Structural studies of silicon oxynitride layers formed by low energy ion implantation

Silicon oxynitride (Si_xO_yN_z) layers were synthesized by implanting ¹⁶O₂⁺ and ¹⁴N₂⁺ 30 keV ions in 1:1 ratio with fluences ranging from 5 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻² into single crystal silicon at room temperature. Rapid thermal annealing (RTA) of the samples was carried out at different temperatures in nitrogen ambient for 5 min. The FTIR studies show that the structures of ion-beam synthesized oxynitride layers are strongly dependent on total ion-fluence and annealing temperature. It is found that the structures formed at lower ion fluences (∼1 × 10¹⁷ ions cm⁻²) are homogenous oxygen-rich silicon oxynitride. However, at higher fluence levels (∼1 × 10¹⁸ ions cm⁻²) formation of homogenous nitrogen rich silicon oxynitride is observed due to ion-beam induced surface sputtering effects. The Micro-Raman studies on 1173 K annealed samples show formation of partially amorphous oxygen and nitrogen rich silicon oxynitride structures with crystalline silicon beneath it for lower and higher ion fluences, respectively. The Ellipsometry studies on 1173 K annealed samples show an increase in the thickness of silicon oxynitride layer with increasing ion fluence. The refractive index of the ion-beam synthesized layers is found to be in the range 1.54-1.96.     

Study on the behavior of oxygen atoms in swift heavy ion irradiated CeO2 by means of synchrotron radiation X-ray photoelectron spectroscopy

To study the effects of swift heavy ion irradiation on cerium dioxide (CeO₂), CeO₂ sintered pellets were irradiated with 200 MeV Xe ions at room temperature. For irradiated and unirradiated samples, the spectra of X-ray photoelectron spectroscopy (XPS) were measured. XPS spectra for the irradiated samples show that the valence state of Ce atoms partly changes from +4 to +3. The amount of Ce³⁺ state was quantitatively obtained as a function of ion-fluence. The relative amount of oxygen atom displacements, which are accompanied by the decrease in Ce valence state, is 3-5%. This value is too large to be explained in terms of elastic interactions between CeO₂ and 200 MeV ions. The experimental result suggests the contribution of 200 MeV Xe induced electronic excitation to the displacements of oxygen atoms.     

Swift heavy ion induced structural modifications in zircon and scheelite phases of ThGeO4

Structural modifications in the zircon and scheelite phases of ThGeO₄ induced by swift heavy ions (93 MeV Ni⁷⁺) at different fluences as well as pressure quenching effects are reported. X-ray diffraction and Raman measurements at room temperature on the irradiated zircon phase of ThGeO₄ indicate the occurrence of stresses that lead to a reduction of the cell volume up to 2% followed by its transformation to a mixture of nano-crystalline and amorphous scheelite phases. Irradiation of the zircon phase at liquid nitrogen temperature induces amorphization at a lower fluence (7.5 × 10¹⁶ ions/m²), as compared to that at room temperature (6 × 10¹⁷ ions/m²). Scheelite type ThGeO₄ irradiated at room temperature undergoes complete amorphization at a lower fluence of 7.5 × 10¹⁶ ions/m² without any volume reduction. The track radii deduced from X-ray diffraction measurements on room temperature irradiated zircon, scheelite and low temperature irradiated zircon phases of ThGeO₄ are, 3.9, 3.5 and 4.5 nm, respectively. X-ray structural investigations on the zircon phase of ThGeO₄ recovered after pressurization to about 3.5 and 9 GPa at ambient temperature show the coexistence of zircon and disordered scheelite phases with a larger fraction of scheelite phase occurring at 9 GPa. On the other hand, the scheelite phase quenched from 9 GPa shows crystalline scheelite phase pattern.     

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.     

Swift heavy ion irradiation induced texturing in NiO thin films

NiO thin films grown on Si(1 0 0) substrate by electron beam evaporation and sintered at 500 and 700 °C were irradiated with 120 MeV Au⁹⁺ ions. The FCC structure of the sintered films was retained up to the highest fluence (3 × 10¹³ ions cm⁻²) of irradiation. In the low fluence (?1 × 10¹³ ions cm⁻²) regime however, the evolution of the XRD pattern with fluence showed a wide variation, critically depending upon their initial microstructure. Though irradiation is known to induce disorder in the structure, we observe improvement in crystallization and texturing at intermediate fluences of irradiation.     

Catastrophic processes in dielectrics in irradiation by high-current electron beams

The results of the research in explosive decomposition of heavy metal azides initiated by electric (“streamer”) charges induced by high-current electron beam have been considered. A physical model for initiation of heavy metal azides explosive decomposition by electron beam has been suggested. The model suggests formation of strong electric field in the sample and its neutralization by ultrasound anode charges. The streamer front generates “hot spots” which start the formation of explosive decomposition sites in a condensed reactive material.     

Second crossover energy of insulating materials using stationary electron beam under normal incidence

The purpose of this paper is to give some aspects of charging effects on dielectric materials submitted to continuous electron beam irradiation in a scanning electron microscope (SEM). When the dielectric is irradiated continuously, the so-called total yield approach (TYA) used to predict the sign of the charge appeared on electron irradiated insulators fails because the charge accumulated in the dielectric interferes with the electrons emission processes. Based on previous experimental and theoretical works found in the literature, an analysis of the evolution of the electron yield curves σ = f(E₀) of insulators during irradiation is given. The aim of this work is firstly to determine experimentally the second crossover energy E_2C under continuous electron irradiation (charging conditions) and secondly to demonstrate that the charge balance occurs at this beam energy and not at E₂ the energy deduced from non-charging conditions (pulse primary electron beam experiments) as commonly asserted. It is however possible to apply the TYA by substituting the critical energy E₂ for E_2C. The experimental procedure is based on simultaneous time dependent measurements of surface potential, leakage current and displacement current. The study underlines the difference between the landing energy of primary electrons E_L at the steady state and the second crossover energy, E_2C, for charged samples. Some preliminary results are also obtained concerning the influence of the incident beam density on the energy E_2C. The samples used for this study are PMMA, polycrystalline silicone dioxide (p-SiO₂), polycrystalline alumina (p-Al₂O₃) and soda lime glass (SLG).     

Radiation damage evolution in ceramics

A review is presented of recent results on radiation damage production, defect accumulation and dynamic annealing in a number of ceramics, such as silicon carbide, zircon and zirconia. Under energetic particle irradiation, ceramics can undergo amorphization by the accumulation of point defects and defect clusters (silicon carbide) or direct impact amorphization (zircon). Ceramics that resist radiation-induced amorphization have mechanisms to dissipate the primary knock-on atom energy, such as replacement collision sequences that leave the lattice undisturbed and low-energy cation site exchange. The presence of engineered mobile defects, such as structural vacancies in stabilized zirconia, can dynamically anneal radiation damage. Thus, defect engineering is a promising strategy to design radiation tolerance for applications such as nuclear waste disposal.     

Defects creation in sapphire by swift heavy ions: A fluence depending process

Single crystals of sapphire (α-Al₂O₃) were irradiated at GANIL with 0.7 MeV/amu xenon ions corresponding to an electronic stopping power of 21 keV/nm. Several fluences were applied between 5 × 10¹¹ and 2 × 10¹⁴ ions/cm². Irradiated samples were characterized using optical absorption spectroscopy. This technique exhibited the characteristic bands associated with F and F⁺ centers defects. The F centers density was found to increase with the fluence following two different kinetics: a rapid increase for fluences less than 10¹³ ions/cm² and then, a slow increase for higher fluences. For fluences less than 10¹³ ions/cm², results are in good agreement with those obtained by Canut et al. [B. Canut, A. Benyagoub, G. Marest, A. Meftah, N. Moncoffre, S.M.M. Ramos, F. Studer, P. Thévenard, M. Toulemonde, Phys. Rev. B 51 (1995) 12194]. In the fluences range: 10¹³-10¹⁴ ions/cm², the F centers defects creation process is found to be different from the one evidenced for fluences less than 10¹³ ions/cm².     

Modification of the etching properties of x-cut Lithium Niobate by ion implantation

In this work x-cut Lithium Niobate crystals were implanted with 0.5 MeV O ions (nuclear stopping regime), 5 MeV O ions (sub-threshold electronic stopping regime) and 12.5 MeV Ti ions (ion track regime) at the fluences required for the formation of a surface fully disordered layer. The damage depth profiles were determined by RBS-channeling. Wet etching was performed at room temperature in 50% HF:H₂O solution. The data indicated an exponential dependence of the etching rate on the damage concentration. Independently of the damage regime, once random level in the RBS-channeling spectra was attained we measured the same etching rate (50-100 nm/s) and the same volume expansion (∼10%) in all samples. These results indicate that the fully disordered layers obtained by electronic damage accumulation have the same chemical properties of those obtained by conventional nuclear damage accumulation and therefore they can be defined “amorphous”. The impressive etching selectivity of ion implanted regions makes this process suitable for sub-micro machining of Lithium Niobate.     

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.     

Evidence of nanostructure formation in Ge oxide by crystallization induced by swift heavy ion irradiation

Ge oxide films were irradiated with 150 MeV Ag ions at fluences varying between 10¹² and 10¹⁴ ions/cm². The irradiation-induced changes were monitored by FT-IR spectroscopy, atomic force microscopy, X-ray diffraction and photoluminescence spectroscopy. The FT-IR spectra indicate stoichiometric changes and an increase in Ge content on irradiation. X-ray diffraction shows a crystallization of the irradiated films and presence of both Ge and GeO₂ phases. The Ge nanocrystal size, as calculated from Scherrer’s formula, was around 30 nm. The morphological changes, observed in atomic force microscopy, also indicate formation of nanostructures upon ion irradiation and a uniform growth is observed for a fluence of 1 × 10¹⁴ ions/cm².     

Modification of a shell model for the study of the radiation effects in BaTiO3

In order to study the radiation effects in BaTiO₃ ferroelectric crystal, a previously developed shell model is modified. The modifications include adding the ZBL universal potentials at short distances and distance-dependent spring constants for core-shell interactions. The phase transition sequences in BaTiO₃ were correctly reproduced using molecular dynamics simulations with this modified shell model. Also, the calculated Frenkel pair formation energies agree well with results obtained by first principles calculations, which suggests that this model is suitable for the simulation of the radiation effects in BaTiO₃. The dependence of polarization on the number of oxygen vacancies was also studied.     

Radiation damage in ZnO ion implanted at 15 K

Commercial O-face (0 0 0 1) ZnO single crystals were implanted with 200 keV Ar ions. The ion fluences applied cover a wide range from 5 × 10¹¹ to 7 × 10¹⁶ cm⁻². The implantation and the subsequent damage analysis by Rutherford backscattering spectrometry (RBS) in channelling geometry were performed in a special target chamber at 15 K without changing the target temperature of the sample. To analyse the measured channelling spectra the computer code DICADA was used to calculate the relative concentration of displaced lattice atoms.Four stages of the damage evolution can be identified. At low ion fluences up to about 2 × 10¹³ cm⁻² the defect concentration increases nearly linearly with rising fluence (stage I). There are strong indications that only point defects are produced, the absolute concentration of which is reasonably given by SRIM calculations using displacement energies of E_d(Zn) = 65 eV and E_d(O) = 50 eV. In a second stage the defect concentration remains almost constant at a value of about 0.02, which can be interpreted by a balance between production and recombination of point defects. For ion fluences around 5 × 10¹⁵ cm⁻² a second significant increase of the defect concentration is observed (stage III). Within stage IV at fluences above 10¹⁶ cm⁻² the defect concentration tends again to saturate at a level of about 0.5 which is well below amorphisation. Within stages III and IV the damage formation is strongly governed by the implanted ions and it is appropriate to conclude that the damage consists of a mixture of point defects and dislocation loops.     

Swelling and optical properties of Si3N4 films irradiated in the electronic regime

Silicon nitride layers of 140 nm thickness were deposited on silicon wafers by low pressure chemical vapour deposition (LPCVD) and irradiated at GANIL with Pb ions of 110 MeV up to a maximum fluence of 4 × 10¹³ cm⁻². As shown in a previous work these irradiation conditions, characterized by a predominant electronic slowing-down (S_e = 19.3 keV nm⁻¹), lead to damage creation and formation of etchable tracks in Si₃N₄. In the present study we investigated other radiation-induced effects like out of plane swelling and refractive index decrease. From profilometry, step heights as large as 50 nm were measured for samples irradiated at the highest fluences (>10¹³ cm⁻²). From optical spectroscopy, the minimum reflectivity of the target is shifted towards the high wavelengths at increasing fluences. These results evidence a concomitant decrease of density and refractive index in irradiated Si₃N₄. Additional measurements, performed by ellipsometry, are in full agreement with this interpretation.     

Heavy ion beam induced phenomena in polytetrafluoroethylene

This paper describes the results on thermal and chemical analysis of polytetrafluoroethylene (PTFE) film stack after high-energy heavy ion beam irradiation under atmospheric fields at room temperature. After high-energy C⁶⁺ ion beam irradiation, the PTFE film stack was separated one by one, and then the various measurements such as differential scanning calorimetric (DSC) analysis and solid-state ¹⁹F magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy were performed to get information of the chemical reaction and structural change at the localized positions. By ion beam irradiation for PTFE at room temperature, it is suggested that the abnormal phenomena due to the change of morphology could be observed by DSC analysis. In the solid-state ¹⁹F-MAS-NMR spectroscopy of ion irradiated PTFE film including Bragg peak region, several new signals were observed besides the intense peak of -CF₂- at −124 ppm. The detected new signals in ion irradiated PTFE should be due to the changed chemical structures. The signals, which are assigned, to the tertiary carbon group with branching site (Y-type crosslinking site), perfluoro-propylene site and chain end methyl site were directly detected, though it was under the oxidation condition. Thus, although it was under the oxidation condition, the branching or crosslinking reaction was taken place with the chain scission in the matrix. Moreover, the branched chain length would become short, compared with EB-crosslinked PTFE. Hence, it could be suggested that the irradiation of heavy ion beam induced large amounts of intermediate species, compared with EB or γ-ray irradiation, and then, those would be reacted with each other in the localized area. Especially, in region of the Bragg peak, the ion beam induced more large amounts of intermediate species than in the other region.     

Microstructural evolution of the China Low Activation Martensitic (CLAM) steel irradiated by H and He ion beams

China Low Activation Martensitic (CLAM) steel was irradiated at room temperature with different doses of He⁺ and H⁺ ion beams. TEM indicated that the microstructure of unirradiated CLAM steel consisted of laths, grain boundaries, dislocations and carbides. Electron diffraction patterns revealed that the microstructure of carbides at grain boundaries was primarily dominated by M₂₃C₆ carbide. Vacancy clusters were induced into the matrix after irradiation. TEM-EDX of carbides and matrices of unirradiated and post-irradiated samples were performed to investigate the composition of carbides and the effect of irradiation on the composition of carbides. Carbides from unirradiated and irradiated specimens at grain boundaries were found to be enriched with Cr. For irradiated specimens, concentrations of Cr increased as the irradiation dose was increased. Cr enrichment could lead to precipitation of additional phase.     

Scintillation light produced by low-energy beams of highly-charged ions

Measurements have been performed of scintillation light intensities emitted from various inorganic scintillators irradiated with low-energy beams of highly-charged ions from an electron beam ion source (EBIS) and an electron cyclotron resonance ion source (ECRIS). Beams of xenon ions Xe^q+ with various charge states between q = 2 and q = 18 have been used at energies between 5 and 17.5 keV per charge generated by the ECRIS. The intensity of the beam was typically varied between 1 and 100 nA. Beams of highly charged residual gas ions have been produced by the EBIS at 4.5 keV per charge and with low intensities down to 100 pA. The scintillator materials used are flat screens of P46 YAG and P43 phosphor. In all cases, scintillation light emitted from the screen surface was detected by a CCD camera. The scintillation light intensity has been found to depend linearly on the kinetic ion energy per time deposited into the scintillator, while up to q = 18 no significant contribution from the ions’ potential energy was found. We discuss the results on the background of a possible use as beam diagnostics, e.g. for the new HITRAP facility at GSI, Germany.     

Investigation by slow positron beam of defects in CLAM steel induced by helium and hydrogen implantation

Hydrogen and helium ion beams delivering different doses are used in the ion implantation, at room temperature, of China Low Activation Martensitic (CLAM) steel and the induced defects studied by Doppler broadening of gamma-rays generated in positron annihilation. Defect profiles are analysed in terms of conventional S and W parameters, measures of relative contributions of low and high-momentum electrons in the annihilation peak, as functions of incident positron energies E up to 30 keV. The behaviours of the S-E, W-E and S-W plots under different implantation doses indicate clearly that the induced defect size has obvious variation with depth, taking values that interpolate between surface and bulk values, and depend mainly on helium ion fluences. The S-W plot indicates that two types of defects have formed after ion implantation.