Modulation of intrinsic defects in vertically grown ZnO nanorods by ion implantation.

Intrinsic defects created by chemically inert gas (Xe) ion implantation in vertically grown ZnO nanorods are studied by optical and X-ray absorption spectroscopy (XAS). The surface defects produced due to dynamic sputtering by ion beams control the fraction of O and Zn with ion fluence, which helps in tuning the optoelectronic properties. The forbidden Raman modes related to Zn interstitials and oxygen vacancies are observed because of the weak Fröhlich interaction, which arises due to disruption of the long-range lattice order. The evolution of the lattice disorder is identified by O K-edge and Zn K-edge scans of XAS. The hybridization strength between the O 2p and Zn 4p states increases with ion fluence and modulates the impact of intrinsic defects. The ion irradiation induced defects also construct intermediate defects bands which reduce the optical bandgap. Density functional theory (DFT) calculations are used to correlate the experimentally observed trend of bandgap narrowing with the origin of electronic states related to Zn interstitial and O vacancy defects within the forbidden energy gap in ZnO. Our finding can be beneficial to achieve enhanced conductivity in ZnO by accurately varying the intrinsic defects through ion irradiation, which may work as a tuning knob to control the optoelectronic properties of the system.

Thermoelectric properties of GaN with carrier concentration modulation: an experimental and theoretical investigation.

The present work investigates the less explored thermoelectric properties of the n-type GaN semiconductor by combining both experimental and computational tools. The Seebeck coefficients of GaN epitaxial thin films were experimentally measured in the wide temperature range from 77 K to 650 K in steps of ∼10 K covering both low and high-temperature regimes as a function of the carrier concentration (2 × 1016, 2 × 1017, 4 × 1017 and 8 × 1017 cm-3). The measured Seebeck coefficient at room temperature was found to be highest (-374 µV K-1) at the lowest concentration of 4 × 1016 cm-3, and decreases in magnitude monotonically (-327.6 µV K-1, -295 µV K-1, -246 µV K-1 for 2 × 1017, 4 × 1017, 8 × 1017 cm-3, respectively) as the sample carrier concentration increases. The Seebeck coefficient remains negative in the entire temperature range under study indicating that electrons are the dominant carriers. To understand the temperature-dependent behaviour, we also carried out the electronic structure and transport coefficient calculations using the Tran-Blaha modified Becke-Johnson (TB-mBJ) potential and semiclassical Boltzmann transport theory implemented in WIEN2k and BoltzTraP code, respectively. The experimentally observed carrier concentrations were used in the calculations. The estimated results obtained under constant relaxation time approximations provide a very good agreement between the theoretical and experimental data of Seebeck coefficients in the temperature range from 260 to 625 K.

Mechanistic insights into the interaction between energetic oxygen ions and nanosized ZnFe2O4: XAS-XMCD investigations.

The interactions of energetic ions with multi-cation compounds and their consequences in terms of changes in the local electronic structure, which may facilitate intriguing hybridization between O 2p and metal d orbitals and magnetic ordering, are the subject of debate and require a deep understanding of energy transfer processes and magnetic exchange mechanisms. In this study, nanocrystals of ZnFe2O4 were exposed to O7+ ions with an energy of 100 MeV to understand, qualitatively and quantitatively, the metal-ligand field interactions, cation migration and magnetic exchange interactions by employing X-ray absorption fine structure measurements and X-ray magnetic circular dichroism to get deeper mechanistic insights. Nanosized zinc ferrite nanoparticles (NPs) with a size of ∼16 nm synthesized in the cubic spinel phase exhibited deterioration of the crystalline phase when 100 MeV O7+ ions passed through them. However, the size of these NPs remained almost the same. The behaviour of crystal deterioration is associated with the confinement of heat in this interaction. The energy confined inside the nanoparticles promotes cation redistribution as well as the modification of the local electronic structure. Prior to this interaction, almost 42% of Zn2+ ions occupied AO4 tetrahedra; however, this value increased to 63% after the interaction. An inverse effect was observed for metal ion occupancies in BO6 octahedra. The L-edge spectra of Fe and Zn reveal that the spin and valence states of the metal ions were not affected by this interaction. This effect is also supported by K-edge measurements for Fe and Zn. The t2g/eg intensity ratio in the O K-edge spectra decreased after this interaction, which is associated with detachment of Zn2+ ions from the lattice. The extent of hybridization, as estimated from the ratio of the post-edge to the pre-edge region of the O K-edge spectra, decreased after this interaction. The metal-oxygen and metal-metal bond lengths were modified as a result of this interaction, as determined from extended X-ray absorption fine structure measurements. These measurements further support the observation of cation migration from AO4 tetrahedra to AO6 octahedra and vice versa. The Fe L-edge magnetic circular dichroism spectra indicate that Fe3+ ions occupying sites in AO4 tetrahedra and BO6 octahedra exhibited antiferromagnetic-like ordering prior to this interaction. The NPs that interacted with energetic O ions displayed a different kind of magnetic ordering.

The influence of carbon concentration on the electronic structure and magnetic properties of carbon implanted ZnO thin films.

The influence of carbon concentration on the electronic and magnetic properties of C-implanted ZnO thin films has been studied using synchrotron radiation based X-ray absorption spectroscopic techniques and vibrating sample magnetometer measurements. 20 keV carbon ions were implanted in ZnO films with different fluences (2 × 1016, 4 × 1016 and 6 × 1016 ions per cm2). The pristine ZnO film shows diamagnetic behaviour while the C-implanted films exhibit room temperature ferromagnetism. Our first-principles calculations based on density functional theory show an appreciable magnetic moment only when the implanted C atom sits either in the O-site (2 µB) or in the interstitial position (1.88 µB), whereas the C atom in the Zn substitutional position does not possess any magnetic moment. X-ray absorption near edge structure analysis at the O K-edge reveals that the charge transfer from O-2p to the C-defect site causes the ferromagnetism in the C-implanted ZnO film at low fluence. However at high fluence, the implanted C replaces the lattice and produces more Zn vacancies, as evidenced by extended X-ray absorption fine structure studies at the Zn K-edge, which favors the ferromagnetism. The persistence of the implanted carbon and ferromagnetism of the C-implanted ZnO film has also been studied by isothermal annealing at 500 °C and discussed in detail.

Ion induced dewetting of Au-Si on a SiO2 surface: composite nanodot evolution and wettability transition.

A nanodot array morphology gradually develops on SiO2 surface when a thin bi-layer of Au and Si undergoes ion irradiation. An increasing amount of gold silicide is detected as islands on the insulator surface evolve into nanodots as a function of increasing ion fluence. Different stages of evolution from islands to nanodots are found to be driven by the localized melting of Au along the ion-track and dewetting of the metal film. Dewetting is accompanied by sputter-erosion and mixing of Au and Si at the bi-layer interface due to ion energy deposition. Interestingly, a gradual transition in wettability of the surface from the hydrophilic to the hydrophobic one is observed with the growth of nanodots, which is correlated with the compositional variation. The experimental results indicate a route towards the controlled growth of composite nanodots on an insulator surface having hydrophobic properties using ion irradiation.

Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions.

A unique strategy for scavenging free radicals in situ on exposure to gamma irradiation in polyethylene (PE) nanocomposites is presented. Blends of ultra-high molecular weight PE and linear low-density PE (PEB) and their nanocomposites with graphene (GPEB) were prepared by melt mixing to develop materials for biomedical implants. The effect of gamma irradiation on the microstructure and mechanical properties was systematically investigated. The neat blend and the nanocomposite were subjected to gamma-ray irradiation in order to improve the interfacial adhesion between PE and graphene sheets. Structural and thermal characterization revealed that irradiation induced crosslinking and increased the crystallinity of the polymer blend. The presence of graphene further enhanced the crystallinity via crosslinks between the polymer matrix and the filler on irradiation. Graphene was found to scavenge free radicals as confirmed by electron paramagnetic resonance spectroscopy. Irradiation of graphene-containing polymer composites resulted in the largest increase in modulus and hardness compared to either irradiation or addition of graphene to PEB alone. This study provides new insight into the role of graphene in polymer matrices during irradiation and suggests that irradiated graphene-polymer composites could emerge as promising materials for use as articulating surfaces in biomedical implants.

Perspectives on metal induced crystallization of a-Si and a-Ge thin films.

In recent times, the metal induced crystallization (MIC) process in amorphous semiconductors (a-Si and a-Ge) has been extensively investigated by many researchers due to potential applications of crystalline semiconductors in high-density data storage devices, flat panel displays, and high performance solar cells. In this context, we have presented a review on different schemes of MIC in metal/a-Si and metal/a-Ge bilayer films (with stacking change) on various substrates under different annealing conditions. The parameters, which limit crystallization of a-Si and a-Ge have been analyzed and discussed extensively keeping in mind their applications in solar cells and flat panel displays. The MIC of a-Si and a-Ge films under ion beam irradiation has also been discussed in detail. At the end, some suggestions to overcome the limitations of the MIC process in producing better crystalline semiconductors have been proposed. We believe that this review article will inspire readers to perform a thorough investigation on various aspects of MIC for further development of high efficiency solar cells and high quality flat panel displays.

Design and development of a compact ion implanter and plasma diagnosis facility based on a 2.45 GHz microwave ion source.

A project on developing a 2.45 GHz microwave ion source based compact ion implanter and plasma diagnostic facility has been taken up by the Central University of Punjab, Bathinda. It consists of a double-wall ECR plasma cavity, a four-step ridge waveguide, an extraction system, and an experimental beam chamber. The mechanical design has been carried out in such a way that both types of experiments, plasma diagnosis and ion implantation, can be easily accommodated simultaneously and separately. To optimize microwave coupling to the ECR plasma cavity, a four-step ridge waveguide is designed. Microwave coupling simulation for the ECR plasma cavity has been performed at different power inputs using COMSOL Multiphysics. An enhanced electric field profile has been obtained at the center of the ECR plasma cavity with the help of a four-step ridge waveguide compared to the WR284 waveguide. The magnetic field distribution for two magnetic rings and the extraction system's focusing properties have been simulated using the computer simulation technique. A tunable axial magnetic field profile has been obtained with a two permanent magnetic ring arrangement. The dependency of the beam emittance and beam current on accelerating voltages up to 50 kV has been simulated with different ions. It shows that ion masses have a great impact on the beam emittance and output current. This facility has provision for in situ plasma diagnosis using a Langmuir probe and optical emission spectroscopy setups. This system will be used for ion implantation, surface patterning, and studies of basic plasma sciences.

An assessment on crystallization phenomena of Si in Al/a-Si thin films via thermal annealing and ion irradiation.

In the present study, crystallization of amorphous-Si (a-Si) in Al/a-Si bilayer thin films under thermal annealing and ion irradiation has been investigated for future solar energy materials applications. In particular, the effect of thickness ratio (e.g. in Al : a-Si, the ratio of the Al and a-Si layer thickness) and temperature during irradiation on crystallization of the Si films has been explored for the first time. Two sets of samples with thickness ratio 1 : 1 (set-A: 50 nm Al/50 nm a-Si) and thickness ratio 1 : 3 (set-B: 50 nm Al/150 nm a-Si) have been prepared on thermally oxidized Si-substrates. In one experiment, thermal annealing of the as-prepared sample (of both the sets) has been done at different temperatures of 100 °C, 200 °C, 300 °C, 400 °C, and 500 °C. Significant crystallization was found to initiate at 200 °C with the help of thermal annealing, which increased further by increasing the temperature. In another experiment, ion irradiation on both sets of samples has been carried out at 100 °C and 200 °C using 100 MeV Ni7+ ions with fluences of 1 × 1012 ions per cm2, 5 × 1012 ions per cm2, 1 × 1013 ions per cm2, and 5 × 1013 ions per cm2. Significant crystallization of Si was observed at a remarkably low temperature of 100 °C under ion irradiation. The samples irradiated at 100 °C show better crystallization than the samples irradiated at 200 °C. The maximum crystallization of a-Si has been observed at a fluence of 1 × 1012 ions per cm2, which was found to decrease with increasing ion fluence at both temperatures (i.e. 100 °C & 200 °C). The crystallization of a-Si is found to be better for set-B samples as compared to set-A samples at all the fluences and irradiation temperatures. The present work is aimed at developing the understanding of the crystallization process, which may have significant advantages for designing crystalline layers at lower temperature using appropriate masks for irradiation at the desired location. The detailed mechanisms behind all the above observations are discussed in this paper.

Investigations on the in vitro bioactivity of swift heavy oxygen ion irradiated hydroxyapatite.

The effect of swift heavy oxygen ion irradiation of hydroxyapatite on its in vitro bioactivity was studied. The irradiation experiment was performed using oxygen ions at energy of 100 MeV with 1 x 10(12) and 1 x 10(13) ions/cm2 fluence range. The irradiated samples were characterized by glancing angle X-ray diffraction (GXRD), photoluminescence spectroscopy (PL) and scanning electron microscopy (SEM). GXRD showed that irradiated samples exhibited better crystallinity. The irradiated samples revealed an increase in PL intensity. In addition, the irradiated hydroxyapatite was found to have enhanced bioactivity.

Development of Ge nanoparticles embedded in GeO2 matrix.

Germanium (Ge) nanoparticles have attracted a lot of attention due to their excellent optical properties. In this paper, we report on the formation of Ge nanoparticles embedded in GeO2 matrix prepared by electron beam evaporation and subsequent annealing. Transmission electron microscopy (TEM) studies clearly indicate the formation of Ge nanocrystals in the films annealed at 500 degrees C. Fourier transform infrared (FTIR) spectroscopic studies are carried out to verify the evolution of the structure after annealing at each stage. Micro-Raman analysis also confirms the formation of Ge nanoparticles in the annealed films. Development of Ge nanoparticles is also established by photoluminescence (PL) analysis. Surface morphology study is carried out by atomic force microscopy (AFM). It shows the evolution of granular structure of the films with increasing annealing temperature.

Formation of TiO2 nanorings due to rapid thermal annealing of swift heavy ion irradiated films.

Amorphous thin films of TiO2 deposited by Pulsed Laser Deposition (PLD) method are irradiated by Swift Heavy Ion (SHI) beam. The irradiated films are subsequently annealed by Rapid Thermal Annealing (RTA) method. Atomic Force Microscopy (AFM) study reveals formation of nano-rings on the surface after RTA processing. Phase change is identified by Glancing Angle X-ray Diffraction (GAXRD) and Raman spectroscopy. Optical characterisation is carried out by UV-VIS absorption spectroscopy. Though no shift of absorption edge is observed after irradiation, RTA processing does show redshift.

Synthesis of nanodimensional TiO2 thin films.

Nanodimensional TiO2 has wide application in the field of photocatalysis, photovoltaic and photochromic devices. In present investigation TiO2 thin films deposited by pulsed laser deposition method are irradiated by 100 MeV Ag ion beam to achieve growth of nanophases. The nanostructure evolution is characterized by atomic force microscopy (AFM). The phases of TiO2 formed after irradiation are identified by glancing angle X-ray diffraction and Raman spectroscopy. The particle radius estimated by AFM varies from 10-13 nm. Anatase phase of TiO2 is formed after irradiation. The blue shift observed in UV-VIS absorption spectra indicates the nanostructure formation. The shape and size of nanoparticles formed due to high electronic excitation depend upon thickness of the film.

Measurements and analysis of bremsstrahlung x-ray spectrum obtained in NANOGAN electron cyclotron resonance ion source.

From the ECR plasma, hot electrons leak across the magnetic lines of force and by striking the plasma chamber produce bremsstrahlung x-rays. The wall bremsstrahlung gives information on the confinement status of hot electron. In our studies, experimental measurements are carried out in NANOGAN electron cyclotron resonance (ECR) ion source for the wall bremsstrahlung x-rays and the results are presented. While optimizing a particular charge state in ECR ion source, experimental parameters are adjusted to get a maximum current. The wall bremsstrahlung components are studied in these cases for understanding the hot electron confinement conditions.

Setup for in situ deep level transient spectroscopy of semiconductors during swift heavy ion irradiation.

A computerized system for in situ deep level characterization during irradiation in semiconductors has been set up and tested in the beam line for materials science studies of the 15 MV Pelletron accelerator at the Inter-University Accelerator Centre, New Delhi. This is a new facility for in situ irradiation-induced deep level studies, available in the beam line of an accelerator laboratory. It is based on the well-known deep level transient spectroscopy (DLTS) technique. High versatility for data manipulation is achieved through multifunction data acquisition card and LABVIEW. In situ DLTS studies of deep levels produced by impact of 100 MeV Si ions on Aun-Si(100) Schottky barrier diode are presented to illustrate performance of the automated DLTS facility in the beam line.

Nanocrystalline SnO2 formation using energetic ion beam.

Nanocrystalline tin oxide (SnO2) thin films grown by RF magnetron sputtering technique were characterized by UV-Visible absorption spectroscopy and Photoluminescence spectroscopy. From atomic force microscopic (AFM) and Glancing angle X-ray diffraction (GAXRD) measurements, the radius of grains was found to be approximately 6+/-2 nm. The thin films were bombarded with 250 keV Xe2+ ion beam to observe the stability of nanophases against radiation. For ion bombarded films, optical absorption band edge is shifted towards red region. Atomic force microscopy studies show that the radius of the grains was increased to approximately 8 +/- 1 nm and the grains were nearly uniform in size. The size of the grains has been reduced after ion bombardment in the case of films grown on Si. During this process, defects such as vacancies, voids were generated in the films as well as in the substrates. Ion bombardment induces local temperature increase of thin films causing melting of films. Ion beam induced defects enhances the diffusion of atoms leading to uniformity in size of grains. The role of matrix on ion beam induced grain growth is discussed.

Nanostructuring of InP surface by low-energy ion beam irradiation.

The InP nanodots of size 55 to 100 nm and height 25 to 30 nm have been synthesized by low-energy Ar+-ion irradiation with different ion energies. Sizes and size distributions of the dots strongly depend on growth conditions. Rapid thermal annealed (RTA) of the patterned surface shows cluster formation for annealing temperature 400 degrees C and above. Raman investigations reveal optical phonon softening due to correlation length shortening and broadening of the optical modes from the patterned surface. The softening is due to confinement of phonons in embedded nanocrystallites within the patterned surface along with surface nanodots, and broadening is attributed to their size distributions, which increases with increase in ion energy. The lattice damage recovery is observed from the patterned surface subjected to RTA, which exhibits upward shift of the LO and TO phonons due to the presence of complex interfacial stress, associated with the removal of crystal defects with RTA.

Work Function Modulation of Molybdenum Disulfide Nanosheets by Introducing Systematic Lattice Strain.

Tuning the surface electronic properties of 2D transition metal dichalcogenides such as Molebdenum disulfide (MoS2) nanosheets is worth exploring for their potential applications in strain sensitive flexible electronic devices. Here in, the correlation between tensile strain developed in MoS2 nanosheets during swift heavy ion irradiation and corresponding modifications in their surface electronic properties is investigated. With prior structural characterization by transmission electron microscopy, chemically exfoliated MoS2 nanosheets were exposed to 100 MeV Ag ion irradiation at varying fluence for creation of controlled defects. The presence of defect induced systematic tensile strain was verified by Raman spectroscopy and X-ray Diffraction analysis. The effect of ion irradiation on in-plane mode is observed to be significantly higher than that on out-of-plane mode. The contribution of irradiation induced in-plane strain on modification of the surface electronic properties of nanosheets was analyzed by work function measurement using scanning Kelvin probe microscopy. The work function value is observed to be linearly proportional to tensile strain along the basal plane indicating a systematic shifting of Fermi surface with fluence towards the valence band.

Synthesis of nanocrystalline tin oxide thin film by swift heavy ion irradiation.

Nanocrystals of tin oxide were formed in e-beam evaporated films by swift heavy ion (SHI) irradiation. The nucleation of nanocrystals occurred due to electronic excitation by swift heavy ion. Nanophase thin films are characterized systematically by HRTEM, GAXRD, EDX, and UV/NIS absorption techniques. Nanocrystals having size of 8 nm radius are synthesized in different substrates during swift heavy ion irradiation and without subsequent annealing. SHI induced nanocrystallization could be achieved in both crystalline and non-crystalline substrates.

The direct injection of intense ion beams from a high field electron cyclotron resonance ion source into a radio frequency quadrupole.

The ion current achievable from high intensity ECR sources for highly charged ions is limited by the high space charge. This makes classical extraction systems for the transport and subsequent matching to a radio frequency quadrupole (RFQ) accelerator less efficient. The direct plasma injection (DPI) method developed originally for the laser ion source avoids these problems and uses the combined focusing of the gap between the ion source and the RFQ vanes (or rods) and the focusing of the rf fields from the RFQ penetrating into this gap. For high performance ECR sources that use superconducting solenoids, the stray magnetic field of the source in addition to the DPI scheme provides focusing against the space charge blow-up of the beam. A combined extraction/matching system has been designed for a high performance ECR ion source injecting into an RFQ, allowing a total beam current of 10 mA from the ion source for the production of highly charged (238)U(40+) (1.33 mA) to be injected at an ion source voltage of 60 kV. In this design, the features of IGUN have been used to take into account the rf-focusing of an RFQ channel (without modulation), the electrostatic field between ion source extraction and the RFQ vanes, the magnetic stray field of the ECR superconducting solenoid, and the defocusing space charge of an ion beam. The stray magnetic field is shown to be critical in the case of a matched beam.