Ion irradiation as a tool for modifying the surface and optical properties of plasma polymerised thin films

Radio frequency (R.F.) glow discharge polyterpenol thin films were prepared on silicon wafers and irradiated with I10+ ions to fluences of 1 × 1010 and 1 × 1012 ions/cm2. Post-irradiation characterisation of these films indicated the development of well-defined nano-scale ion entry tracks, highlighting prospective applications for ion irradiated polyterpenol thin films in a variety of membrane and nanotube-fabrication functions. Optical characterisation showed the films to be optically transparent within the visible spectrum and revealed an ability to selectively control the thin film refractive index as a function of fluence. This indicates that ion irradiation processing may be employed to produce plasma-polymer waveguides to accommodate a variety of wavelengths. XRR probing of the substrate-thin film interface revealed interfacial roughness values comparable to those obtained for the uncoated substrate's surface (i.e., both on the order of 5 Å), indicating minimal substrate etching during the plasma deposition process.

Measurement of sensitivities for the thermal recording of laser beams

A simple technique for determining the energy sensitivities for the thermographic recording of laser beams is described. The principle behind this technique is that, if a laser beam with a known spatial distribution such as a Gaussian profile is used for imaging, the radius of the thermal image formed depends uniquely on the intensity of the impinging beam. Thus by measuring the radii of the images produced for different incident beam intensities the minimum intensity necessary (that is, the threshold) for thermographic imaging is found. The diameter of the laser beam can also be found from this measurement. A simple analysis based on the temperature distribution in the laser heated material shows that there is an inverse square root dependence on pulse duration or period of exposure for the energy fluence of the laser beam required, both for the threshold and the subsequent increase in the size of the recording. It has also been shown that except for low intensity, long duration exposure on very low conductivity materials, heat losses are not very significant.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

Irradiation effects in graphene and related materials

Nanomaterials with a hexagonally ordered atomic structure, e.g., graphene, carbon and boron nitride nanotubes, and white graphene (a monolayer of hexagonal boron nitride) possess many impressive properties. For example, the mechanical stiffness and strength of these materials are unprecedented. Also, the extraordinary electronic properties of graphene and carbon nanotubes suggest that these materials may serve as building blocks of next generation electronics. However, the properties of pristine materials are not always what is needed in applications, but careful manipulation of their atomic structure, e.g., via particle irradiation can be used to tailor the properties. On the other hand, inadvertently introduced defects can deteriorate the useful properties of these materials in radiation hostile environments, such as outer space. In this thesis, defect production via energetic particle bombardment in the aforementioned materials is investigated. The effects of ion irradiation on multi-walled carbon and boron nitride nanotubes are studied experimentally by first conducting controlled irradiation treatments of the samples using an ion accelerator and subsequently characterizing the induced changes by transmission electron microscopy and Raman spectroscopy. The usefulness of the characterization methods is critically evaluated and a damage grading scale is proposed, based on transmission electron microscopy images. Theoretical predictions are made on defect production in graphene and white graphene under particle bombardment. A stochastic model based on first-principles molecular dynamics simulations is used together with electron irradiation experiments for understanding the formation of peculiar triangular defect structures in white graphene. An extensive set of classical molecular dynamics simulations is conducted, in order to study defect production under ion irradiation in graphene and white graphene. In the experimental studies the response of carbon and boron nitride multi-walled nanotubes to irradiation with a wide range of ion types, energies and fluences is explored. The stabilities of these structures under ion irradiation are investigated, as well as the issue of how the mechanism of energy transfer affects the irradiation-induced damage. An irradiation fluence of 5.5x10^15 ions/cm^2 with 40 keV Ar+ ions is established to be sufficient to amorphize a multi-walled nanotube. In the case of 350 keV He+ ion irradiation, where most of the energy transfer happens through inelastic collisions between the ion and the target electrons, an irradiation fluence of 1.4x10^17 ions/cm^2 heavily damages carbon nanotubes, whereas a larger irradiation fluence of 1.2x10^18 ions/cm^2 leaves a boron nitride nanotube in much better condition, indicating that carbon nanotubes might be more susceptible to damage via electronic excitations than their boron nitride counterparts. An elevated temperature was discovered to considerably reduce the accumulated damage created by energetic ions in both carbon and boron nitride nanotubes, attributed to enhanced defect mobility and efficient recombination at high temperatures. Additionally, cobalt nanorods encapsulated inside multi-walled carbon nanotubes were observed to transform into spherical nanoparticles after ion irradiation at an elevated temperature, which can be explained by the inverse Ostwald ripening effect. The simulation studies on ion irradiation of the hexagonal monolayers yielded quantitative estimates on types and abundances of defects produced within a large range of irradiation parameters. He, Ne, Ar, Kr, Xe, and Ga ions were considered in the simulations with kinetic energies ranging from 35 eV to 10 MeV, and the role of the angle of incidence of the ions was studied in detail. A stochastic model was developed for utilizing the large amount of data produced by the molecular dynamics simulations. It was discovered that a high degree of selectivity over the types and abundances of defects can be achieved by carefully selecting the irradiation parameters, which can be of great use when precise pattering of graphene or white graphene using focused ion beams is planned.

Nanomechanical properties of silicon surfaces nanostructured by excimer laser

Excimer laser irradiation at ambient temperature has been employed to produce nanostructured silicon surfaces. Nanoindentation was used to investigate the nanomechanical properties of the deformed surfaces as a function of laser parameters, such as the angle of incidence and number of laser pulses at a fixed laser fluence of 5 J cm(-2). A single-crystal silicon 311] surface was severely damaged by laser irradiation and became nanocrystalline with an enhanced porosity. The resulting laser-treated surface consisted of nanometer-sized particles. The pore size was controlled by adjusting the angle of incidence and the number of laser pulses, and varied from nanometers to microns. The extent of nanocrystallinity was large for the surfaces irradiated at a small angle of incidence and by a high number of pulses, as confirmed by x-ray diffraction and Raman spectroscopy. The angle of incidence had a stronger effect on the structure and nanomechanical properties than the number of laser pulses.

Effects of thermal annealing on the properties of zirconia films prepared by ion-assisted deposition

The effect of thermal annealing in the range 300–800 °C on the properties of zirconia films prepared by ion assisted deposition was studied. It was found that at low temperature the cubic phase is formed. This phase is stable up to 700 °C. All the films exhibit a monophasic monoclinic structure at 800 °C. The stress, estimated from X-ray patterns, shows a transition from tensile to compressive with increasing ion fluence. The refractive index and extinction coefficient do not seem to change appreciably up to 700 °C, showing a marked degradation thereafter. Single step annealing to the highest temperature was found to result in better stability than multistep annealing.

Study of electrical properties of pulsed excimer laser deposited strontium titanate films

Polycrystalline SrTiO3 films were prepared by pulsed excimer laser ablation on Si and Pt coated Si substrates. Several growth parameters were varied including ablation fluence, pressure, and substrate temperature. The structural studies indicated the presence of [100] and [110] oriented growth after annealing by rapid thermal annealing at 600-degrees-C for 60 s. Deposition at either lower pressures or at higher energy densities encouraged film growth with slightly preferred orientation. The scanning electron microscopy studies showed the absence of any significant particulates on the film surface. Dielectric studies indicated a dielectric constant of 225, a capacitance density of 3.2 fF/mum2, and a charge density of 40 fC/mum for films of 1000 nm thick. The dc conductivity studies on these films suggested a bulk limited space charge conduction in the high field regime, while the low electric fields induced an ohmic conduction. Brief time dependent dielectric breakdown studies on these films, under a field of 250 kV/cm for 2 h, did not exhibit any breakdown, indicating good dielectric strength.

Study of the electrical properties of pulsed laser ablated (Ba0.5Sr0.5)TiO3 thin films

The laser ablated barium strontium titanate (BST) thin films were characterized in terms of composition, structure, microstructure and electrical properties. Films deposited at 300 degrees C under 50 mTorr oxygen pressure and 3 J cm(-2) laser fluence and further annealed at 600 degrees C in flowing oxygen showed a dielectric constant of 467 and a dissipation factor of 0.02. The room-temperature current-voltage characteristics revealed a space charge limited conduction (SCLC) mechanism, though at low fields the effect of the electrodes was predominant. The conduction mechanism was thoroughly-investigated in terms of Schottky emission at low fields, and bulk-limited SCLC at high fields. The change over to the bulk-limited conduction process from the electrode-limited Schottky emission was, attributed to the process of tunneling through the electrode interface at high fields resulting into the lowering of the electrode contact resistance and consequently giving rise to a bulk limited conduction process. The predominance of SCLC mechanism in the films suggests that the bulk properties are only revealed if the depletion width at the electrode interface is thin enough to allow the tunneling process to take place. This condition is only favorable if the him thickness is high or if the doping concentration is high enough. In the present case the film thickness ranged from 0.3 to 0.7 mu m which was suitable to show the transition mentioned above. (C) 1999 Elsevier Science S.A. All rights reserved.

Effect of lithium ion irradiation on the transport and optical properties of Bridgman grown n-type InSb single crystals

Single crystal (100) wafers of n-InSb were implanted with 50 MeV Li3+ ions at various fluences ranging from 10(10) to 10(14) ions/cm(2) at room temperature. Investigations of the optical, electrical, and structural properties of the as-grown, irradiated, annealed wafers were carried out by infrared and Raman spectroscopies, Hall measurements, and high resolution x-ray diffraction (HRXRD). In the case of samples irradiated with an ion fluence of 1.6x10(14) ions/cm(2), electrical measurements at 80 K reveal that there is a decrease in carrier concentration from 8.5x10(15) (for unirradiated) to 1.1x10(15)/cm(3) and an increase in mobility from 5.4x10(4) to 1.67x10(5) cm(2)/V s. The change in carrier concentration is attributed to the creation of electron trap centers induced by ion beam irradiation and the increase in mobility to the formation of electrical inactive complexes. Nevertheless, even with the irradiation at 1.6x10(14) ions/cm(2) fluence the crystalline quality remains largely unaffected, as is seen from HRXRD and Raman studies. (C) 2001 American Institute of Physics.

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.

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.

Radiation resistance of PFN and PNM-PT relaxor ferroelectrics

The relaxor ferroelectric compositions Pb(Fe1/2Nb1/2)O-3 (PEN) and [Pb(Mg1/3Nb2/3)O-3](0.8)-[PbTiO3](0.2) (PMN-PT) are studied for their radiation response to the high energy heavy ions (50 MeV Li3+, fluence 1 X 10(13)-1 X 10(14) ions/cm(2)) in terms of their structural, dielectric and piezoelectric properties. There was no change in the crystallinity of both the compositions after irradiation as seen from the XRD. The PEN composition did not show much change in the dielectric constant but the value of T-m decreased by 8degreesC. The PMN-PT composition showed an increase in the dielectric constant with increase in the irradiation fluence from 1 x 10(13) to 1 X 10(14) ions/cm(2) with no change in the value of T-m. The piezoelectric coefficient decreased in both the samples after irradiation. Among the compositions studied, PEN is observed to be more radiation resistant to changes in structural and dielectric properties than PM-PT. (C) 2003 Elsevier Ltd. All rights reserved.

Pseudo-time particle filtering for diffuse optical tomography

We recast the reconstruction problem of diffuse optical tomography (DOT) in a pseudo-dynamical framework and develop a method to recover the optical parameters using particle filters, i.e., stochastic filters based on Monte Carlo simulations. In particular, we have implemented two such filters, viz., the bootstrap (BS) filter and the Gaussian-sum (GS) filter and employed them to recover optical absorption coefficient distribution from both numerically simulated and experimentally generated photon fluence data. Using either indicator functions or compactly supported continuous kernels to represent the unknown property distribution within the inhomogeneous inclusions, we have drastically reduced the number of parameters to be recovered and thus brought the overall computation time to within reasonable limits. Even though the GS filter outperformed the BS filter in terms of accuracy of reconstruction, both gave fairly accurate recovery of the height, radius, and location of the inclusions. Since the present filtering algorithms do not use derivatives, we could demonstrate accurate contrast recovery even in the middle of the object where the usual deterministic algorithms perform poorly owing to the poor sensitivity of measurement of the parameters. Consistent with the fact that the DOT recovery, being ill posed, admits multiple solutions, both the filters gave solutions that were verified to be admissible by the closeness of the data computed through them to the data used in the filtering step (either numerically simulated or experimentally generated). (C) 2011 Optical Society of America

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be similar to 30 GPa at the deposition pressure of 8 Pa. (C) 2011 Elsevier B.V. All rights reserved.

Compositionally modulated Pb(Mg1/3Nb2/3)O-3-PbTiO3 relaxor thin films deposited by pulsed excimer laser ablation technique

Thin films of (1-x)Pb(Mg1/3Nb2/3)O-3 - xPbTiO(3) (x = 0.1 to 0.3)(PMN-PT) were deposited on the platinum coated silicon substrate by pulsed excimer laser ablation technique. A template layer of LaSr0.5Co0.5O3 (LSCO) was deposited on platinum substrate prior to the deposition of PMN-PT thin films. The composition and the structure of the films were modulated via proper variation of the deposition parameter such as substrate temperature, laser fluence and thickness of the template layers. We observed the impact of the thickness of LSCO template layer on the orientation of the films. A room temperature dielectric constant varying from 2000 to 4500 was noted for different composition of the films. The dielectric properties of the films were studied over the frequency range of 100 Hz - 100 kHz over a wide range of temperatures. The films exhibited the relaxor- type behavior that was characterized by the frequency dispersion of the temperature of dielectric constant maxima (T-m) and also diffuse phase transition. C1 Indian Inst Sci, Mat Res Ctr, Bangalore, Karnataka 560012 India.