Ion beam modification of porous silicon using high energy Au ions and its impact on photoluminescence spectra

This paper presents investigation of impact of high-energy ion-irradiation on properties of light emitting porous silicon (PS) through photoluminescence (PL) spectroscopy. Irradiation was performed with 100 MeV Au⁺⁷ ions from a pelletron accelerator at ion doses in 10¹⁰-10¹⁴ cm⁻² range. The effect was associated with a blueshift (∼40 nm) and an enhancement of the PL intensity, in general. The efficiency and stability of PL with respect to ambients was seen to be relatively improved. The PL properties of PS were found to be stable against low to medium dose irradiation (<10¹³ cm⁻²), whereas, higher dose led to further degradation of the optical properties. The effects have been explained in terms of a decrease in the non-radiative recombination probability of electron-hole pairs due to chemical restructuring of the surface and a reduced crystallite size as a result of irradiation.     

Effects of evolving surface morphology on yield during focused ion beam milling of carbon

We investigate evolving surface morphology during focused ion beam bombardment of C and determine its effects on sputter yield over a large range of ion dose (10¹⁷-10¹⁹ ions/cm²) and incidence angles (Θ = 0-80°). Carbon bombarded by 20 keV Ga⁺ either retains a smooth sputtered surface or develops one of two rough surface morphologies (sinusoidal ripples or steps/terraces) depending on the angle of ion incidence. For conditions that lead to smooth sputter-eroded surfaces there is no change in yield with ion dose after erosion of the solid commences. However, for all conditions that lead to surface roughening we observe coarsening of morphology with increased ion dose and a concomitant decrease in yield. A decrease in yield occurs as surface ripples increase wavelength and, for large Θ, as step/terrace morphologies evolve. The yield also decreases with dose as rippled surfaces transition to have steps and terraces at Θ = 75°. Similar trends of decreasing yield are found for H₂O-assisted focused ion beam milling. The effects of changing surface morphology on yield are explained by the varying incidence angles exposed to the high-energy beam.     

Photoluminescence and Raman studies of Xe ion-implanted diamonds: Dependence on implantation dose

We report on photoluminescence and Raman studies of Xe ion-implanted diamond. Several natural and high-purity artificial diamonds implanted within the wide dose range of 10¹⁰-5×10¹⁴ ion/cm² were studied. The room temperature luminescence of the Xe center consists of two zero phonon lines, at 813 nm (strong) and 794 nm (weak). The dose dependences of photoluminescence and Raman spectra were studied. For doses less than 10¹³ ion/cm², the luminescence intensity grows with the implantation dose linearly. The defect-induced photoluminescence quenching was observed for doses equal or more than 10¹³ ion/cm². Possible models of the Xe center will be discussed. The nature of damages induced by ion implantation at different doses was analyzed using micro-Raman spectroscopy.     

EPR and photoacoustic studies on 30 kev H ion-implanted n-GaAs

Electron paramagnetic resonance (EPR) measurements are carried out on the 30 keV H⁺ion-implanted, Si-doped GaAs(1 0 0) for various doses from 10¹⁴ to 10¹⁷ cm⁻². The results are correlated with photoacoustic and photoluminescence measurements. All the measurements confirm the sign change of charge carrier at a dose of 10¹⁵ cm⁻².     

Ar irradiation of Si nanocrystal-doped SiO2: Evolution of photoluminescence

We report the evolution of photoluminescence (PL) of Si nanocrystals (nc-Si) embedded in a matrix of SiO₂ during Ar⁺ ion bombardment. The integrated intensity of nc-Si PL falls down drastically before the Ar⁺ ion fluence of 10¹⁵ ions cm⁻², and then decreases slowly with the increasing ion fluence. At the meantime, the PL peak position blueshifts steadily before the fluence of 10¹⁵ ions cm⁻², and then changes in an oscillatory manner. Also it is found that the nc-Si PL of the Ar⁺-irradiated sample can be partly recovered after annealing at 800 °C in nitrogen, but can be almost totally recovered after annealing in oxygen. The results confirm that the ion irradiation-induced defects are made up of oxygen vacancies, which absorb light strongly. The oscillatory peak shift of nc-Si can be related to a size-distance distribution of nc-Si in SiO₂.     

Investigation of FIB irradiation damage in La0.7Sr0.3MnO3 thin films

In this work we analyse systematically how morphological and magnetotransport properties of manganite thin films are affected by the damage induced by focused ion beam (FIB) irradiation. We irradiate different areas of the same sample with doses ranging from 5×10¹² to 3×10¹⁷ ions/cm² and we find that the film becomes swollen for doses up to 10¹⁶ ions/cm² and is eventually eroded by ion milling for further irradiation. On the other hand, transport properties are much more sensitive to FIB irradiation: the metal–insulator transition temperature is found to decrease monotonically with increasing doses up to 1.8×10¹³ ions/cm². At doses higher than 5.6×10¹³ ions/cm² the metallic state is completely suppressed and likely, also ferromagnetism.     

Enhanced photo-response of thin-film structures with nanocrystals

Thin-film multilayers with dielectric and semiconductor nanolayers of 200-10 nm thicknesses have been deposited by thermal evaporation onto irradiation-resistive substrates using pure crystals as evaporated targets. Some multilayers were γ-irradiated in air at room temperature with dose of 83 kGy. X-ray diffraction and microscopy studies reveal that the multilayers consist of nanometer-sized crystals with cubic structure and defined size. Film structures were oriented along the (1 1 1) plane. Absorption spectra of non-irradiated LiF nanocrystals of 100 nm size and those of initial crystals give evidence of metal colloids presence. Photoluminescence spectra of γ-irradiated nanostructures with various LiF content show the enhancement of F₃⁺-colour centres excitation in the region of metal colloids absorption and the increase is observed between emission intensities of F₃⁺ and F₂ centers with respect to initial crystals γ-coloured in identical conditions. Emission intensities of both centers under excitation in the M band correlate with LiF content. These effects, which are related to high-quality nanocrystals, but at the same time depend strongly on the defect content, especially as far as their 1-2 ps nonlinearities are concerned, could depend on nanocrystal purity and metal excess collection in their boundaries regions.     

Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation

The graft polymerization of acrylic acid (AAc) was carried out onto poly(tetrafluoroethylene) (PTFE) films that had been pretreated with remote argon plasma and subsequently exposed to oxygen to create peroxides. Peroxides are known to be the species responsible for initiating the graft polymerization when PTFE reacts with AAc. We chose different parameters of remote plasma treatment to get the optimum condition for introducing maximum peroxides (2.87 × 10⁻¹¹ mol/cm²) on the surface. The influence of grafted reaction conditions on the grafting degree was investigated. The maximum grafting degree was 25.2 μg/cm². The surface microstructures and compositions of the AAc grafted PTFE film were characterized with the water contact angle meter, Fourier-transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Contact angle measurements revealed that the water contact angle decreased from 108° to 41° and the surface free energy increased from 22.1 × 10⁻⁵ to 62.1 × 10⁻⁵ N cm⁻¹ by the grafting of the AAc chains. The hydrophilicity of the PTFE film surface was greatly enhanced. The time-dependent activity of the grafted surface was better than that of the plasma treated film.     

Topological and chemical investigation on super-hydrophobicity of PTFE surface caused by ion irradiation

Super-hydrophobic PTFE surfaces were obtained by irradiation of 200 keV Xe⁺ ion with the fluence of 6.2×10¹³ ions/cm². The contact angle of water on such surface is as large as 161±3°. SEM and XPS were used to investigate how the topological and chemical changes affect the wettability of the irradiated surface. Needle like structures at nanometer scale caused by irradiation are considered to be the reason of the super-hydrophobicity. The formation of oxygen containing group and defluorination effect on the treated surface are inferred to have negative contribution to the hydrophobic optimization of PTFE surface.     

Thermoluminescence and photoluminescence of LiNaSO4:Eu irradiated with 24 and 48 MeV Li ion beam

Thermoluminescence (TL) of LiNaSO₄:Eu phosphor, irradiated with 24 and 48 MeV ⁷Li ions at different fluences in the range 5×10⁹-1×10¹² ion/cm², has been studied. The samples from the same batch were also exposed to γ-rays from a Cs¹³⁷ source for comparative studies. The TL glow curves of the materials, irradiated with ⁷Li ions, have similar structures to that of γ-irradiated sample. They have a simple structure with a prominent peak at 412 K along with small one at around 481 K. The intensity ratios of 412-481 K peaks have been observed to increase with fluence increasing, while that of γ-irradiated sample shows a reverse trend. This could be attributed to the changes in the recombination center populations due to ⁷Li ions, that have been implanted inside the matrix of LiNaSO₄:Eu, during irradiation and might also act as a source for new trapping and luminescent centers. The implantation has been confirmed by TRIM calculations. The penetration depths (where the ion comes to rest) are found to be 145 and 463 μm corresponding to 24 and 48 MeV ion beam energies, respectively, which are less than the thickness of the sample chips (∼800 μm). The efficiencies of LiNaSO₄:Eu to 24 and 48 MeV ⁷Li ions measured relative to γ-rays of Cs¹³⁷ are found to be 0.007 and 0.024, respectively. Theoretical analysis of the glow curves of the samples irradiated by ⁷Li ions and γ-rays were done by glow curve deconvolution method to determine trapping parameters of various peaks. The experimentally observed linearity/sublinearity has been discussed in the frame of track interaction model. Photoluminescence studies in the ⁷Li ions irradiated and un-irradiated samples show that europium ions have incorporated in the host in their divalent (emission at 440 nm) as well as trivalent (emissions at 594, 615 and 700 nm) forms. The intensities of the emission bands of these ions have been observed to increase with fluence increasing.     

Surface modification of porous poly(tetrafluoraethylene) film by a simple chemical oxidation treatment

A simple, inexpensive and environmental chemical treatment process, i.e., treating porous poly(tetrafluoroethylene) (PTFE) films by a mixture of potassium permanganate solution and nitric acid, was proposed to improve the hydrophilicity of PTFE. To evaluate the effectiveness of this strong oxidation treatment, contact angle measurement was performed. The effects of treatment time and temperature on the contact angle of PTFE were studied as well. The results showed that the chemical modification decreased contact angle of as-received PTFE film from 133 ± 3° to 30 ± 4° treated at 100 °C for 3 h, effectively converting the hydrophobic PTFE to a hydrophilic PTFE matrix. The changes in chemical structure, surface compositions and crystal structure of PTFE were examined by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), environmental scanning electron microscopy (ESEM), X-ray diffraction (XRD), respectively. It was found that the F/C atomic ratio decreased from untreated 1.65-0.10 treated by the mixture at 100 °C for 3 h. Hydrophilic groups such as carbonyl (CO) and hydroxyl (OH) were introduced on the surface of PTFE after treatment. Furthermore, hydrophilic compounds K_0.27MnO₂·0.54H₂O was absorbed on the surface of porous PTFE film. Both the introduction of hydrophilic groups and absorption of hydrophilic compounds contribute to the significantly decreased contact angle of PTFE.     

The influence of space irradiated PIN photodetector on BER in satellite laser communication system

By analyzing the radiation dose on PIN photodetectors in space radiation environment, the variation of photocurrent and dark current after radiation is obtained. On the basis, the bit error rate of satellite laser communication based on space radiation dose of PIN photodetectors is established. According to simulation, when radiation dose is about 1.6 × 10³ Gy and 7 × 10⁴ Gy, bit error rate reaches 10⁻⁶ induced by 50 MeV and 10 MeV protons separately; and when radiation dose is within the range of 5 × 10 Gy–6 × 10⁵ Gy, electrons and gamma-ray irradiation also cause increase in bit error rate to 10⁻⁶. The principle of damage dose on bit error rate is investigated, and the influence of decision threshold on bit error rate is further discussed. The result shows that when radiation dose is 1 MGy, if decision threshold is increased from 4.3 × 10⁻⁷ A to 5.5 × 10⁻⁷ A, bit error rate will decrease about 4 orders of magnitude. Hence, a proper decision threshold can improve system bit error rate efficiently.     

Characterization of structural modifications in poly-tetra-fluoroethylene induced by electron beam irradiation

The effects of electron beam irradiation doses on the poly-tetra-fluoroethylene (PTFE) have been studied. Several techniques, such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical properties and Fourier transform infrared spectroscopy (FTIR) were applied to characterize the PTFE samples and to study the radiation effects on the crystal structure of the polymer.The irradiation dose up to 150 kGy showed an increase in the crystallinity degree of PTFE, which has been observed and confirmed during the DSC and XRD measurements. The increase in crystallinity was attributed to the scissions of the chain in the amorphous region. Moreover, the number-average molecular weights were estimated from the heat of crystallization measured by DSC technique. The results indicated that the molecular weights were decreased by increasing the heat of crystallization due to irradiation with doses up to 150 kGy. Radiation resistance of the irradiated and non-irradiated PTFE was investigated during its mechanical properties at room temperature. The dose at half value of the elongation at break is about 3.10 kGy while the dose at half value of the tensile strength is about 1.70 kGy.     

On the surface trapping parameters of polytetrafluoroethylene block

Surface flashover phenomena under high electric field are closely related to the surface characteristics of a solid insulating material between energized electrodes. Based on measuring the surface potential decaying curve of polytetrafluoroethylene (PTFE) block charged by a needle-plane corona discharge, its surface trapping parameters are calculated with the isothermal current theory, and the correlative curve between the surface trap density and its energy level is obtained. The maximum density of electron traps and hole traps in the surface layer of PTFE presents a similar value of ∼2.7 × 10¹⁷ eV⁻¹ m⁻³, and the energy level of its electron and hole traps is of about 0.85-1.0 eV and 0.80-0.90 eV, respectively. Via the X-ray photoelectron spectroscopy (XPS) technique, the F, C, K and O elements are detected on the surface of PTFE samples, and F shows a remarkable atom proportion of ∼73.3%, quite different from the intrinsic distribution corresponding to its chemical formula. The electron traps are attributed to quantities of F atoms existing on the surface of PTFE due to its molecular chain with C atoms surrounded by F atoms spirally. It is considered that the distortions of chemical and electronic structure on solid surface are responsible for the flashover phenomena occurring at a low applied voltage.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and short chain alcohol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and methanol and ethanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA). Using measured contact angle values the relationships between cos θ, adhesion tension and surface tension of the solutions were determined, and on their basis the critical surface tension of PTFE and PMMA wetting was calculated. The obtained average value of the critical surface tension of PTFE wetting is lying in the range of the PTFE surface tension values which can be found in the literature, while for PMMA it is even lower than the Lifshitz-van der Waals component of its surface tension. From the relationship between the adhesion and surface tension and Lucassen-Reynders equation it results that in the case of PTFE the adsorption at the PTFE-solution and solution-air interfaces is the same, which was confirmed by a linear relationship between the cos θ and 1/γ_LV and intercept on cos θ axis equal to −1. However, for PMMA the adsorption of the surface active agents at solution-air interface is higher than at PMMA-solution. Using the values of the contact angle the values of the adhesion work of solution to the PTFE and PMMA surface were also determined, which are constant for PTFE, but for PMMA decrease with alcohol concentration increase. Next, using the contact angle values in the Young equation, the PTFE(PMMA)-solution interface tension was also calculated. The obtained values of PTFE-solution interface tension were compared with those evaluated from the Szyszkowski, Connors and Fainerman and Miller equations, and good agreement between these values was observed for all series of TX-100 and alcohol mixtures at a low alcohol concentration.     

Characterization and ion-induced degradation of cross-linked poly(methyl methacrylate) studied using time of flight secondary ion mass spectrometry

In this study, a series of random copolymers of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) were prepared as surface-initiated polymer (SIP) films on silicon substrates using atom transfer radical polymerization. Positive and negative ion static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to characterize SIP films with different MMA/EGDMA monomer ratios in an attempt to quantify their surface composition. However, matrix effects in the positive and negative ion modes led to preferential secondary ion generation from the EGDMA monomer and suppression of secondary ions characteristic of the MMA monomer, precluding accurate quantification using standard linear quantification methods. Ion-induced degradation of these films under 5 keV SF₅⁺ bombardment was also examined to determine the effect of cross-linking on the accumulation of ion-induced damage. Increasing incorporation of the EGDMA cross-linker in the SIP films decreased the sputter rate and increased the rate of damage accumulation under extended (>10¹⁴ ions/cm²) 5 keV SF₅⁺ bombardment. Comparison of the ion bombardment data with thermal degradation of cross-linked PMMA suggests that the presence of the cross-linker impedes degradation by depolymerization, resulting in ion-induced damage accumulation. The increased rate of ion-induced damage accumulation with increased cross-link density also suggests that polymers that can form cross-links during ion bombardment are less amenable to depth profiling using polyatomic primary ions.     

Thermal and optical studies on unirradiated and γ-irradiated polyester track detector

Thermal and optical properties of unirradiated and γ-irradiated polyester track detector films in the dose range of 0–14.5 Mrad have been studied by thermogravimetry (TG) and UV-Visible spectroscopic technique. The samples were irradiated with ⁶⁰Co γ-rays for doses of 4.7, 8.1 and 14.5 Mrad. The TG studies indicate that unirradiated and the γ-irradiated samples degrade in two steps. The kinetics of the two steps of degradation were also evaluated from the TG curves. Irradiation enhances the degradation rate and the effect increases further with increasing radiation dose. The optical band gaps of the unirradiated as well as the irradiated samples were also determined from the UV-Visible spectra. These studies can be used for the estimation of γ-dose using changes in absorbance and the activation energy due to γ-irradiation.     

Quantitative ToF-SIMS studies of protein drug release from biodegradable polymer drug delivery membranes

Biodegradable polymers are of interest in developing strategies to control protein drug delivery. The protein that was used in this study is Keratinocyte Growth Factor (KGF) which is a protein involved in the re-epithelialization process. The protein is stabilized in the biodegradable polymer matrix during formulation and over the course of polymer degradation with the use of an ionic surfactant Aerosol-OT (AOT) which will encapsulate the protein in an aqueous environment. The release kinetics of the protein from the surface of these materials requires precise timing which is a crucial factor in the efficacy of this drug delivery system.Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used in the same capacity to identify the molecular ion peak of the surfactant and polymer and use this to determine surface concentration. In the polymer matrix, the surfactant molecular ion peak was observed in the positive and negative mode at m/z 467 and 421, respectively. These peaks were determined to be [AOT + Na⁺] and [AOT − Na⁺]. These methods are used to identify the surfactant and protein from the polymer matrix and are used to measure the rate of surface accumulation. The second step was to compare this accumulation rate with the release rate of the protein into an aqueous solution during the degradation of the biodegradable film. This rate is compared to that from fluorescence spectroscopy measurements using the protein autofluorescence from that released into aqueous solution [C.M. Mahoney, J. Yu, A. Fahey, J.A.J. Gardella, SIMS depth profiling of polymer blends with protein based drugs, Appl. Surf. Sci. 252 (2006), 6609-6614.].     

The influence of the cholesterol microenvironment in tissue sections on molecular ionization efficiencies and distributions in ToF-SIMS

High-resolution images of cholesterol were obtained from Lymnaea stagnalis nervous tissue using metal-assisted (MetA) time-of-flight secondary ion mass spectrometry (ToF-SIMS). The spatial distributions of different pseudomolecular ions of cholesterol [M − H]⁺, [M − OH]⁺ and [2M + Au]⁺, illustrate the influence of the tissue microenvironment on the ionization efficiencies of these ions. These biological matrix effects result in differences in localizations of molecular ions derived from the same molecular species.     

Thermal expansion coefficient of alumina films developed by oxidation of a FeCrAl alloy determined by a deflection technique

Thermal expansion coefficients of α alumina films formed by oxidation of an oxide dispersion strengthened (ODS) FeCrAl alloy have been determined between 20 and 900 °C using an original deflection test. This technique is based on the curvature of a dissymmetrical sample consisting of a thin and elongated metallic substrate covered on one of its large sides by an oxide film. The average value of the expansion coefficient of the compact columnar α alumina film is found to equal 10.3 × 10⁻⁶ K⁻¹ which is higher than most values given in the literature.