric increase in memory window with the applied gate voltage is observed for the ferroelectric thin films on a p-type Si substrate. A ferroelectric P-E hysteresis loop was observed for all the compositions. The spontaneous polarization (P-s) and coercive field (E-c) of 0.6 mu C/cm(2) and 45 kV/cm were obtained for Zn0.85Li0.15O thin films. These observations reveal that partial replacement of host Zn by Li ions induces a ferroelectric phase in the wurtzite-ZnO semiconductor. The dc transport studies revealed an Ohmic behavior in the lower-voltage region and space-charge-limited conduction prevailed at higher voltages. The optical constants were evaluated from the transmission spectrum and it was found that Li substitution in ZnO enhances the dielectric constant.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti(62.5)Si(37.5) thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe(+) ion beam to an ion fluence of about 10(16) ions-cm(-2). Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti(5)Si(3) intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

Characterization of microstructure in laser-surface-alloyed layers of aluminum on nickel

In order to obtain basic understanding of microstructure evolution in laser-surface-alloyed layers, aluminum was surface alloyed on a pure nickel substrate using a CO2 laser. By varying the laser scanning speed, the composition of the surface layers can be systematically varied. The Ni content in the layer increases with increase in scanning speed. Detailed cross-sectional transmission electron microscopic study reveals complexities in solidification behavior with increased nickel content. It is shown that ordered B2 phase forms over a wide range of composition with subsequent precipitation of Ni2Al, an ordered omega phase in the B2 matrix, during solid-state cooling. For nickel-rich alloys associated with higher laser scan speed, the fcc gamma phase is invariably the first phase to grow from the liquid with solute trapping. The phase reorders in the solid state to yield gamma' Ni3Al. The phase competes with beta AlNi, which forms massively from the liquid. The beta AlNi transforms martensitically to a 3R structure during cooling in solid state. The results can be rationalized in terms of a metastable phase diagram proposed earlier. However, the results are at variance with earlier studies of laser processing of nickel-rich alloys.

Evolution of metastable phases during crystallization of pulsed laser deposited amorphous Al–Fe films

Amorphous thin films of different Al–Fe compositions were produced by plasma/vapor quenching during pulsed laser deposition. The chosen compositions Al72Fe28, Al40Fe60, and Al18Fe82 correspond to Al5Fe2 and B2-ordered AlFe intermetallic compounds and α–Fe solid solution, respectively. The films contained fine clusters that increased with iron content. The sequences of phase evolution observed in the heating stage transmission electron microscopy studies of the pulsed laser ablation deposited films of Al72Fe28, Al40Fe60, and Al18Fe82 compositions showed evidence of composition partitioning during crystallization for films of all three compositions. This composition partitioning, in turn, resulted in the evolution of phases of compositions richer in Fe, as well as richer in Al, compared to the overall film composition in each case. The evidence of Fe-rich phases was the B2 phase in Al72Fe28 film, the L12- and DO3-ordered phases in Al40Fe60 film, and the hexagonal ε–Fe in the case of the Al18Fe82 film. On the other hand, the Al-rich phases were Al13Fe4 for both Al72Fe28 and Al40Fe60 films and DO3 and Al5Fe2 phases in the case of Al18Fe82 film. We believe that this tendency of composition partitioning during crystallization from amorphous phase is a consequence of the tendency of clustering of the Fe atoms in the amorphous phase during nucleation. The body-centered cubic phase has a nucleation advantage over other metastable phases for all three compositions. The amorphization of Al18Fe82 composition and the evolution of L12 and ε–Fe phases in the Al–Fe system were new observations of this work.

Synthesis and Microstructure of Laser Surface Alloyed Al–Sn–Si Layer on Commercial Aluminum Substrate

A new type of bearing alloy containing ultrafine sized tin and silicon dispersions in aluminum was designed using laser surface alloying and laser remelting techniques. The microstructures of these non-equilibrium processed alloys were studied in detail using scanning and transmission electron microscopy. The microstructures revealed three distinct morphologies of tin particles namely elongated particles co-existing with silicon, globular particles, and very fine particles. Our detailed analyses using cellular growth theories showed that the formation of these globular tin particles was due to the pinching off of the tin rich liquid in the inter-cellular space by the growth of aluminum secondary dendrite arms. Evidence of fine recrystallized aluminum grains at the top layer due to constrained solidification was shown. Thermal analyses suggested that melting of the spherical shaped tin particles was controlled by the binary aluminum-tin eutectic reaction, whereas non-spherical tin particles melted via the tin-silicon eutectic reaction.

The ω Phase Formation during Laser Cladding and Remelting of Quasicrystal Forming AlCuFe on Pure Aluminum

We report the formation ω phase in the remelted layers during laser cladding and remelting of quasicrystal forming Al65Cu23.3Fe11.7 alloy on pure aluminum. The ω phase is absent in the clad layers. In the remelted layer, the phase nucleates at the periphery of the primary icosahedral phase particles. A large number of ω phase particles forms enveloping the icosahedral phase growing into aluminum rich melt, which solidify as α-Al solid solution. On the other side it develops an interface with aluminum. A detailed transmission electron microscopic analysis shows that ω phase exhibits orientation relationship with icosahedral phase. The composition analysis performed using energy dispersive x-ray analyzer suggests that this phase has composition higher aluminum than the icosahedral phase. The analysis of the available phase diagram information indicates that the present results represent large departure from equilibrium conditions. A possible scenario of the evolution of the ω phase has been suggested.

Formation of amorphous xenon nanoclusters and microstructure evolution in pulsed laser deposited Ti62.5Si37.5 thin films during Xe ion irradiation

As deposited amorphous and crystallized thin films of Ti 37.5% Si alloy deposited by pulsed laser ablation technique were irradiated with 100 keV Xe+ ion beam to an ion fluence of about 1016 ions-cm−2. Transmission electron microscopy revealed that the implanted Xe formed amorphous nanosized clusters in both cases. The Xe ion-irradiation favors nucleation of a fcc-Ti(Si) phase in amorphous films. However, in crystalline films, irradiation leads to dissolution of the Ti5Si3 intermetallic phase. In both cases, Xe irradiation leads to the evolution of similar microstructures. Our results point to the pivotal role of nucleation in the evolution of the microstructure under the condition of ion implantation.

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.

Laser‐Induced Turbulence

In a recent experiment on laser beam transmission through an absorbing gas, the critical Reynold's number for the flow, induced by the heating of the gas, to become turbulent was found to be less than 30, which is many orders of magnitude smaller than that for pure shear flow in pipes. It is shown here that a Rayleigh number is the more appropriate criterion to characterize the stability of flow in this situation, and its value estimated in two limiting cases is found to bracket the expected critical Rayleigh number for vertical concentric cylinders.

The omega phase formation during laser cladding and remelting of quasicrystal forming AlCuFe on pure aluminum

We report the formation omega phase in the remelted layers during laser cladding and remelting of quasicrystal forming Al65Cu23.3Fe11.7 alloy on pure aluminum. The omega phase is absent in the clad layers. In the remelted layer, the phase nucleates at the periphery of the primary icosahedral phase particles. A large number of omega phase particles forms enveloping the icosahedral phase growing into aluminum rich melt, which solidify as alpha-Al solid solution. On the other side it develops an interface with aluminum. A detailed transmission electron microscopic analysis shows that omega phase exhibits orientation relationship with icosahedral phase. The composition analysis performed using energy dispersive x-ray analyzer suggests that this phase has composition higher aluminum than the icosahedral phase. The analysis of the available phase diagram information indicates that the present results represent large departure from equilibrium conditions. A possible scenario of the evolution of the omega phase has been suggested.

Laser- induced optical properties change in Sb10S40Se50 chalcogenide thin films: An investigation through FTIR and XPS measurements

Chalcogenide glasses are interesting materials for their infrared transmitting properties and photo-induced effects. This paper reports the influence of light on the optical properties of Sb10S40Se50 thin films. The amorphous nature and chemical composition of the deposited film was studied by X-ray diffraction and energy dispersive X-ray analysis (EDAX). The optical constants, i.e., refractive index, extinction coefficient, and optical band gap as well as film thickness are determined from the measured transmission spectra using the Swanepoel method. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. The dispersion energy parameter was found to be less for the laser-irradiated film, which indicates the laser-irradiated film is more microstructurally disordered as compared to the as-prepared film. It is observed that laser-irradiation of the films leads to decrease in optical band gap (photo-darkening) while increase in refractive index. The decrease in the optical band gap is explained on the basis of change in nature of films due to chemical disorderness and the increase in refractive index may be due to the densification of films with improved grain structure because of microstructural disorderness in the films. The optical changes are supported by X-ray photoelectron spectroscopy data. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Epitaxial Co metal thin film grown by pulsed laser deposition using oxide target

We report here the growth of epitaxial Co metal thin film on c-plane sapphire by pulsed laser deposition (RD) using Co:ZnO target utilizing the composition inhomogeneity of the corresponding plasma. Two distinct plasma composition regions have been observed using heavily alloyed Co0.6Zn0.4O target. The central and intense region of the plasma grows Co:ZnO film; the extreme tail grows only Co metal with no trace of either ZnO or Co oxide In between the two extremes, mixed phases (Co +Co-oxides +Co:ZnO) were observed. The Co metal thin film grown in this way shows room temperature ferromagnetism with large in plane magnetization similar to 1288 emu cm(-3) and a coerciviLy of similar to 230 Oe with applied field parallel to the film-substrate interface. Carrier density of the film is similar to 10(22) cm(-3). The film is epiLaxial single phase Co metal which is confirmed by both X-ray diffraction and transmission electron microscopy characierizaLions. Planar Hall Effect (PHE) and Magneto Optic Kerr Effect (MOKE) measurements confirm that the film possesses similar attributes of Co metal. The result shows that the epiLaxial Co metal thin film can be grown from its oxides in the PLD. (C) 2014 Elsevier B.V. All rights reserved.

Photo-induced optical bleaching in Ge12Sb25S63 amorphous chalcogenide thin films: effect of 532 nm laser illumination

The photo-induced effects of Ge12Sb25S63 films illuminated with 532 nm laser light are investigated from transmission spectra measured by FTIR spectroscopy. The material exhibits photo-bleaching (PB) when exposed to band gap light for a prolonged time in a vacuum. The PB is ascribed to structural changes inside the film as well as surface photooxidation. The amorphous nature of thin films was detected by x-ray diffraction. The chemical composition of the deposited thin films was examined by energy dispersive x-ray analysis (EDAX). The refractive indices of the films were obtained from the transmission spectra based on an inverse synthesis method and the optical band gaps were derived from optical absorption spectra using the Tauc plot. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. It was found that the mechanism of the optical absorption follows the rule of the allowed non-direct transition. Raman and x-ray photoelectron spectra (XPS) were measured and decomposed into several peaks that correspond to the different structural units which support the optical changes.

Effect of laser irradiation on optical properties of Ge12Sb25Se63 amorphous chalcogenide thin films

The change in photo-induced optical properties in thermally evaporated Ge12Sb25Se63 chalcogenide thin film under 532-nm laser illumination has been reported in this paper. The structure and composition of the film have been examined by X-ray diffraction and energy dispersive X-ray analysis, respectively. The optical properties such as refractive index, extinction coefficient and thickness of the films have been determined from the transmission spectra based on inverse synthesis method and the optical band gap has been derived from optical absorption spectra using the Tauc plot. It has been found that the mechanism of the optical absorption is due to allowed indirect transition. The optical band gap increases by 0.05 eV causing photo-bleaching mechanism, while refractive index decreases because of reduction in structural disordering. Deconvolution of Raman and X-ray photoelectron spectra into several peaks provides different structural units, which supports the optical photo-bleaching.

Nonequilibrium microstructures and their evolution in a Fe-Cr-W-Ni-C laser clad coating

The laser-solidified microstructural and compositional characterization and phase evolution during tempering at 963 K were investigated using an analytical transmission electron microscope with energy dispersive X-ray analysis. The cladded alloy, a powder mixture of Fe, Cr, W, Ni, and C with a weight ratio of 10:5:1:1:1, was processed with a 3 kW continuous wave CO2 laser. The processing parameters were 16 mm/s beam scanning speed, 3 mm beam diameter. 2 kW laser power, and 0.3 g/s feed rate. The coating was metallurgically bonded to the substrate, with a maximum thickness of 730 mu m, a microhardness of about 860 Hv and a volumetric dilution ratio of about 6%. Microanalyses revealed that the cladded coating possessed the hypoeutectic microstructure comprising the primary dendritic gamma-austenite and interdendritic eutectic consisted of gamma-austenite and M7C3 carbide. The gamma-austenite was a non-equilibrium phase with extended solid solution of alloying elements and a great deal of defect structures, i.e. a high density of dislocations, twins, and stacking faults existed in gamma phase. During high temperature aging, in situ carbide transformation occurred of M7C3 to M23C6 and M6C. The precipitation of M23C6, MC and M2C carbides from austenite was also observed.