Spray Pyrolysed Zinc Oxide Thin Films : Effects of Doping and Ion Beam Irradiation

In recent years scientists have made rapid and significant advances in the field of semiconductor physics. One of the most important fields of current interest in materials science is the fundamental aspects and applications of conducting transparent oxide thin films (TCO). The characteristic properties of such coatings are low electrical resistivity and high transparency in the visible region. The first semitransparent and electrically conducting CdO film was reported as early as in 1907 [1]. Though early work on these films was performed out of purely scientific interest, substantial technological advances in such films were made after 1940. The technological interest in the study of transparent semiconducting films was generated mainly due to the potential applications of these materials both in industry and research. Such films demonstrated their utility as transparent electrical heaters for windscreens in the aircraft industry. However, during the last decade, these conducting transparent films have been widely used in a variety of other applications such as gas sensors [2], solar cells [3], heat reflectors [4], light emitting devices [5] and laser damage resistant coatings in high power laser technology [6]. Just a few materials dominate the current TCO industry and the two dominant markets for TCO’s are in architectural applications and flat panel displays. The architectural use of TCO is for energy efficient windows. Fluorine doped tin oxide (FTO), deposited using a pyrolysis process is the TCO usually finds maximum application. SnO2 also finds application ad coatings for windows, which are efficient in preventing radiative heat loss, due to low emissivity (0.16). Pyrolitic tin oxide is used in PV modules, touch screens and plasma displays. However indium tin oxide (ITO) is mostly used in the majority of flat panel display (FPD) applications. In FPDs, the basic function of ITO is as transparent electrodes. The volume of FPD’s produced, and hence the volume of ITO coatings produced, continues to grow rapidly. But the current increase in the cost of indium and the scarcity of this material created the difficulty in obtaining low cost TCOs. Hence search for alternative TCO materials has been a topic of active research for the last few decades. This resulted in the development of binary materials like ZnO, SnO2, CdO and ternary materials like II Zn2SnO4, CdSb2O6:Y, ZnSO3, GaInO3 etc. The use of multicomponent oxide materials makes it possible to have TCO films suitable for specialized applications because by altering their chemical compositions, one can control the electrical, optical, chemical and physical properties. But the advantages of using binary materials are the easiness to control the chemical compositions and depositions conditions. Recently, there were reports claiming the deposition of CdO:In films with a resistivity of the order of 10-5 ohm cm for flat panel displays and solar cells. However they find limited use because of Cd-Toxicity. In this regard, ZnO films developed in 1980s, are very useful as these use Zn, an abundant, inexpensive and nontoxic material. Resistivity of this material is still not very low, but can be reduced through doping with group-III elements like In, Al or Ga or with F [6]. Hence there is a great interest in ZnO as an alternative of ITO. In the present study, we prepared and characterized transparent and conducting ZnO thin films, using a cost effective technique viz Chemical Spray Pyrolysis (CSP). This technique is also suitable for large area film deposition. It involves spraying a solution, (usually aqueous) containing soluble salts of the constituents of the desired compound, onto a heated substrate.

Characterization of radio frequency plasma using Langmuir probe and optical emission spectroscopy

The radio frequency plasma generated during the sputtering of Indium Tin Oxide target using Argon was analyzed by Langmuir probe and optical-emission spectroscopy. The basic plasma parameters such as electron temperature and ion density were evaluated. These studies were carried out by varying the RF power from 20 to 50 W. A linear increase in ion density and an exponential decrease in electron temperature with rf power were observed. The measured plasma parameters were then correlated with the properties of ITO thin films deposited under similar plasma conditions.

Time evolution of Nd:YAG laser-induced plasma from GdBa2Cu3O7 high-Tc superconductor

In order to characterise the laser ablation process from high-Tc superconductors, the time evolution of plasma produced by a Q-switching Nd:YAG laser from a GdBa2Cu3O7 superconducting sample has been studied using spectroscopic and ion-probe techniques. It has been observed that there is a fairly large delay for the onset of the emission from oxide species in comparison with those from atoms and ions of the constituent elements present in the plasma. Faster decay occurs for emission from oxides and ions compared with that from neutral atoms. These observations support the view that oxides are not directly produced from the target, but are formed by the recombination process while the plasma cools down. Plasma parameters such as temperature and velocity are also evaluated.

Anomalous profile of a self-reversed resonance line from Ba+ in a laser produced plasma from YBa2Cu307

A laser produced plasma from the multielement solid target YBa2Cu3O7 is generated using 1.06 μm, 9 ns pulses from a Q-switched Nd:YAG laser in air at atmospheric pressure. A time resolved analysis of the profile of the 4554.03 Å resonance line emission from Ba II at various laser power densities has been carried out. It has been found that the line has a profile which is strongly self-reversed. It is also observed that at laser power densities equal to or exceeding 1.6×1011 W cm−2, a third peak begins to develop at the centre of the self-reversed profile and this has been interpreted as due to the anisotropic resonance scattering (fluorescence). The number densities of singly ionized barium ions evaluated from the width of the resonance line as a function of time delay with respect to the beginning of the laser pulse give typical values of the order of 1019 cm−3. The higher ion concentrations existing at smaller time delays are seen to decrease rapidly. The Ba II ions in the ground state resonantly absorb the radiation and this absorption is maximum around 120 ns after the laser pulse.

Structural, electrical and electrochemical characterization of high frequency magnetron sputtered spinel oxide cathode films for lithium ion battery applications

The main challenges in the deposition of cathode materials in thin film form are the reproduction of stoichiometry close to the bulk material and attaining higher rates of deposition and excellent crystallinity at comparatively lower annealing temperatures. There are several methods available to develop stoichiometric thin film cathode materials including pulsed laser deposition; plasma enhanced chemical vapor deposition, electron beam evaporation, electrostatic spray deposition and RF magnetron sputtering. Among them the most versatile method is the sputtering technique, owing to its suitability for micro-fabricating the thin film batteries directly on chips in any shape or size, and on flexible substrates, with good capacity and cycle life. The main drawback of the conventional sputtering technique using RF frequency of 13.56MHz is its lower rate of deposition, compared to other deposition techniques A typical cathode layer for a thin film battery requires a thickness around one micron. To deposit such thick layers using convention RF sputtering, longer time of deposition is required, since the deposition rate is very low, which is typically 10-20 Å/min. This makes the conventional RF sputtering technique a less viable option for mass production in an economical way. There exists a host of theoretical and experimental evidences and results that higher excitation frequency can be efficiently used to deposit good quality films at higher deposition rates with glow discharge plasma. The effect of frequencies higher than the conventional one (13.56MHz) on the RF magnetron sputtering process has not been subjected to detailed investigations. Attempts have been made in the present work, to sputter deposit spinel oxide cathode films, using high frequency RF excitation source. Most importantly, the major challenge faced by the thin film battery based on the LiMn2O4 cathode material is the poor capacity retention during charge discharge cycling. The major causes for the capacity fading reported in LiMn2O4cathode materials are due to, Jahn-Teller distortion, Mn2+ dissolution into the electrolyte and oxygen loss in cathode material during cycling. The work discussed in this thesis is an attempt on overcoming the above said challenges and developing a high capacity thin film cathode material.

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Plasma polymerization of C[subscript 4]F[subscript 8] thin film on high aspect ratio silicon molds

High aspect ratio polymeric micro-patterns are ubiquitous in many fields ranging from sensors, actuators, optics, fluidics and medical. Second generation PDMS molds are replicated against first generation silicon molds created by deep reactive ion etching. In order to ensure successful demolding, the silicon molds are coated with a thin layer of C[subscript 4]F[subscript 8] plasma polymer to reduce the adhesion force. Peel force and demolding status are used to determine if delamination is successful. Response surface method is employed to provide insights on how changes in coil power, passivating time and gas flow conditions affect plasma polymerization of C[subscript 4]F[subscript 8].

Do magnetospheric shear Alfvén waves generate sufficient electron energy flux to power the aurora?

Using a self-consistent drift-kinetic simulation code, we investigate whether electron acceleration owing to shear Alfvén waves in the plasma sheet boundary layer is sufficient to cause auroral brightening in the ionosphere. The free parameters used in the simulation code are guided by in situ observations of wave and plasma parameters in the magnetosphere at distances >4 RE from the Earth. For the perpendicular wavelength used in the study, which maps to ∼4 km at 110 km altitude, there is a clear amplitude threshold which determines whether magnetospheric shear Alfvén waves above the classical auroral acceleration region can excite sufficient electrons to create the aurora. Previous studies reported wave amplitudes that easily exceed this threshold; hence, the results reported in this paper demonstrate that auroral acceleration owing to shear Alfvén waves can occur in the magnetosphere at distances >4 RE from the Earth.

Electron trapping in shear Alfvén waves that power the aurora

Results from 1D Vlasov drift-kinetic plasma simulations reveal how and where auroral electrons are accelerated along Earth’s geomagnetic field. In the warm plasma sheet, electrons become trapped in shear Alfven waves, preventing immediate wave damping. As waves move to regions with larger vTe=vA, their parallel electric field decreases, and the trapped electrons escape their influence. The resulting electron distribution functions compare favorably with in situ observations, demonstrating for the first time a self-consistent link between Alfven waves and electrons that form aurora.

DK-1D: a drift-kinetic simulation tool for modelling the shear Alfvén wave and its interaction with collisionless plasma

We present a highly accurate tool for the simulation of shear Alfven waves (SAW) in collisionless plasma. SAW are important in space plasma environments because for small perpendicular scale lengths they can support an electric field parallel to the ambient magnetic field. Electrons can be accelerated by the parallel electric field and these waves have been implicated as the source of vibrant auroral displays. However, the parallel electric field carried by SAW is small in comparison to the perpendicular electric field of the wave, making it difficult to measure directly in the laboratory, or by satellites in the near-Earth plasma environment. In this paper, we present a simulation code that provides a means to study in detail the SAW-particle interaction in both space and laboratory plasma. Using idealised, small-amplitude propagating waves with a single perpendicular wavenumber, the simulation code accurately reproduces the damping rates and parallel electric field amplitudes predicted by linear theory for varying temperatures and perpendicular scale lengths. We present a rigorous kinetic derivation of the parallel electric field strength for small-amplitude SAW and show that commonly-used inertial and kinetic approximations are valid except for where the ratio of thermal to Alfv\'{e}n speed is between 0.7 and 1.0. We also present nonlinear simulations of large-amplitude waves and show that in cases of strong damping, the damping rates and parallel electric field strength deviate from linear predictions when wave energies are greater than only a few percent of the plasma kinetic energy, a situation which is often observed in the magnetosphere. The drift-kinetic code provides reliable, testable predictions of the parallel electric field strength which can be investigated directly in the laboratory, and will help to bridge the gap between studies of SAW in man-made and naturally occuring plasma.

A comparison between ion characteristics observed by the POLAR and DMSP spacecraft in the high-latitude magnetosphere

We study here the injection and transport of ions in the convection-dominated region of the Earth’s magnetosphere. The total ion counts from the CAMMICE MICS instrument aboard the POLAR spacecraft are used to generate occurrence probability distributions of magnetospheric ion populations. MICS ion spectra are characterised by both the peak in the differential energy flux, and the average energy of ions striking the detector. The former permits a comparison with the Stubbs et al. (2001) survey of He2+ ions of solar wind origin within the magnetosphere. The latter can address the occurrences of various classifications of precipitating particle fluxes observed in the topside ionosphere by DMSP satellites (Newell and Meng, 1992). The peak energy occurrences are consistent with our earlier work, including the dawn-dusk asymmetry with enhanced occurrences on the dawn flank at low energies, switching to the dusk flank at higher energies. The differences in the ion energies observed in these two studies can be explained by drift orbit effects and acceleration processes at the magnetopause, and in the tail current sheet. Near noon at average ion energies of _1 keV, the cusp and open LLBL occur further poleward here than in the Newell and Meng survey, probably due to convectionrelated time-of-flight effects. An important new result is that the pre-noon bias previously observed in the LLBL is most likely due to the component of this population on closed field lines, formed largely by low energy ions drifting earthward from the tail. There is no evidence here of mass and momentum transfer from the solar wind to the LLBL by nonreconnection coupling. At higher energies (_2–20 keV), we observe ions mapping to the auroral oval and can distinguish between the boundary and central plasma sheets. We show that ions at these energies relate to a transition from dawnward to duskward dominated flow, this is evidence of how ion drift orbits in the tail influence the location and behaviour of the plasma populations in the magnetosphere.

Temporal and spatial variability of auroral forms in the 10–14 MLT sector: Relationship to plasma convection and solar wind-magnetosphere coupling

Ground-based observations of dayside auroral forms and magnetic perturbations in the arctic sectors of Svalbard and Greenland, in combination with the high-resolution measurements of ionospheric ion drift and temperature by the EISCAT radar, are used to study temporal/spatial structures of cusp-type auroral forms in relation to convection. Large-scale patterns of equivalent convection in the dayside polar ionosphere are derived from the magnetic observations in Greenland and Svalbard. This information is used to estimate the ionospheric convection pattern in the vicinity of the cusp/cleft aurora. The reported observations, covering the period 0700-1130 UT, on January 11, 1993, are separated into four intervals according to the observed characteristics of the aurora and ionospheric convection. The morphology and intensity of the aurora are very different in quiet and disturbed intervals. A latitudinally narrow zone of intense and dynamical 630.0 nm emission equatorward of 75 degrees MLAT, was observed during periods of enhanced antisunward convection in the cusp region. This (type 1 cusp aurora) is considered to be the signature of plasma entry via magnetopause reconnection at low magnetopause latitudes, i.e. the low-latitude boundary layer (LLB I,). Another zone of weak 630.0 nm emission (type 2 cusp aurora) was observed to extend up to high latitudes (similar to 79 degrees MLAT) during relatively quiet magnetic conditions, when indications of reverse (sunward) convection was observed in the dayside polar cap. This is postulated to be a signature of merging between a northward directed IMF (B-z > 0) and the geomagnetic field poleward of the cusp. The coexistence of type 1 and 2 auroras was observed under intermediate circumstances. The optical observations from Svalbard and Greenland were also used to determine the temporal and spatial evolution of type 1 auroral forms, i.e. poleward-moving auroral events occurring in the vicinity of a rotational convection reversal in the early post-noon sector. Each event appeared as a local brightening at the equatorward boundary of the pre-existing type 1 cusp aurora, followed by poleward and eastward expansions of luminosity. The auroral events were associated with poleward-moving surges of enhanced ionospheric convection and F-layer ion temperature as observed by the EISCAT radar in Tromso. The EISCAT ion flow data in combination with the auroral observations show strong evidence for plasma flow across the open/closed field line boundary.

Identifying the Open-Closed Field Line Boundary

Of all the various definitions of the polar cap boundary that have been used in the past, the most physically meaningful and significant is the boundary between open and closed field lines. Locating this boundary is very important as it defines which regions and phenomena are on open field lines and which are on closed. This usually has fundamental implications for the mechanisms invoked. Unfortunately, the open-closed boundary is usually very difficult to identify, particularly where it maps to an active reconnection site. This paper looks at the topological reconnection classes that can take place, both at the magnetopause and in the cross-tail current sheet and discusses the implications for identifying the open-closed boundary when reconnection is giving velocity filter dispersion of signatures. On the dayside, it is shown that the dayside boundary plasma sheet and low-latitude boundary layer precipitations are well explained as being on open field lines, energetic ions being present because of reflection of central plasma sheet ions off the two Alfvén waves launched by the reconnection site (the outer one of which is the magnetopause). This also explains otherwise anomalous features of the dayside convection pattern in the cusp region. On the nightside, similar considerations place the open-closed boundary somewhat poleward of the velocity-dispersed ion structures which are a signature of the plasma sheet boundary layer ion flows in the tail.

Relationship of dayside auroral precipitations to the open-closed separatrix and the pattern of convective flow

The implications are discussed of acceleration of magnetospheric ions by reflection off two magnetopause Alfvén waves, launched by the reconnection site into the inflow regions on both sides of the boundary. The effects of these waves on the ion populations, predicted using the model described by Lockwood et al. [1996], offer a physical interpretation of all the various widely used classifications of precipitation into the dayside ionosphere, namely, central plasma sheet, dayside boundary plasma sheet (BPS), void, low-latitude boundary layer (LLBL), cusp, mantle, and polar cap. The location of the open-closed boundary and the form of the convection flow pattern are discussed in relation to the regions in which these various precipitations are typically found. Specifically, the model predicts that both the LLBL and the dayside BPS precipitations are on newly opened field lines and places the convection reversal within the LLBL, as is often observed. It is shown that this offers solutions to a number of paradoxes and problems that arise if the LLBL and BPS precipitations are thought of as being on closed field lines. This model is also used to make quantitive predictions of the longitudinal extent and latitudinal width of the cusp, as a function of solar wind density.

Ion populations on open field lines within the dayside low-latitude boundary layer: theory and observations during a transient event

We analyze of ion populations observed by the NOAA-12 satellite within dayside auroral transients. The data are matched with an open magnetopause model which allows for the transmission of magnetosheath ions across one or both of the two Alfvén waves which emanate from the magnetopause reconnection site. It also allows for reflection and acceleration of ions of magnetospheric origin by these waves. From the good agreement found between the model and the observations, we propose that the events and the low-latitude boundary precipitation are both on open field lines.