Structural characterizations and the third-order nonlinear optical properties of poly(2,5-didecyloxy)phenylene films modified by N ions implantation

Poly(2,5-didecyloxy)phenylene (PDDOP) films implanted by 30 keV nitrogen ions (N⁺) with the dose rang of 10¹⁵-10¹⁷ ions/cm² were characterized by FTIR-ATR spectra, UV-VIS spectra and X-ray photoelectron spectroscopy, which showed that the C-H bonds of the PDDOP films were largely broken and new bonds like CC, CN and CN were formed as the increasing ion fluence. The third-order nonlinear optical susceptibilities (χ⁽³⁾) were measured by degenerate four-wave mixing (DFWM) technique at 532 nm. The results demonstrated that the (χ⁽³⁾) value of PDDOP films was maximized to 4.19 × 10⁻¹¹ esu at an ion dose of 1.15 × 10¹⁷ ions/cm², which was 4.4 times larger than that of the pristine film. The enhanced third-order nonlinear properties may attribute to the enlarged expansion coefficient and the enhanced absorption coefficient of the bombarded films at proper N⁺ ions dose.     

Mixing of Cr and Si atoms induced by noble gas ions irradiation of Cr/Si bilayers

Cr/Si bilayers were irradiated at room temperature with 120 keV Ar, 140 keV Kr and 350 keV Xe ions to fluences ranging from 10¹⁵ to 2 × 10¹⁶ ions/cm². The thickness of Cr layer evaporated on Si substrate was about 400 Å. Rutherford backscattering spectrometry (RBS) was used to investigate the atomic mixing induced at the Cr-Si interface as function of the incident ion mass and fluence. We observed that for the samples irradiated with Ar ions, RBS yields from both Cr layer and Si substrate are the same as before the irradiation. There is no mixing of Cr and Si atoms, even at the fluence of 2 × 10¹⁶ ions/cm². For the samples irradiated with Kr ions, a slight broadening of the Cr and Si interfacial edges was produced from the fluence of 5 × 10¹⁵ ions/cm². The broadening of the Cr and Si interfacial edges is more pronounced with Xe ions particularly to the fluence of 10¹⁶ ions/cm². The interface broadening was found to depend linearly on the ion fluence and suggests that the mixing is like a diffusion controlled process. The experimental mixing rates were determined and compared with values predicted by ballistic and thermal spike models. Our experimental data were well reproduced by the thermal spikes model.     

Introduction of conductivity on non-conducting polyaniline by low-energy proton implantation

The semiconductor characteristics of a non-conducting polyaniline pellet can be modified by implantation of low-energy protons, that is, the resistivity became less than 50 Ω cm by proton doping at the fluence rate and fluence of 4 × 10¹¹ ions/cm²/s and 1 × 10¹⁵ ions/cm², respectively. The resistivity increased with the increasing fluence rate of the protons. FT/IR spectra have shown that a new band resulted from the appearance of N⁺-H due to the proton implantation.     

Raman investigation of incident N-, Xe-ions induced effects in ZnO thin films

Highly c-axis orientation ZnO thin films with hundreds nanometers in thickness have been deposited on (1 0 0) Si substrate by RF magnetron sputtering. These films are implanted at room temperature by 80 keV N-ions with fluences from 5.0 × 10¹⁴ to 1.0 × 10¹⁷ ions/cm², implanted by 400 keV Xe-ions with 2.0 × 10¹⁴ to 2.0 × 10¹⁶ ions/cm², irradiated by 3.64 MeV Xe-ions with 1.0 × 10¹² to 1.0 × 10¹⁵ ions/cm², or irradiated by 308 MeV Xe-ions with 1.0 × 10¹² to 5.0 × 10¹⁴ ions/cm², respectively. Then the ZnO films are investigated using a Raman spectroscopy. The obtained Raman spectra show that a new Raman peak located at about 578 cm⁻¹ relating to simple defects or disorder phase appears in all ZnO films after ion implantation/irradiation, a new Raman peak at about 275 cm^-1 owing to N-activated zinc-like vibrations is observed in the N-implanted samples. Moreover, a new Raman peak at about 475 cm⁻¹ is only seen in the samples after 400 keV and 3.64 MeV Xe-ions bombardment. The area intensity of these peaks increases with increasing ion fluence. The effects of ion fluence, element chemical activity, atom displacements induced by nuclear collisions as well as energy deposition on the damage process of ZnO films under ion implantation/irradiation are discussed briefly.     

Investigations on the structural and optical properties of the swift heavy ion irradiated 6HSiC

Single crystal 6HSiC wafers have been irradiated with 150 MeV Ag¹²⁺ ions with fluences ranging from 1 × 10¹¹ to 1 × 10¹³ ions/cm² at 300 K. The defect accumulation as a function of fluence was studied to determine changes in structural and optical properties. The variation in the fundamental Raman modes of the crystalline 6HSiC due to irradiation has been correlated with the disorder accumulation. The creation of defect states due to irradiation in the bandgap affects the blue-green photoluminescence emission in the irradiated samples. The UV-Visible absorption studies support the existence of defect states in the bandgap which is observed by the shift in the absorption edge towards the lower energy side with increasing fluence. Time Correlated Single Photon Counting photoluminescence decay results suggest that the existing defect states are radiative, exhibiting three lifetimes when irradiated with a fluence 5 × 10¹¹ ions/cm². The total number of lifetime components was reduced for a fluence 1 × 10¹³ ions/cm² as the defect states produced increase the non-radiative defect centres. These results suggest that the accumulation of defects due to irradiation at fluences 5 × 10¹¹ and 1 × 10¹³ ions/cm² are degenerate configurations which exhibit multiple lifetimes in photoluminescence studies. It is inferred that the optically active defect states influence the transition rate of charge carriers in this device material.     

High fluence nitrogen implantation in Al/Ti multilayers

We have studied the effects of high fluence nitrogen ion implantation on the structural changes in Al/Ti multilayers, with the aim of achieving multilayered metal-nitrides. The starting structures consisted of 10 alternate sputter-deposited Al and Ti films, with a total thickness of 270 nm, on (1 0 0) Si substrates. They were implanted with 200 keV , to 1 × 10¹⁷ and 2 × 10¹⁷ at/cm², the projected range being around half-depth of the multilayers. Structural characterization was performed by Rutherford backscattering, Auger electron spectroscopy and transmission electron microscopy. It was found that ion implantation to the higher fluence induces a full intermixing of Al/Ti layers, resulting in a multilayered structure with different content of Al, Ti and N. The applied method can be interesting for preparation of graded (Al,Ti)N multilayers, with a controlled content of nitrogen and a controlled level of Al-Ti intermixing within the structures.     

Study on preventing segregation of erbium atoms to a silicon surface by annealing in oxygen atmosphere at high temperature

The damage produced by implantation of Er ions of 400 keV at a fluence of 5 × 10¹⁵ ions/cm² in silicon was investigated by Rutherford backscattering spectrometry with 2.1 MeV He²⁺ ions with multiple scattering models. It was found that the damage around the Si surface was almost removed after annealing in oxygen and nitrogen atmospheres successively at 1000 °C, and only a small portion of the Er atoms segregated to the silicon surface. Most of the Er atoms diffused to deeper depths because of the affinity of Er for oxygen.     

Surface exfoliation and defect structures in Si induced by 160 keV He and 110 keV H ion implantation

Cz n-type Si(100) wafers were implanted at room temperature with 160 keV He ions at a fluence of 5 × 10¹⁶/cm² and 110 keV H ions at a fluence of 1 × 10¹⁶/cm², singly or in combination. Surface phenomena and defect microstructures have been studied by various techniques, including scanning electron microscopy (SEM), atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM). Surface exfoliation and flaking phenomena were only observed on silicon by successive implantation of He and H ions after subsequent annealing at temperatures above 400 °C. The surface phenomena show strong dependence on the thermal budget. At annealing temperatures ranging from 500 to 700 °C, craters with size of about 10 μm were produced throughout the silicon surface. As increasing temperature to 800 °C, most of the implanted layer was sheared, leaving structures like islands on the surface. AFM observations have demonstrated that the implanted layer is mainly transfered at the depth around 960 nm, which is quite consistent with the range of the ions. XTEM observations have revealed that the additional low fluence H ion implantation could significantly influence thermal growth of He-cavities, which gives rise to a monolayer of cavities surrounded by a large amount of dislocations and strain. The surface exfoliation effects have been tentatively interpreted in combination of AFM and XTEM results.     

Lattice expansion and evolution of damage buildup in Be-implanted InAs

The lattice expansion in InAs single crystal, due to ion-implantation by 80 keV Be ions with the implantation fluencies ranging from 1 × 10¹² to 2 × 10¹⁶ cm⁻², has been investigated by using high resolution X-ray diffraction (HRXRD), transmission electron microscopy (TEM), and Rutherford backscattering spectrometry/channeling (RBS/C). In order to clarify the evolution of damage buildup, the nonlinear maximum perpendicular strain ε_m as a function of the Be fluence was obtained and analyzed. The curve of ε_m vs. Be fluence is subdivided into five regions, each having a different damage accumulation behavior. The involved probable mechanisms of microstructural variation in InAs due to Be implantation of different fluencies are analyzed in detail.     

Ion beam induced defects in solids studied by optical techniques

Optical methods can provide important insights into the mechanisms and consequences of ion beam interactions with solids. This is illustrated by four distinctly different systems.X- and Y-cut LiNbO₃ crystals implanted with 8 MeV Au³⁺ ions with a fluence of 1 × 10¹⁷ ions/cm² result in gold nanoparticle formation during high temperature annealing. Optical extinction curves simulated by the Mie theory provide the average nanoparticle sizes. TEM studies are in reasonable agreement and confirm a near-spherical nanoparticle shape but with surface facets. Large temperature differences in the nanoparticle creation in the X- and Y-cut crystals are explained by recrystallisation of the initially amorphised regions so as to recreate the prior crystal structure and to result in anisotropic diffusion of the implanted gold.Defect formation in alkali halides using ion beam irradiation has provided new information. Radiation-hard CsI crystals bombarded with 1 MeV protons at 300 K successfully produce F-type centres and V-centres having the structure as identified by optical absorption and Raman studies. The results are discussed in relation to the formation of interstitial iodine aggregates of various types in alkali iodides. Depth profiling of and aggregates created in RbI bombarded with 13.6 MeV/A argon ions at 300 K is discussed.The recrystallisation of an amorphous silicon layer created in crystalline silicon bombarded with 100 keV carbon ions with a fluence of 5 × 10¹⁷ ions/cm² during subsequent high temperature annealing is studied by Raman and Brillouin light scattering.Irradiation of tin-doped indium oxide (ITO) films with 1 MeV protons with fluences from 1 × 10¹⁵ to 250 × 10¹⁵ ions/cm⁻² induces visible darkening over a broad spectral region that shows three stages of development. This is attributed to the formation of defect clusters by a model of defect growth and also high fluence optical absorption studies. X-ray diffraction studies show evidence of a strained lattice after the proton bombardment and recovery after long period storage. The effects are attributed to the annealing of the defects produced.     

Oxidation resistance of Y-implanted steel using accelerator based techniques

The thermal oxidation behavior in air of Y-implanted (fluence 2 × 10¹⁷ ions/cm²) and non-implanted stainless steel AISI-321 samples was investigated using the ¹⁶O(d,p)¹⁷O nuclear reaction and Rutherford backscattering spectrometry (RBS). The oxidation temperature was 650 and 900 °C and the duration of the thermal treatment 48 hours. The influence of the implantation energy (40, 55 and 80 keV) on the oxidation behavior of stainless steel was also studied. An improvement of the oxidation resistance of the Y-implanted samples with increasing implantation energy was observed. Additional secondary ion mass spectroscopy (SIMS) measurements of the samples implanted by 40 keV Y-ions also indicated a slight chromium depletion of their near-surface layers. Mechanisms attempting to explain the experimental results are proposed.     

Fabrication and nuclear analysis of isotopic N and N ion-implanted silicon standards

The fabrication of reliable isotopic nitrogen standards is achieved in Si through ¹⁴N and ¹⁵N ion implantation. 60 keV and ions were implanted at 400 °C up to ∼60% peak atomic concentration, yielding nitrogen-saturated silicon layers as measured using resonant nuclear reaction analysis. No isotopic effect has been observed. The nitrogen standards are validated by measurements of stability under ion irradiation. No significant desorption of nitrogen is observed either under a ⁴He⁺ ion fluence of 3.36 × 10¹⁶ cm⁻² or under a ¹H⁺ ion fluence of 8.60 × 10¹⁷ cm⁻², giving strong evidence that isotopic nitrogen standards can be achieved.     

FTIR and RBS study of ion-beam synthesized buried silicon oxide layers

Single crystal silicon samples were implanted at 140 keV by oxygen (¹⁶O⁺) ion beam to fluence levels of 1.0 × 10¹⁷, 2.5 × 10¹⁷ and 5.0 × 10¹⁷ cm⁻² to synthesize buried silicon oxide insulating layers by SIMOX (separation by implanted oxygen) process at room temperature and at high temperature (325 °C). The structure and composition of the ion-beam synthesized buried silicon oxide layers were investigated by Fourier transform infrared (FTIR) and Rutherford backscattering spectroscopy (RBS) techniques. The FTIR spectra of implanted samples reveal absorption in the wavenumber range 1250-750 cm⁻¹ corresponding to the stretching vibration of Si-O bonds indicating the formation of silicon oxide. The integrated absorption band intensity is found to increase with increase in the ion fluence. The absorption peak was rather board for 325 °C implanted sample. The FTIR studies show that the structures of ion-beam synthesized buried oxide layers are strongly dependent on total ion fluence. The RBS measurements show that the thickness of the buried oxide layer increases with increase in the oxygen fluence. However, the thickness of the top silicon layer was found to decrease with increase in the ion fluence. The total oxygen fluence estimated from the RBS data is found to be in good agreement with the implanted oxygen fluence. The high temperature implantation leads to increase in the concentration of the oxide formation compared to room temperature implantation.     

Implantation of anatase thin film with 100 keV Fe ions: Damage formation and magnetic behaviour

We have investigated the damage morphology and magnetic properties of titanium dioxide thin films following implantation with Fe ions. The titanium dioxide films, having a polycrystalline anatase structure, were implanted with 100 keV ⁵⁶Fe⁺ ions to a total fluence of 1.3 × 10¹⁶ ions/cm². The ion bombardment leads to an amorphized surface with no indication of the presence of secondary phases or Fe clusters. The ion-beam induced damage manifested itself by a marked change in surface morphology and film thickness. A room temperature ferromagnetic behaviour was observed by SQUID in the implanted sample. It is believed that the ion-beam induced damage and defects in the polycrystalline anatase film were partly responsible for the observed magnetic response.     

Ferroelectricity in Li-implanted ZnO thin films

ZnO:Li thin films were prepared by implantation of ZnO with a Li ion fluence 5 × 10¹⁶ ions/cm² at implantation energies of 50, 100, 200 keV. Ferroelectric characterization of the implanted samples revealed a clear hysteresis in the polarization-field curves. The origin of the ferroelectricity can be attributed to an off-center dipole caused by the large difference in ionic radii between the host Zn (0.74 Å) and the dopant Li (0.60 Å). ZnO:Li films which were implanted at 200 keV and annealed at a temperature of 700 ^°C exhibited a well-defined polarization hysteresis loop, with a remanent polarization of 0.8 μC/cm² and coercive field of 8.2 kV/cm, at room temperature. The dielectric phase transition was observed in the temperature range from 340 to 360 K. It is concluded that this novel ferroelectric phase transition in ZnO:Li results from the small structural distortion induced along the c-axis.     

Oxygen depth profiling in Kr-implanted polycrystalline alpha titanium by means of O(α,α)O resonance scattering

The ¹⁶O(α,α)¹⁶O resonance scattering was applied to study the effects of ion implantation on the oxygen distribution in the near surface region of polycrystalline titanium implanted with 180 keV krypton ions at fluences, ranging between 1 × 10¹⁴ and 5 × 10¹⁵ Kr⁺/cm². Two sample sets were chosen: as-received polycrystalline titanium discs rolled and annealed in half-hard condition which had a thick oxygen layer and similar samples in which this surface layer was removed by polishing. An increase of the mean oxygen concentration observed in both unpolished and polished samples at low fluence suggests a knock-on implantation of surface oxygen atoms. At high fluence, an overall decrease in the mean oxygen concentration and mean oxygen depth suggests an out-diffusion of near-surface oxygen atoms.     

Structural characterization of buried nitride layers formed by nitrogen ion implantation in silicon

The synthesis of buried silicon nitride insulating layers was carried out by SIMNI (separation by implanted nitrogen) process using implantation of 140 keV nitrogen (¹⁴N⁺) ions at fluence of 1.0 × 10¹⁷, 2.5 × 10¹⁷ and 5.0 × 10¹⁷ cm⁻² into 〈1 1 1〉 single crystal silicon substrates held at elevated temperature (410 °C). The structures of ion-beam synthesized buried silicon nitride layers were studied by X-ray diffraction (XRD) technique. The XRD studies reveal the formation of hexagonal silicon nitride (Si₃N₄) structure at all fluences. The concentration of the silicon nitride phase was found to be dependent on the ion fluence. The intensity and full width at half maximum (FWHM) of XRD peak were found to increase with increase in ion fluence. The Raman spectra for samples implanted with different ion fluences show crystalline silicon (c-Si) substrate peak at wavenumber 520 cm⁻¹. The intensity of the silicon peak was found to decrease with increase in ion fluence.     

Ion irradiation effects on surface mechanical behavior and shrinkage of hybrid sol-gel derived silicate thin films

A study of the effects of ion irradiation on the surface mechanical behavior and shrinkage of organic/inorganic modified silicate thin films was performed. The films were synthesized by sol-gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. The sol viscosity and the spin velocity were adjusted so that the films produced had a final thickness ranging from 580 to 710 nm after heat treatment. The ion species and incident energies used were selected such that the projected ion range was greater than the film thickness, resulting in fully irradiated films. After heat treatment at 300 °C for 10 min, the films were irradiated with 125 keV H⁺, 250 keV N²⁺ and 2 MeV Cu⁺ ions with fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ ions/cm². Both hardness and reduced elastic modulus were seen to exhibit a monotonic increase with fluence for all three ion species. Also, H loss was found to increase monotonically with increase in fluence, while the film thickness was found to decrease with increase in fluence.     

Lateral straggling and its influence on lateral diffusion in implantation with a focused ion beam

Parallel stripes of nanostructures on an n-type Si substrate have been fabricated by implanting 30 keV Ga⁺ ions from a focused ion beam (FIB) source at three different fluences: 1 × 10¹⁵, 2 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Two sets of implantation were carried out. In one case, during implantation the substrate was held at room temperature and in the other case at 400 °C. Photoemission electron microscopy (PEEM) measurements were carried out on these samples. The implanted parallel stripes, each with a nominal dimension of 4000 × 100 nm², appear as bright regions in the PEEM image. Line scans of the intensities from PEEM images were recorded along and across these stripes. Intensity profile at the edges of a line scan is broader for the implantation carried out at 400 °C compared to room temperature. From the analysis of this intensity profile lateral diffusion coefficient of Ga in silicon was estimated assuming that the PEEM intensity is proportional to Ga concentration. The diffusion coefficient at 400 °C has been estimated to be ∼10⁻¹⁵ m²/s. No significant dependence of diffusion coefficient on ion fluence was observed in the fluence range investigated here. Radiation enhanced diffusion has been discussed in the light of the associated defect distribution due to lateral straggling of the implanted ions.     

Effects of O swift heavy ion irradiation on indium oxide thin films

Indium oxide thin films deposited by spray pyrolysis were irradiated by 100 MeV O⁷⁺ ions with different fluences of 5 × 10¹¹, 1 × 10¹² and 1 × 10¹³ ions/cm². X-ray diffraction analysis confirmed the structure of indium oxide with cubic bixbyite. The strongest (2 2 2) orientation observed from the as-deposited films was shifted to (4 0 0) after irradiation. Furthermore, the intensity of the (4 0 0) orientation was decreased with increasing fluence together with an increase in (2 2 2) intensity. Films irradiated with maximum fluence exhibited an amorphous component. The mobility of the as-deposited indium oxide films was decreased from ∼78.9 to 43.0 cm²/V s, following irradiation. Films irradiated with a fluence of 5 × 10¹¹ ions/cm² showed a better combination of electrical properties, with a resistivity of 4.57 × 10⁻³ Ω cm, carrier concentration of 2.2 × 10¹⁹ cm⁻³ and mobility of 61.0 cm²/V s. The average transmittance obtained from the as-deposited films decreased from ∼81% to 72%, when irradiated with a fluence of 5 × 10¹¹ ions/cm². The surface microstructures confirmed that the irregularly shaped grains seen on the surface of the as-deposited films is modified as “radish-like” morphology when irradiated with a fluence of 5 × 10¹¹ ions/cm².