Sputter Deposited High Capacity Li2-xMnO3-y Films for Thin Film Battery Application

Lithium manganese oxide (Li2-xMnO3-y) thin films have been deposited from activated Li2MnO3 powder by radio frequency magnetron sputtering for the first time in the literature and subjected to electrochemical characterization. Physicochemical characterization by X-ray diffraction has revealed the formation of the thin films with crystallographic phase identical to that of the powder target made of Li2-xMnO3-y. The Li:Mn atomic ratio for the powder and film are calculated by X-ray photoelectron spectroscopy and it is found to be 1.6:1.0. From galvanostatic charge discharge studies, a specific discharge capacity of 139 mu Ah mu m(-1) cm(-2) was obtained when cycled between 2.00 and 3.50 V vs Li/Li+. Additionally the rate capability of the thin film electrodes was studied by subjecting the cells to charge-discharge cycling at different current densities in the range from 10 mu A cm(-2) to 100 mu A cm(-2). (C) 2013 The Electrochemical Society. All rights reserved.

Note on high aspect-ratio SU-8 micromechanical structures using mask-less direct laser writing

We report high aspect-ratio micromechanical structures made of SU-8 polymer, which is a negative photoresist. Mask-less direct writing with 405 nm laser is used to pattern spin-cast SU-8 films of thickness of more than 600 um. As compared with X-ray lithography, which helps pattern material to give aspect ratios of 1:50 or higher, laser writing is a less expensive and more accessible alternative. In this work, aspect ratios up to 1:30 were obtained on narrow pillars and cantilever structures. Deep vertical patterning was achieved in multiple exposures of the surface with varying dosages given at periodic intervals of sufficient duration. It was found that a time lag between successive exposures at the same location helps the material recover from the transient changes that occur during exposure to the laser. This gives vertical sidewalls to the resulting structures. The time-lags and dosages were determined by conducting several trials. The micromechanical structures obtained with laser writing are compared with those obtained with traditional UV lithography as well as e-beam lithography. Laser writing gives not only high aspect ratios but also narrow gaps whereas e-beam can only give narrow gaps over very small depths. Unlike traditional UV lithography, laser writing does not need a mask. Furthermore, there is no adjustment for varying the dosage in traditional UV lithography. A drawback of this method compared to UV lithography is that the writing time increases. Some test structures as well as a compliant microgripper are fabricated.

Effect of chemical treatment on surface characteristics of sputter deposited Ti-rich NiTi shape memory alloy thin-films

NiTi thin-films were deposited by DC magnetron sputtering from single alloy target (Ni/Ti: 45/55 aL.%). The rate of deposition and thickness of sputter deposited films were maintained to similar to 35 nm min(-1) and 4 mu m respectively. A set of sputter deposited NiTi films were selected for specific chemical treatment with the solution comprising of de-ionized water, HF and HNO3 respectively. The influence of chemical treatment on surface characteristics of NiTi films before and after chemical treatment was investigated for their structure, micro-structure and composition using different analytical techniques. Prior to chemical treatment, the composition of NiTi films using energy dispersive X-ray dispersive spectroscopy (EDS), were found to be 51.8 atomic percent of Ti and 48.2 atomic percent of Ni. The structure and morphology of these films were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD investigations, demonstrated the presence of dominant Austenite (110) phase along with Martensite phase, for untreated NiTi films whereas some additional diffraction peaks viz. (100), (101), and (200) corresponding to Rutile and Anatase phase of Titanium dioxide (TiO2) along with parent Austenite (110) phase were observed for chemically treated NiTi films. FTIR studies, it can be concluded that chemically treated films have higher tendency to form metal oxide/hydroxide than the untreated NiTi films. XPS investigations, demonstrated the presence of Ni-free surface and formation of a protective metal oxide (TiO2) layer on the surface of the films, in both the cases. The extent of the formation of surface oxide layer onto the surface of NiTi films has enhanced after chemical treatment. (C) 2014 Elsevier B.V. All rights reserved.

Impedance spectroscopy of novel hybrid composite films of polyvinylbutyral (PVB)/functionalized mesoporous silica

Polyvinyl butyral/functionalized mesoporous silica hybrid composite films have been fabricated by solution casting technique with various weight percentages of functionalized silica. A polyol (tripentaerythritol-electron rich component), which acts as an electron donor to the polymer backbone, was added to enhance the conductivity. The prepared composites were characterized by Fourier transformed infrared spectroscopy and the morphology was evaluated by scanning electron microscopy. Dielectric properties of these freestanding composites were studied using the two-probe method. The dielectric constant and impedance value decreased with the increase in applied frequency as well as with the increase in functionalized silica content in the polyvinyl butyral matrix. An increase in conductivity of the PVB/functionalized silica composites was also observed. (C) 2013 Elsevier Ltd. All rights reserved.

Effect of post-deposition annealing on transverse piezoelectric coefficient and vibration sensing performance of ZnO thin films

The present experimental study investigates the influence of post-deposition annealing on the transverse piezoelectric coefficient (d(31)) value of ZnO thin films deposited on a flexible metal alloy substrate, and its relationship with the vibration sensing performance. Highly c-axis oriented and crystalline ZnO thin films were deposited on flexible Phynox alloy substrate via radio frequency (RF) reactive magnetron sputtering. ZnO thin film samples were annealed at different temperatures ranging from 100 degrees C to 500 degrees C, resulting in the temperature of 300 degrees C determined as the optimum annealing temperature. The crystallinity, morphology, microstructure, and rms surface roughness of annealed ZnO thin films were systematically investigated by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM), respectively. The piezoelectric d(31) coefficient value was measured by 4-point bending method. ZnO thin film annealed at 300 degrees C was highly c-axis oriented, crystalline, possesses fine surface morphology with uniformity in the grain size. This film showed higher d(31) coefficient value of 7.2 pm V-1. A suitable in-house designed and developed experimental set-up, for evaluating the vibration sensing performance of annealed ZnO thin films is discussed. As expected the ZnO thin film annealed at 300 degrees C showed relatively better result for vibration sensing studies. It generates comparatively higher peak output voltage of 147 mV, due to improved structural and morphological properties, and higher piezoelectric d(31) coefficient value. (C) 2014 Elsevier B. V. All rights reserved.

Control of magnetization reversal in oriented strontium ferrite thin films

Oriented Strontium Ferrite films with the c axis orientation were deposited with varying oxygen partial pressure on Al2O3(0001) substrate using Pulsed Laser Deposition technique. The angle dependent magnetic hysteresis, remanent coercivity, and temperature dependent coercivity had been employed to understand the magnetization reversal of these films. It was found that the Strontium Ferrite thin film grown at lower (higher) oxygen partial pressure shows Stoner-Wohlfarth type (Kondorsky like) reversal. The relative importance of pinning and nucleation processes during magnetization reversal is used to explain the type of the magnetization reversal with different oxygen partial pressure during growth. (C) 2014 AIP Publishing LLC.

Direct hexagonal transition of amorphous (Ge2Sb2Te5)(0.9)Se-0.1 thin films

Ge2Sb2Te5 (GST) is well known for its phase change properties and applications in memory and data storage. Efforts are being made to improve its thermal stability and transition between amorphous and crystalline phases. Various elements are doped to GST to improve these properties. In this work, Se has been doped to GST to study its effect on phase change properties. Amorphous GST film crystallized in to rock salt (NaCl) type structure at 150 degrees C and then transformed to hexagonal structure at 250 degrees C. Interestingly, Se doped GST ((GST)(0.9)Se-0.1) film crystallized directly into hexagonal phase and the intermediate phase of NaCl is not observed. The crystallization temperature (T-c) of (GST)(0.9)Se-0.1 is around 200 degrees C, which is 50 degrees C higher than the T-c of GST. For (GST)(0.9)Se-0.1, the threshold switching occurs at about 4.5V which is higher than GST (3 V). Band gap (E-opt) values of as deposited films are calculated from Tauc plot which are 0.63 eV for GST and 0.66 eV for (GST)(0.9)Se-0.1. The E-opt decreases for the films annealed at higher temperatures. The increased T-c, E-opt, the contrast in resistance and the direct transition to hexagonal phase may improve the data readability and thermal stability in the Se doped GST film. (C) 2014 AIP Publishing LLC.

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

Using an Office Inkjet Printer to Define the Formation of Copper Films on Paper

A low-cost fabrication process for forming conductive copper lines on paper is presented. An office inkjet printer was used to deposit desired patterns of silver nitrate and tannic acid solutions sequentially on paper. Silver nitrate was instantaneously reduced in situ on paper by tannic acid at room temperature to form silver nanoparticles, which acted as catalysts for the subsequent electroless deposition of copper. The copper films were 1.8 mu m thick, and the sheet resistance of the copper film on paper was 9 Omega/square. A dual monopole ultrawide band antenna was fabricated on paper and its performance was equivalent to that of a similar antenna fabricated on a copper-film covered Kapton substrate using conventional lithographic processes. The paper-based conductive copper films fabricated using the facile process presented herein will aid the development of low-cost flexible circuits and sensors.

Temperature dependent electrical behaviour of Cu2SnS3 films

The temperature dependent electrical properties of the dropcasted Cu2SnS3 films have been measured in the temperature range 140 K to 317 K. The log I versus root V plot shows two regions. The region at lower bias is due to electrode limited Schottky emission and the higher bias region is due to bulk limited Poole Frenkel emission. The ideality factor is calculated from the ln I versus V plot for different temperatures fitted with the thermionic emission model and is found to vary from 6.05 eV to 12.23 eV. This large value is attributed to the presence of defects or amorphous layer at the Ag / Cu2SnS3 interface. From the Richardson's plot the Richardson's constant and the barrier height were calculated. Owing to the inhomogeneity in the barrier heights, the Richardson's constant and the barrier height were also calculated from the modified Richardson's plot. The I-V-T curves were also fitted using the thermionic field emission model. The barrier heights were found to be higher than those calculated using thermionic emission model. From the fit of the I-V-T curves to the field emission model, field emission was seen to dominate in the low temperature range of 140 K to 177 K. The temperature dependent current graphs show two regions of different mechanisms. The log I versus 1000/T plot gives activation energies E-a1 = 0.367095 - 0.257682 eV and E-a2 = 0.038416 - 0.042452 eV. The log ( I/T-2) versus 1000/T graph gives trap depths Phi(o1) = 0.314159 - 0.204752 eV and Phi(o2) = 0.007425- 0.011163 eV. With increasing voltage the activation energy E-a1 and the trap depth Phi(o1) decrease. From the ln (IT1/ 2) versus 1/T-1/ 4 graph, the low temperature region is due to variable range hopping mechanism and the high temperature region is due to thermionic emission. (C) 2014 Author(s).

Near-infrared photoactive Cu3BiS3 thin films by co-evaporation

Semiconducting Cu3BiS3 (CBS) thin films were deposited by co-evaporation of Cu, Bi elemental metallic precursors, with in situ sulphurisation, using a quartz effusion cell. Cu3BiS3 thin films were structurally characterized by XRD and FE-SEM. The chemical bonding of the ions was examined by XPS. As deposited films were demonstrated for metal-semiconductor-metal near IR photodectection under lamp and laser illuminations. The photo current amplified to three orders and two orders of magnitude upon the IR lamp and 60 m W cm(-2) 1064 nm IR laser illuminations, respectively. Larger grains, made up of nano needle bunches aided the transport of carriers. Transport properties were explained based on the trap assisted space charge conduction mechanism. Steady state detector parameters like responsivity varied from 1.04 AW(-1) at 60 m Wcm(-2) to 0.22 AW(-1) at 20 m Wcm(-2). Detector sensitivity of 295 was found to be promising and further could be tuned for better responsivity and efficiency in utilization of near infra-red photodetector. (C) 2014 AIP Publishing LLC.

The influence of mesoporous silica in low T-g cyclic olefin copolymer nanocomposite films: Mechanical and moisture barrier studies

In this study, mesoporous silica-cyclic olefin copolymer nanocomposite films were fabricated by solution casting. With an increase in silica loading, the stiffness of the matrix increased. The nanocomposite film shows increased strain to failure with moisture after aging by matrix plasticization. The storage modulus and loss factor for samples with silica content show better results compared with pristine polymer, as indicated by dynamic mechanical analysis. The interaction between filler-polymer chain exhibit hydrophobicity compared to the neat polymer. Water absorption studies at room temperature and near the T-g of the polymer (similar to 64 degrees C) were carried out. The nanocomposites up to 4 wt% filler reduces the water diffusion by forming hydrogen and chemical bonding. The result by calcium degradation test method for moisture permeability and Schottky structured organic device encapsulation under weathering condition confirms the effective reinforcement effect of silica particles in the matrix. (C) 2014 Elsevier Ltd. All rights reserved.

Optical, photo-acoustic and electrical switching studies of amorphous GeS2 thin films

This paper reports optical, photo-acoustic and electrical switching investigations of GeS2 amorphous thin films of different thicknesses, deposited on glass substrates in vacuum. The Tauc parameter (B (1/2)) and Urbach energy (E (U)) have been determined from the transmittance spectra, to understand the changes in structural disorder; it is found that B (1/2) increases whereas E (U) decreases as the thickness of the films increases. Based on the results, it is suggested that bond re-arrangement, i.e. transformation from homopolar bonds to heteropolar bonds, takes place with increase in thickness. The thermal diffusivity values of GeS2 thin films also show the presence of a chemically ordered network in the GeS2 thin films. Further, it is found that these films exhibit memory-type electrical switching. The observed variation in the switching voltages has been understood on the basis of increase in chemical order.

Evaluation. of Transverse Piezoelectric Coefficient of ZnO Thin Films Deposited on Different Flexible Substrates: A Comparative Study on the Vibration Sensing Performance

We report on the systematic comparative study of highly c-axis oriented and crystalline piezoelectric ZnO thin films deposited on four different flexible substrates for vibration sensing application. The flexible substrates employed for present experimental study were namely a metal alloy (Phynox), metal (aluminum), polyimide (Kapton), and polyester (Mylar). ZnO thin films were deposited by an RF reactive magnetron sputtering technique. ZnO thin films of similar thicknesses of 700 +/- 30 nm were deposited on four different flexible substrates to have proper comparative studies. The crystallinity, surface morphology, chemical composition, and roughness of ZnO thin films were evaluated by respective material characterization techniques. The transverse piezoelectric coefficient (d(31)) value for assessing the piezoelectric property of ZnO thin films on different flexible substrates was measured by a four-point bending method. ZnO thin films deposited on Phynox alloy substrate showed relatively better material characterization results and a higher piezoelectric d(31) coefficient value as compared to ZnO films on metal and polymer substrates. In order to experimentally verify the above observations, vibration sensing studies were performed. As expected, the ZnO thin film deposited on Phynox alloy substrate showed better vibration sensing performance. It has generated the highest peak to peak output voltage amplitude of 256 mV as compared to that of aluminum (224 mV), Kapton (144 mV), and Mylar (46 mV). Therefore, metal alloy flexible substrate proves to be a more suitable, advantageous, and versatile choice for integrating ZnO thin films as compared to metal and polymer flexible substrates for vibration sensing applications. The present experimental study is extremely important and helpful for the selection of a suitable flexible substrate for various applications in the field of sensor and actuator technology.