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.     

The new Cyclone 18/9 beam transport line at the CNA (Sevilla) for high energy PIXE applications

The Cyclone 18/9 cyclotron system at the Centro Nacional de Aceleradores (Sevilla, Spain) is commonly used to create short life radioisotopes for PET applications. Besides, an external beam transport line has been recently installed in one of the target ports with two major purposes: to study the effects of 18 MeV protons irradiation on the behaviour of electronic devices for space applications and to complement the analysis of materials using our 3 MV tandem accelerator with the PIXE measurements at high energy.In this work, the main elements of our beamline will be briefly described and the first PIXE application will be presented. The usual PIXE, in the analysis of archaeological metallic objects, using around 3 MeV protons requires having a shiny area. Our purpose is to obtain a deeper determination of the bulk composition bombarding with 18 MeV protons through the corroded samples surfaces, without polishing the ancient object. To check this methodology high energy PIXE has been performed on two fibulae of the Later Bronze Age and First Iron Age, coming from the area around Sevilla.     

International Atomic Energy Agency intercomparison of ion beam analysis software

Ion beam analysis (IBA) includes a group of techniques for the determination of elemental concentration depth profiles of thin film materials. Often the final results rely on simulations, fits and calculations, made by dedicated codes written for specific techniques. Here we evaluate numerical codes dedicated to the analysis of Rutherford backscattering spectrometry, non-Rutherford elastic backscattering spectrometry, elastic recoil detection analysis and non-resonant nuclear reaction analysis data. Several software packages have been presented and made available to the community. New codes regularly appear, and old codes continue to be used and occasionally updated and expanded. However, those codes have to date not been validated, or even compared to each other. Consequently, IBA practitioners use codes whose validity, correctness and accuracy have never been validated beyond the authors’ efforts. In this work, we present the results of an IBA software intercomparison exercise, where seven different packages participated. These were DEPTH, GISA, DataFurnace (NDF), RBX, RUMP, SIMNRA (all analytical codes) and MCERD (a Monte Carlo code). In a first step, a series of simulations were defined, testing different capabilities of the codes, for fixed conditions. In a second step, a set of real experimental data were analysed. The main conclusion is that the codes perform well within the limits of their design, and that the largest differences in the results obtained are due to differences in the fundamental databases used (stopping power and scattering cross section). In particular, spectra can be calculated including Rutherford cross sections with screening, energy resolution convolutions including energy straggling, and pileup effects, with agreement between the codes available at the 0.1% level. This same agreement is also available for the non-RBS techniques. This agreement is not limited to calculation of spectra from particular structures with predetermined parameters, but also extends to extracting information from real data. In particular, we have shown data from an Sb implanted sample where the Sb fluence was certified with an uncertainty of 0.6%. For this sample, and using SRIM03 stopping powers for 1.5 MeV ⁴He in Si, the codes were able to extract the Sb fluence with an average 0.18% deviation from the certified value and a 0.11% agreement between the codes. Thus IBA is a suitable technique for accurate analysis where traceability is critical. These results confirm that available IBA software packages are, within their design limitations, consistent and reliable. The protocol established may be readily applied to validate future IBA software as well.     

A method for very low fluence implantations using Rutherford scattering

A simple method for extremely low fluence ion implantation is described. It is based on implanting ions which are Rutherford backscattered (RBS) from a thin gold layer into the desired target. This method enables ion implantations to be carried out, as are needed to realize quantum centers on the atomic scale to serve as qubits and other nano sized devices. The required implantation fluences are orders of magnitude below the commonly-used current integration capabilities; hence control on the implanted fluence is usually complicated. The described method enables control on the implanted fluence even when extremely low. The dependence of the energy and fluence of scattered ions on the angle and scattering target thickness is analyzed by using SRIM simulations. These are verified for the case of N scattering implantation by direct counting in a surface barrier detector and for the case of Xe by counting the tracks that scattered and implanted Xe ions leaved in HOPG as viewed by scanning probe microscopy.     

Micro-crystalline inclusions analysis by PIXE and RBS

A characteristic feature of the nuclear microprobe using a 3 MeV proton beam is the long range of particles (around 70 μm in light matrices). The PIXE method, with EDS analysis and using the multilayer approach for treating the X-ray spectrum allows the chemistry of an intra-crystalline inclusion to be measured, provided the inclusion roof and thickness at the impact point of the beam (Z and e, respectively) are known (the depth of the inclusion floor is Z + e). The parameter Z of an inclusion in a mineral can be measured with a precision of around 1 μm using a motorized microscope. However, this value may significantly depart from Z if the analyzed inclusion has a complex shape. The parameter e can hardly be measured optically. By using combined RBS and PIXE measurements, it is possible to obtain the geometrical information needed for quantitative elemental analysis. This paper will present measurements on synthetic samples to investigate the advantages of the technique, and also on natural solid and fluid inclusions in quartz. The influence of the geometrical parameters will be discussed with regard to the concentration determination by PIXE. In particular, accuracy of monazite micro-inclusion dating by coupled PIXE-RBS will be presented.     

Production and characterization of thin Li targets fabricated by ion implantation

Very high fluence implantation of ⁷Li⁺ ions was used to promote the formation of a thin and high density ⁷Li target in the surface region of Al samples. The implanted volume was characterized by particle induced gamma-ray emission, Rutherford backscattering spectrometry, X-ray photoelectron spectroscopy and nuclear reaction analysis, revealing that the implanted surface is a combination of Li₂CO₃, metallic lithium, LiOH and C, with almost no Al present. Radiation damage effects by proton beams were studied by observing the evolution of the ⁷Li(p, α)⁴He nuclear reaction yield with the accumulated charge, at different proton energies, revealing high stability of the produced Li target.     

Development of a novel reaction chamber for ion beam analysis of large samples

A novel vacuum chamber for ion beam analysis of large-size industrial samples - whose analysis are not feasible in conventional ion beam analysis reaction chambers - has been designed, fabricated and successfully tested. Using the newly developed chamber, both PIXE and RBS analyses could be carried out at the same time and on the same point of the samples. Ion beam analysis using this novel chamber lacks the disadvantages of external beam analysis and benefits the advantages of in-vacuum analysis. This has been achieved by designing a tiny open port in the wall of the reaction chamber to be sealed with a small flat area of sample body where its analysis is of interest. As a case study, two samples of gas turbine blades, a corroded one at highly corrosive environment and a refurbished one after application of certain coatings are analysed using the novel chamber. Experimental results confirm the performance and capability of the reaction chamber.     

Critical issues in the formation of quantum computer test structures by ion implantation

The formation of quantum computer test structures in silicon by ion implantation enables the characterization of spin readout mechanisms with ensembles of dopant atoms and the development of single atom devices. We briefly review recent results in the characterization of spin dependent transport and single ion doping and then discuss the diffusion and segregation behaviour of phosphorus, antimony and bismuth ions from low fluence, low energy implantations as characterized through depth profiling by secondary ion mass spectrometry (SIMS). Both phosphorus and bismuth are found to segregate to the SiO₂/Si interface during activation anneals, while antimony diffusion is found to be minimal. An effect of the ion charge state on the range of antimony ions, ¹²¹Sb²⁵⁺, in SiO₂/Si is also discussed.     

Characterisation of an enamelled metallic object found in Guerrero Negro (Baja California) by PIXE and RBS techniques

The coast of Guerrero Negro (Baja California) has been known for a long time by archaeologists for its shipwrecks. Archaeologists are recovering objects that come from sunken Spanish galleons in the colonial period, and reach the American coast in the frontier of the USA with Mexico.An enamelled metallic object was found next to the beach in Guerrero Negro. We have analysed the piece with proton induced X-ray emission (PIXE) and Rutherford backscattering (RBS) in an attempt to establish whether the object could come from one of the colonial shipwrecks and to valuate its cleaning process.Scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) have been also performed in three samples taken from the object in order to observe the heterogeneity of the material.The materials found revealed the presence of typical lead-glass enamels from with pigments such as cuprite (red), or lead-tin yellow used in colonial times. The metallic part consisted of brass. As for the cleaning process, the average efficiency considered as the weight% of chlorine removed, was of 83.4% for brass and 100% for enamels.     

Compositional analysis of atom beam co-sputtered metal-silica nanocomposites by Rutherford backscattering spectrometry

Metal:SiO₂ (metal: Ni, Ag, Au) nanocomposite films of different compositions have been prepared by atom beam co-sputtering. The estimation of composition of films is done theoretically using sputtering yield and relative area of metal and SiO₂. The sputtering yields used for estimation of composition are calculated by three theoretical methods: Monte Carlo simulations (SRIM code), Sigmund’s theory and Sigmund’s theory modified by Anderson and Bay. Rutherford backscattering spectrometry (RBS) is also used to analyze the composition of the nanocomposite films. RUMP simulations of RBS data are performed. The errors in theoretical calculations and RBS results are estimated. It is found that SRIM is more appropriate for Ni:SiO₂ nanocomposite films, while modified Sigmund’s theory based method is better for Ag:SiO₂ and Au:SiO₂ nanocomposite films. The possible sources of errors in theoretical methods with respect to experimental (RBS) results are also discussed.     

Analysis of C, N and O in aerosol collected on an organic backing using internal blank measurements and variable beam size

A method with low MDL (minimum detection limit) was developed for analysis of carbon (C), nitrogen (N) and oxygen (O) in aerosol samples collected on an organic backing. An accelerator-produced beam of protons interacting with the sample and the detection of elastically scattered protons (PESA; particle elastic scattering analysis) and emitted X-rays (PIXE; particle-induced X-ray emission) were the basic components of the setup. The method is based on measurement of internal blank concentrations, i.e. measurement of the blank concentration outside the aerosol deposit in each sample, and the use of two sizes of the beam in order to improve the MDL of the analysis. Large beam size covering the entire aerosol deposit was used to obtain quantitative analysis with PIXE. Small beam was used to obtain relative elemental concentrations with PESA and PIXE, which were transformed to absolute values by the aid of large-beam analysis. The small-size-beam served two purposes: to make internal blank measurements feasible and to improve the signal ratio of aerosol-deposit to backing. Compared with the traditional way of analysis, using a beam that is larger than the deposit and specially prepared blank samples, the new method reduced the MDL of C, N and O by a factor of 130, 70 and 90, respectively. The new method was applied to aerosol samples collected in the upper troposphere and the lowermost stratosphere from the CARIBIC platform. As far as the authors know, these measurements are the first quantitative determinations of C, N and O in the aerosol of this part of the atmosphere. The results show that these elements together with sulfur are major components of the aerosol.     

A Time of Flight-Energy spectrometer for stopping power measurements in Heavy Ion-ERD analysis at iThemba LABS

The quantitative analysis of thin layers using Heavy Ion-Elastic Recoil Detection (HI-ERD) can be reliably performed if the stopping powers of the probing ions and recoils in a given target matrix are known accurately. Unfortunately for many projectile/target combinations experimental data is limited and where available, deviations of up to 50% between experiment and theory have been reported. This presentation describes the assembly of a Time of Flight-Energy (ToF-E) detector system developed for HI-ERD analysis and adapted for stopping power measurements at iThemba LABS. First results from energy loss measurements of 0.1-0.5 MeV/nucleon ²⁸Si and ⁸⁴Kr ions in ZrO₂ are presented and compared with predictions of the widely used SRIM2003 (Stopping Range of Ions in Matter).     

Ion beam studies of InAs/GaAs self assembled quantum dots

Self assembled InAs/GaAs quantum dots (QD’s) emit in the wavelength range (1.3-1.55 μm) revealing an enormous potential to become the active elements of low threshold lasers and light emitting diodes for communication systems. However, the luminescence is dramatically quenched at room temperature (and even below) due to the defects in the GaAs matrix which open non-radiative recombination paths.In this study we combine Rutherford backscattering/channelling (RBS-C) and high resolution X-ray diffraction (HRXRD) to study the structural properties of the InAs/GaAs structures. The InAs/GaAs QD heterostructures were grown by atmospheric pressure metal organic vapour phase epitaxy. Channelling measurements reveal a good crystalline quality along the main axial directions with minimum yields in the range of 4-6% through the entire capping layer. An increase on the dechannelling rate was observed in the region where the InAs quantum dots were buried. The channelling results also give evidence for the presence of defects preferentially oriented. Detailed angular scans in a structure with a 28 nm cap allowed the study of the In orientation with respect to the GaAs matrix and a perfect alignment was found along the growth direction. The strain in the dots shifts the angular curves along the tilt directions.     

Silver surface enrichment controlled by simultaneous RBS for reliable PIXE analysis of ancient coins

Evidence of silver surface enrichment of ancient silver-copper coins has been pointed out in the past years. Surface enrichment can be fortuitous or intentional. In this paper, we have investigated the cleaning procedures usually performed after excavation or in museums. We have shown that chemicals or commercial products routinely used dissolve preferentially the copper phase and consequently contribute to the silver surface enrichment. As a result, surface analyses such as PIXE or XRF can be strongly affected by this effect. By using simultaneously RBS and PIXE, it is possible to check through the silver surface enrichment and then select the reliable measurements, characteristic of the bulk composition. Results on coins recently discovered and mechanically or chemically cleaned are presented.     

Modification of poly(ether ether ketone) by ion irradiation

Poly(ether ether ketone) was irradiated with 3.0 MeV Si²⁺, 3.25 MeV Cu²⁺ and 4.8 MeV Ag²⁺ ions to the fluences from 10¹² to 10¹⁴ cm⁻² and the effects of irradiation were studied using ERDA, RBS and FTIR methods. The irradiation leads to release of hydrogen from the PEEK surface layer modified by the ion beam. The release is mild for low ion fluences but it becomes more pronounced at the ion fluences above 10¹³ cm⁻². At highest ion fluences the hydrogen concentration falls to 20-35% of its initial value. In contrast to hydrogen no significant oxygen release was observed. The kinetic of the hydrogen release is similar for the three ion species. FTIR measurement shows deep structural changes of the polymer structure resulting from the ion irradiation.     

Online time-differential perturbed angular correlation study with an O beam - Residence sites of oxygen atoms in highly oriented pyrolytic graphite

The online time-differential perturbed angular correlation (TDPAC) method was applied to a study of the physical states of a probe ¹⁹F, the β⁻ decay product of ¹⁹O (t_1/2 = 26.9 s), implanted in highly oriented pyrolytic graphite. The observed magnitude of the electric field gradient at the probe nucleus, ∣V_zz∣ = 2.91(17) × 10²² V m⁻², suggests that the incident ¹⁹O atoms are stabilized at an interlayer position with point group C_3v. Exhibiting observed TDPAC spectra having a clear sample-to-detector configuration dependence, we demonstrate the applicability of the present online method with a short-lived radioactive ¹⁹O beam.     

MeV-ion beam analysis of the interface between filtered cathodic arc-deposited a-carbon and single crystalline silicon

Amorphous carbon (a-C) films were deposited on Si(1 0 0) wafers by a filtered cathodic vacuum arc (FCVA) plasma source. A negative electrical bias was applied to the silicon substrate in order to control the incident energy of carbon ions. Effects of the electrical bias on the a-C/Si interface characteristics were investigated by using standard Rutherford backscattering spectrometry (RBS) in the channeling mode with 2.1-MeV He²⁺ ions. The shape of the Si surface peaks of the RBS/channeling spectra reflects the degree of interface disorder due to atomic displacement from the bulk position of the Si crystal. Details of the analysis method developed are described. It was found that the width of the a-C/Si interface increases linearly with the substrate bias voltage but not the thickness of the a-C film.     

Quantification of sodium in ancient Roman glasses with ion beam analysis

Concentrations of light elements (Na, Al, Si) in glass have been profiled by comparing the PIGE yields as a function of beam energy to those of a glass standard in combination with PIXE measurements which are used to determine the specific energy loss of protons in the unknown glasses. The technique has been tested on a known sample and applied to a few Roman natron glasses giving results compatible with the morphology of the archaeological samples, as deduced from microscopy. The results have suggested some considerations on the systematic use of the PIGE technique in the determination of bulk sodium concentration in ancient materials.     

Ion beam synthesis and doping of photonic nanostructures

Optically-active silica nanowires are produced by metal-induced growth on silicon substrates using ion-implantation, with two different strategies employed for their fabrication. The first is based on Er implantation of nanowires produced by a thin-film Pd catalyst layer, and the second employing implanted Er as both the catalyst and dopant. The luminescence properties of the resulting Er-doped silica nanowires are reported and compared with similarly implanted fused silica samples. Comparison shows that the luminescence lifetime of Er is increased by incorporation within the nanowires due to a reduction in the density of available optical states in these structures. Additional details of the synthesis, structure and properties of these functionalised nanowires are also presented.     

Elemental analysis of light constituents in thin plastic films

Experiments with 1-3 MeV ⁴He beams and 2.2-3.2 MeV proton beams have been performed in order to develop a precise and highly sensitive method for the detection and analysis of light elements in threat or drug materials using simultaneously the RBS and ERDA techniques. Commercially available plastic films have been used as samples. The 1 MeV ⁴He beam has been found to be inadequate owing to the rapid destruction of the targets. Best results have been obtained using proton beams with energies higher than 3 MeV. For 3.2 MeV proton beams, ERDA has been used for the analysis of the hydrogen constituent.