Dr. René Heller

Head Ion Beam Analysis
Phone: +49 351 260 3617

Publications - Ion Beam Analysis

Here you are finding current publications that have emerged from user experiments and collaborations with our group.

Year >= 2017
"Online First" included
OU: Ion Beam Analysis (FWIZ-A)

Influence of precursor thin-film quality on the structural properties of large-area MoS2 films grown by sulfurization of MoO3 on c-sapphire

Spanková, M.; Sojková, M.; Dobrocka, E.; Hutár, P.; Bodík, M.; Munnik, F.; Hulman, M.; Chromik, S.

In recent years, molybdenum disulfide (MoS2) has been investigated due to its unique electronic, optical, and mechanical properties with a variety of applications. Sulfurization of pre-deposited MoO3 layers is one of the methods of the preparation of large-area MoS2 thin films. The MoO3 layers have been grown on c-sapphire substrates, using two different techniques (rf sputtering, pulsed laser deposition). The films were subsequently annealed in vapors of sulfur at high temperatures what converted them to MoS2 films. The quality of MoS2 is strongly influenced by the properties of the precursor MoO3 layers. The pre-deposited MoO3, as well as the sulfurized MoS2, have been characterized by several techniques including Raman, Rutherford backscattering spectroscopy, atomic force microscopy, scanning electron microscopy, and X-ray diffraction. Here we compare two types of MoS2 films prepared from different MoO3 layers to determine the most suitable MoO3 layer properties providing good quality MoS2 films for future applications.

Keywords: Molybdenum disulfide; Sulfurization; Sputtering; Pulsed laser deposition; Structural properties

Nanoparticle emission by electronic sputtering of CaF2 single crystals

Alencar, I.; Hatori, M.; Marmitt, G. G.; Trombini, H.; Grande, P. L.; Dias, J. F.; Papaléo, R. M.; Mücklich, A.; Assmann, W.; Toulemonde, M.; Trautmann, C.

Material sputtered from CaF2 single crystals by 180 MeV Au ions impinging at different incidence angles were collected on high-purity amorphous C-coated Cu grids and Si100 wafer catcher surfaces over a broad angular range. These catcher surfaces were characterized complementary by transmission electron microscopy, atomic force microscopy and medium energy ion scattering, revealing the presence of a distribution of partially buried CaF2 nanoparticles in conjunction to a thin layer of deposited CaF2 material. Particle size distributions do not follow simple power laws and depend on the angles of ion incidence and particle detection. It is shown that the particle ejection is directly related to the jet-like component of sputtering, previously observed in ionic crystals, contributing significantly to the total yield. This contribution enhances as the impinging ions approach grazing incidence. Possible scenarios for the emission of particles are discussed in light of these observations.

Keywords: Atomic force microscopyCatcher technique; Nanoparticle; Medium energy ion scattering; Electronic sputtering; Swift heavy ions; Transmission electron microscopy

High carrier mobility epitaxially aligned PtSe2 films grown by one-zone selenization

Sojkova, M.; Dobročka, E.; Hutár, P.; Tašková, V.; Pribusová-Slušná, L.; Stoklas, R.; Píš, I.; Bondino, F.; Munnik, F.; Hulman, M.

Few-layer PtSe2 films are promising candidates for applications in high-speed electronics, spintronics and photodetectors. Reproducible fabrication of large-area highly crystalline films is, however, still a challenge. Here, we report the fabrication of epitaxially aligned PtSe2 films using one-zone selenization of pre-sputtered platinum layers. We have studied the influence of growth conditions onstructural and electrical properties of the films prepared from Pt layers with different initial thickness. The best results were obtained for the PtSe2 layers grown at elevated temperatures (600 °C). The films exhibit signatures for a long-range in-plane ordering resembling an epitaxial growth. The charge carrier mobility determined by Hall-effect measurements is up to 24 cm²/V.s

Keywords: PtSe2; epitaxial films; Laue oscillations; Raman spectroscopy

Unusual scandium enrichments of the Tørdal pegmatites, south Norway. Part I: Garnet as Sc exploration pathfinder

Steffenssen, G.; Müller, A.; Munnik, F.; Friis, H.; Erambert, M.; Kristoffersen, M.; Rosing-Schow, N.

The granitic pegmatites of the Tørdal area in southern Norway have been known for their Sc enrichment for about 100 years. Scandium is a compatible element in garnet. In this study, 32 garnet samples from 16 pegmatite localities across the Tørdal pegmatite field were investigated to determine the Sc distribution within garnets (crystal scale), within pegmatite bodies (pegmatite scale) and across the Tørdal pegmatite field (regional scale). In the Tørdal pegmatites, Sc content in garnet is representative for the Sc bulk composition of pegmatites, defining garnet as a reliable pathfinder mineral for the exploration of Sc mineralization in pegmatite fields. Garnets with highest Sc concentrations of up to 2197 µg/g have a spessartine component ranging from 50 to 60 mol.%. Since most garnets crystallized during the early stage of pegmatite formation (wall zone stage) Sc decreases in the remaining pegmatite melt, as documented by generally decreasing Sc from core to rim of crystals and by the occurrence of late-stage garnets (albite zone stage) with low Sc. Thus, with progressing crystallization Sc decreases in the melt. The regional Sc distribution in the Tørdal pegmatite field revealed that the Skardsfjell-Heftetjern-Høydalen pegmatites have highest Sc enrichments to sub-economic levels, with an average bulk Sc content of 53 µg/g and an average Sc content in garnet of about 1900 µg/g in the Heftetjern 2 pegmatite.
The assumed resources of the Skardsfjell-Heftetjern-Høydalen area are about 125,000 t ore grading c. 50 µg/g Sc resulting in a total of 625 t Sc, which is too small to have economic potential. However, the strong Sc enrichment of the Tørdal pegmatites is unusual for granitic pegmatites, making them a specific Sc deposit type. The amphibolitic host rocks of the Tørdal pegmatites are identified as the source rocks of Sc. The host rocks, which are part of the Nissedal Outlier supracrustals, are enriched in Sc (mean 34 µg/g) compared to average crustal compositions (mean 14 µg/g). Scandium of amphiboles was preferentially released at the onset of partial melting of the amphibolites. Thus, the Sc content in the pegmatite is strongly dependent on the degree of partial melting.

Keywords: scandium; pegmatite; garnet; Sveconorwegian orogeny; Tørdal

Silicon Surface Passivation by ALD-Ga₂O₃: Thermal vs. Plasma-Enhanced Atomic Layer Deposition

Hiller, D.; Julin, J. A.; Chnani, A.; Strehle, S.

Silicon surface passivation by gallium oxide (Ga2O3) thin films deposited by thermal- and plasma-enhanced atomic layer deposition (ALD) over a broad temperature range from 75 °C to 350 °C is investigated. In addition, the role of oxidant (O3 or O-plasma) pulse lengths insufficient for saturated ALD-growth is studied. The material properties are analyzed including the quantification of the incorporated hydrogen. We find that oxidant dose pulses insufficient for saturation provide for both ALD methods generally better surface passivation. Furthermore, different Si surface pretreatments are compared (HF-last, chemically grown oxide, and thermal tunnel oxide). In contrast to previous reports, the annealing time to activate the surface passivation is found to be significantly shorter. The best surface saturation current densities (JOs) or surface recombination velocities (Seff) are 6 and 9 fA/cm² or 0.6 and 1.5 cm/s for n- and p-type Si, respectively. We correlate the surface passivation with the negative fixed charge density (Qfix; field-effect passivation) and the interface defect density (Dit; chemical passivation). It turns out that a high Qfix is present, irrespective of the utilized ALD-method, deposition temperature, or postannealing, whereas low Dit is only achieved fo rplasma-enhanced ALD at low temperatures. A critical H-density of∼10¹⁶ cm−2 is identified as a necessary but not sufficient condition for excellent surface passivation. Finally, contact resistivities are measured to investigate the possibility of using ALD-Ga2O3 as passivating contact material. In order to understand the current-voltage measurements, the energetic positions of the band edges and the Fermi level are determined by ultraviolet photoelectron spectroscopy and Kelvin probe.

Keywords: Atomic layer deposition (ALD); gallium oxide(Ga2O3); hydrogen; silicon surface passivation

Lithium Diffusion in Ion-Beam Sputter-Deposited Lithium-Silicon Layers

Strauss, F.; Hüger, E.; Julin, J. A.; Munnik, F.; Schmidt, H.

Lithium-silicon compounds are used as active material in negative electrodes of Li-ion batteries. The knowledge of Li diffusion in these materials is of importance for an optimization of charging/discharging rates and achievable maximum specific capacity as well as for an understanding of the basic lithiation mechanism. We carried out Li tracer self-diffusion experiments on ion-beam sputter-deposited LixSi(O) thin films for x ~ 0.25 and x ~ 4.5 using LixSi/6LixSi hetero-structures in combination with secondary ion mass spectrometry in line scan like mode. Measurements with elastic recoil detection analysis revealed the presence of a considerable amount of oxygen in the films. The diffusivities follow the Arrhenius law in the temperature range between 300 and 500 °C with an activation energy of 0.8 – 0.9 eV. The film containing a higher amount of Li shows faster diffusion by one order of magnitude. The Li diffusivities in the investigated Li-rich materials are several orders of magnitude higher than in Li-poor LixSi films (x = 0.02 to 0.06) as given in literature because of a lower activation energy. This indicates the presence of a direct interstitial-like mechanism. Oxygen present in samples with the same Li concentration of x = 0.06 also enhances diffusion but does not lead to a reduction in the activation energy.

The role of gas impurities on the optical properties of sputtered Ti(Al)N coatings

Bohovičová, J.; Meško, M.; Méndez, Á.; Julin, J. A.; Munnik, F.; Hübner, R.; Grenzer, J.; Čaplovič, Ľ.; Krause, M.

In this study, we investigated the role of impurities, such as H, C, and O on the optical properties of the Ti(Al)N coatings. For comparison, coatings were prepared by direct-current magnetron sputtering (DC-MS) and high-power impulse magnetron sputtering (HiPIMS) at the same average power. The elemental composition of the thin films was measured by elastic recoil detection analysis. Regardless of the deposition technique used, no significant difference in H and C concentrations were found. The analysis showed, that HiPIMS coatings contain less O impurities than the corresponding DC-MS films, despite the lower deposition rate. The reduced residual O content in HiPIMS coatings can be explained by the cleaning effect of the bombarding ions. Moreover, densification effects presumably suppress post-deposition oxidation. Given the reduced O content, HiPIMS films showed higher optical reflectance for the entire measured spectral range.

  • Lecture (Conference)
    The 15th International Symposium on Sputtering and Plasma Processes, ISSP 2019, 11.-14.06.2019, Kanazawa, Japan
  • Poster
    The 15th International Symposium on Sputtering and Plasma Processes, ISSP 2019, 11.-14.06.2019, Kanazawa, Japan
  • Contribution to proceedings
    The 15th International Symposium on Sputtering and Plasma Processes, ISSP 2019, 11.-14.06.2019, Kanazawa, Japan

Modern Ion Beam Techniques for Elemental Analysis of Surfaces and Interfaces at the nm Scale

Heller, R.

The general trend in technology and science to create, process and analyze small structures on the nm scale leads to new challenges in modern ion beam analysis (IBA). This is accompanied by higher demands on the lateral resolution as well as on high precision determination of elemental compositions on an atomic depth scale.

Thinner layer structures are closely related to an increased sensitivity on external impacts. Even the transport of a sample to the place of analysis under ambient conditions can lead to unwanted (chemical) modifications at the surface. Furthermore, in technological developments not only the state of a system after processing but the process itself may be of particular interest. “Online” IBA under process conditions is thus highly desired.

Classical IBA methods like RBS (Rutherford Backscattering Spectrometry), ERD (Elastic Recoil Detection Analysis), PIXE (Particle Induced X-Ray Emission) or PIGE (Particle Induced Gamma Emission), either applied as broad beam or as a micro probe, can therefore quickly reach their limits.

In the present contribution, we give an overview on recent and ongoing developments of new IBA techniques and approaches at the HZDR Ion Beam Center (IBC) addressing the above-mentioned difficulties. These developments include in particular

  • the implementation of IBA in a helium ion microscope enabling elemental mapping on the nm scale,
  • the unification of different IBA techniques in complex experimental chambers including in-situ capabilities,
  • a new setup for in-operando, online and quantitative analysis of solid-liquid interfaces with sub mono-layer sensitivity,
  • A new low-energy ion laboratory equipped with a Medium Energy Ion Scattering (MEIS) chamber for quantitative elemental depth profiling on the nm scale.

We will give an overview on these techniques and their capabilities. Since the IBC is an international user facility all presented techniques are available for external users experiments.

Keywords: Ion beam analysis; elemental composition; imaging; materials analysis; nano scale; backscattering

  • Poster
    18th European Conference on Applications of Surface and Interface Analysis, 15.-20.09.2019, Dresden, Deutschland

Characterization of Goethe’s prisms by external ion beam

Munnik, F.; Mäder, M.; Heller, R.; Schreiber, A.; Müller, O.

Johann Wolfgang von Goethe is known the world over as a renowned writer. However, he was also involved in scientific studies and has written several scientific books, of which he considered the “Theory of colours” (“Farbenlehre”, 1400 pages published in 1810) his most important work overall. In this work, he characterises colours as arising from the interplay between light and dark. This is in contrast to Newton’s analytical treatment of colour from one century earlier, which is based on the observation that white light can be separated into colours with a prism, that Goethe opposed. Over the centuries, Goethe’s theory was discredited and Newton’s theory prevailed. However, Goethe performed systematic and accurate optical measurements.
For these experiments, he and his partner J. Ritter, who discovered UV-light, used water prisms and glass prisms ordered from a glassmaker in Jena. The aim of current research is to reconstruct these optical experiments and the observed spectra [1]. For this, detailed knowledge of the composition of the glass prisms is important. This knowledge is, for example, also important to evaluate how innovative his prisms were.
Therefore, eleven prisms from Goethe’s estate or from contemporary sources belonging to the Klassik Stiftung Weimar have been analysed at the external beam setup of the Ion Beam Center at the HZDR. A 4 MeV proton beam has been used to acquire PIXE, PIGE and RBS spectra, sometimes on several areas. Care had to be taken to minimise damage by using short measurement times and measuring on inconspicuous areas because the glass quickly showed dark spots under irradiation. The PIXE and PIGE spectra have been used for quantitative analysis in an iterative procedure and the RBS spectra have only been evaluated quantitatively. The results of this analysis and the interpretation are presented in this work.

  • Lecture (Conference)
    16th International Conference on Particle Induced X-ray Emission, 24.-29.03.2019, Caldas da Rainha, Portugal

High energy ion beams as a powerful tool for the surface analysis of the elemental composition of almost any sample

Munnik, F.; Heller, R.

High energy ion beams as a powerful tool for the surface analysis of the elemental composition of almost any sample.

Keywords: Ion Beam Analysis

  • Lecture (others)
    Vortrag am Helmholtz-Zentrum für Umweltforschung GmbH - UFZ, 17.12.2019, Leipzig, Deutschland

Impact of Hydrogen-Rich Silicon Nitride Material Properties on Light-Induced Lifetime Degradation in Multicrystalline Silicon

Bredemeier, D.; Walter, D. C.; Heller, R.; Schmidt, J.

The root cause of “Light and Elevated Temperature Induced Degradation” (LeTID) of the carrier lifetime in multicrystalline silicon (mc-Si) wafers is investigated by depositing hydrogen-rich silicon nitride (SiN x :H) films of different compositions on boron-doped mc-Si wafers. The extent of LeTID observed in mc-Si after rapid thermal annealing (RTA) shows a positive correlation with the amount of hydrogen introduced from the SiN x :H layers into the bulk. The concentration of in-diffused hydrogen is quantified via measuring the resistivity change due to the formation of boron–hydrogen pairs in boron-doped float-zone silicon wafers processed in parallel to the mc-Si wafers. The measurements clearly show that the in-diffusion of hydrogen into the silicon bulk during RTA depends on both the atomic density of the SiN x :H film as well as the film thickness. Importantly, the impact of SiN x :H film properties on LeTID shows the same qualitative dependence as the hydrogen content in the silicon bulk, providing evidence that hydrogen is involved in the LeTID defect activation process.

Keywords: carrier lifetime; hydrogen; LeTID defects; light-induced lifetime degradation; silicon nitride; ulticrystalline silicon

High energy ion beams as a powerful tool for the analysis of the elemental composition of thin layers

Munnik, F.

Keywords: Ion Beam Analysis

  • Lecture (others)
    Kolloquium am Ferdinand-Braun-Institut, Berlin, 29.11.2019, Berlin, Germany

Microstructural evolution and thermal stability of AlCr(Si)N hard coatings revealed by in-situ high-temperature high-energy grazing incidence transmission X-ray diffraction

Jäger, N.; Meindlhumer, M.; Spor, S.; Hruby, H.; Julin, J.; Stark, A.; Nahif, F.; Keckes, J.; Mitterer, C.; Daniel, R.

An extensive understanding about the microstructural evolution and thermal stability of the metastable AlCr(Si)N coating system is of considerable importance for applications facing high temperatures, but it is also a challenging task since several superimposed processes simultaneously occur at elevated temperatures. In this work, three AlCr(Si)N coatings with 0 at.%, 2.5 at.% and 5 at.% Si were investigated by in-situ high-temperature high-energy grazing incidence transmission X-ray diffraction (HT-HE-GIT-XRD) and complementary differential scanning calorimetry and thermogravimetric analysis measurements combined with conventional ex-situ X-ray diffraction. The results revealed (i) a change in the microstructure from columnar to a fine-grained nano-composite, (ii) a reduced decomposition rate of CrN to Cr₂N, also shifted to higher onset temperatures from ∼ 1000 ℃ to above 1100 ℃ and (iii) an increase of lattice defects and micro strains resulting in a significant increase of compressive residual strain with increasing Si content. While the Si-containing coatings in the as-deposited state show a lower hardness of 28 GPa compared to AlCrN with 32 GPa, vacuum annealing at 1100℃ led to an increase in hardness to 29 GPa for the coatings containing Si and a decrease in hardness to 26 GPa for AlCrN. Furthermore, the in-situ HT-HE-GIT-XRD method allowed for simultaneously accessing temperature-dependent variations of the coating microstructure (defect density, grain size), residual strain state and phase stability up to 1100℃. Finally, the results established a deeper understanding about the relationships between the elemental composition of the materials, the resulting microstructure including crystallographic phases and residual strain state, and the coating properties from room temperature up to 1100℃.

Keywords: AlCrSiN; nano-composite; cathodic arc; thermal stability

Thermo-physical properties of coatings in the Ti(B,N) system grown by chemical vapor deposition

Kainz, C.; Schalk, N.; Tkadletz, M.; Saringer, C.; Winkler, M.; Stark, A.; Schell, N.; Julin, J.; Czettl, C.

Hard protective coatings are commonly subjected to temperatures exceeding 1000 °C, which has significant influence on their thermo-physical properties and the associated performance in application. Within the present work, temperature dependent physical properties of coatings within the Ti(B,N) system grown by chemical vapor deposition were correlated with their chemical composition. High-energy X-ray diffraction experiments in inert atmosphere proved that TiN, TiB₂ and ternary TiBxNy coatings with varying B contents are thermally stable up to 1000 °C. First order lattice strains of TiN and TiBxNy coatings diminish during heating, whereas TiB₂ exhibits compressive strain enhancement up to the deposition temperature. Nanocrystalline TiB₂ exhibits more pronounced grain growth during annealing compared to coarse grained columnar TiN. Within the investigated coatings, the mean thermal expansion coefficient decreases as the B content increases. The same trend was observed for the thermal conductivity, which correlates with the grain size of the coatings.

Keywords: Chemical vapor deposition; X-ray diffraction; Ti(B,N); thermal conductivity; strain

High temperature plasma immersion ion implantation using hollow cathode discharges in small diameter metal tubes

Ueda, M.; Silva, C.; de Souza, G. B.; Pichon, L.; Reuther, H.

High temperature nitrogen plasma immersion ion implantation (HT-NPIII) method was used to treat the internal walls of small diameter metal tubes made of SS304 and of Ti6-Al4-V (TAV). Using a lid in one side of the tubes was essential to reach high temperatures of 700-900 °C, necessary for high thermal diffusion of nitrogen in Ti alloy samples placed inside the metal tubes for monitoring the HT-NPIII process. The used metal tubes also reached such high temperatures. New phases of TiN and Ti2N were successfully attained in the TAV samples with the treated layer thickness of more than 1.3 μm for all the tested cases. For tubes made of SS304, HT-NPIII treatments resulted in redeposition of FeN thick layers with high hardness on the surfaces of the internal walls of the tubes and on the monitoring samples. Obtaining such HT-NPIII conditions in these small metallic tubes was possible by achieving high plasma density through hollow cathode discharges inside those tubes. These results were compared to the ones obtained on the nitrogen implantation treatments of TAV samples in moderate to high temperatures carried out previously in the laboratory which indicated the superior performance of the presently reported method of surface modification.

Round Robin: Composition And Thickness of Nitride and Oxide Thin Films Grown by Atomic Layer Deposition

Julin, J.; Sajavaara, T.

A round robin characterization of the elemental composition and thickness of Al₂O₃ and TiN thin films using IBA methods was organized. The samples were grown by atomic layer deposition (ALD) on 200 mm Si wafers. The Al₂O₃ films with different thicknesses (10–100 nm) were deposited using Al(CH₃)₃ and water as precursors at low temperatures, known to produce films with high impurity concentrations and non-stoichiometric O/Al ratio. The TiN films, sandwiched between thinner ALD-Al₂O₃ films, were grown using TiCl₄ and NH₃ precursors. The samples were chosen to represent a typical thin film analysis problem with real-world applications.

The participating institutes were mainly using heavy ion elastic recoil detection analysis (HI-ERDA) as a single measurement technique capable of providing all the requested information. Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA) were employed as multi-technique complementary analysis (so called Total-IBA) or to give partial results. In addition, X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS) were employed as complementary techniques.

The main goal of this study was not to promote the HI-ERDA technique but to identify the possible weaknesses and limitations of different analysis techniques and approaches, and thereafter improve the accuracy and reliability of the results given by the ion beam analysis community. A special emphasis was put on transparency of the results obtained – all the raw measurement data are publicly available for e.g. comparison and educational use via open data portal.

  • Lecture (Conference)
    IBA2019 - 24th International conference on Ion Beam Analysis, 13.-18.10.2019, Antibes, France

Experimental and computational studies of the influence of grain boundaries and temperature on the radiation-induced damage and hydrogen behavior in tungsten

Panizo-Laiz, M.; Díaz-Rodríguez, P.; Rivera, A.; Valles, G.; Martín-Bragado, I.; Perlado, J. M.; Munnik, F.; González-Arrabal, R.

We study the influence of grain boundaries on radiation-induced vacancies, as well as, on the hydrogen (H) behavior in tungsten (W) samples with different grain sizes in the temperature range from 300 K to 573 K, both experimentally and by computer simulations. For this purpose, coarse-grained and nanostructured W samples were sequentially irradiated with carbon (C) and H ions at energies of 665 keV and 170 keV, respectively. A first set of the implanted samples was annealed at 473 K and a second set at 573 K. Object kinetic Monte Carlo simulations were performed to account for experimental outcomes. Results show that the number of vacancies for nanostructured W is always larger than for single crystal W samples in the whole studied temperature range and that the number of vacancies is only reduced in samples with a large density of grain boundaries and at temperatures high enough to activate the vacancy motion (around 573 K). Results also indicate that the migration of H along vacancy free grain boundaries is more effective than along the bulk, and that the retained H is trapped in vacancies located within the grains. These results are used to explain the experimental outcomes.

Thermal expansion of magnetron sputtered TiCxN1-x coatings studied by high-temperature X-ray diffraction

Saringer, C.; Kickinger, C.; Munnik, F.; Mitterer, C.; Schalk, N.; Tkadletz, M.

The coefficient of thermal expansion (CTE) of TiCxN1-x can be adjusted by changing the value x between 0 (i.e. pure TiN) and 1 (pure TiC), which makes this material exceptionally useful as base layer to adapt the mismatch between the CTEs of substrate and coating. However, no comprehensive data on the CTE of sputtered TiCxN1-x has been reported up to now. Thus, in this work eleven coatings with compositions ranging from pure TiN to pure TiC were deposited using non-reactive magnetron sputtering. The elemental and phase composition were obtained by elastic recoil detection analysis and Raman spectroscopy, respectively. Powders of the coating material were analyzed using high-temperature X-ray diffraction between room temperature and up to 1000 °C to determine the temperature dependent lattice parameters. Subsequently, these lattice parameters were fitted using second order polynomials with coefficients linearly depending on the carbon content. Thus, a formula for the CTE of TiCxN1-x valid between 25 and 1000 °C was deduced which showed that at room temperature TiN has the highest CTE of 8.12 × 10-6 K-1. The CTE gradually decreases with increasing carbon content to 7.55 × 10-6 K-1 for pure TiC. While the value for TiC only shows a small increase with temperature, the CTE of TiN increases strongly up to 11.1 × 10-6 K-1 at 1000 °C. The presented formula for the temperature dependent CTE of sputtered TiCxN1-x coatings allows to calculate the required composition for TiCxN1-x base layers, in order to tune their thermal expansion for the use in complex multilayered coatings.

Keywords: Thermal expansion; Titanium carbonitride; High-temperature X-ray diffraction; Physical vapor deposition; Hard coatings

Revealing the Formation Dynamics of the Electric Double Layer by means of in-situ Rutherford Backscattering Spectrometry

Baghban Khojasteh Mohammadi, N.; Apelt, S.; Bergmann, U.; Facsko, S.; Heller, R.

We report on a new versatile experimental setup for in-situ Rutherford backscattering spectrometry at solid- liquid interfaces that enables investigations of electric double layers directly, in-situ and in a quantitative manner. A liquid cell equipped with a three electrode arrangement is mounted in front of the beam line and a thin Si3N4 window down to a thickness of 150 nm separates the vacuum of the detector chamber from the electrolyte in the cell. Since the contribution of the window to the measured spectra is minimized, a large variety of elements at the solid-liquid interface with sensitivities far below one mono layer can be monitored. The attachment of Ba onto the Si3N4 surface as a function of contact time and pH value of the electrolyte solution was chosen as example system. From our measurement we can not only read the evolution of the double layer but also derive limits for the point of zero charge for the Si3N4 surface. Our findings of 5.7 ≤ pH_PZC ≤ 6.2 are in good accordance with values found in the literature obtained by other techniques. Despite the measurements shown in this work, the presented setup allows for a large variety of in-situ investigations at solid-liquid interfaces such as tracing electro-chemical reactions, monitoring segregation, adsorption and dissolution and corrosion processes.

Keywords: Electric Double Layer; in-situ RBS; solid-liquid interface


Upgrade of the ERDA setup at the HZDR 6 MV tandem accelerator

Julin, J.; Aniol, R.; Munnik, F.; Heller, R.

During 2019 the elastic recoil detection (ERD) beamline attached to the 6 MV tandem accelerator at the Helmholtz-Zentrum Dresden-Rossendorf (HZDR) has been modernized completely. Since many of the vacuum and electrical components of the previous setup had been showing signs of aging or failing, the decision was made to replace these and rebuild the setup. Additionally, during 2018 the construction of a new time-of-flight spectrometer for ERD was also completed, and it was seen that the ERD setup as a whole would benefit from a combination of a new chamber, mechanical supports and a control system.

The new setup incorporates the previously used Z-separating Bragg ionization chamber (BIC), which is typically used with 43 MeV 35Cl beam. It is connected to a port on the chamber giving 30 degree scattering angle. The time-of-flight branch is attached to the other side of the chamber at a 40 degree scattering angle. Various beams up to an energy of 20 MeV for 35Cl or 30 MeV for 63Cu can be used, or even higher if hydrogen depth profiling is not necessary. The detector branches can be operated independently of each other, minimizing downtime due to breakdowns of detectors or maintenance. This is exceedingly important since the ion beam center (IBC) is a user facility and the beam time for the 6 MV accelerator is allocated based on proposals and scheduled long in advance to the actual measurement.

This presentation will give an overview of the new ERD setup, including specifics on the design of the new chamber, control and vacuum systems, detectors and data acquisition as well as some experimental data, performance figures and experiences gained during the construction of the setup.

Keywords: IBA; ERDA

  • Poster
    ECAART13 - 13th European Conference on Accelerators in Applied Research and Technology, 05.-10.05.2019, Split, Croatia

Oxyhydride Nature of Rare-Earth-Based Photochromic Thin Films

Cornelius, S.; Colombi, G.; Nafezarefi, F.; Schreuders, H.; Heller, R.; Munnik, F.; Dam, B.

Thin films of rare-earth (RE)−oxygen−hydrogen compounds prepared by reactive magnetron sputtering show a unique color-neutral photochromic effect at ambient conditions. While their optical properties have been studied extensively, the understanding of the relationship between photochromism, chemical composition, and structure is limited. Here we establish a ternary RE−O−H composition-phase diagram based on chemical composition analysis by a combination of Rutherford backscattering and elastic recoil detection. The photochromic films are identified as oxyhydrides with a wide composition range described by the formula REOxH3−2x where 0.5 ≤ x ≤ 1.5. We propose an anion-disordered structure model based on the face-centered cubic unit cell where the O2− and H− anions occupy tetrahedral and octahedral interstices. The optical band gap varies continuously with the anion ratio, demonstrating the potential of band gap tuning for reversible optical switching applications.

Automated Target Model Determination from MEIS Spectra Utilizing an Evolutionary Algorithm

Heller, R.

To extract chemical compositions and layer thicknesses of layered samples from back scattering spectra experimentalists usually have to take the following approach: Simulation of a theoretical spectrum for an initial target configuration and comparison to the measured data followed by the successive re-adjustment of the target model iteratively, until simulation result and experimental spectrum fit together. For multi-layer samples this procedure can get rather time consuming, especially when a series of similar samples with varying layer thickness and/or stoichiometry has to be analyzed.

Although modern IBA spectrum simulation software like SimNRA[1] or WINDF[2] have become quite powerful and handy tools, the analysis of the spectra consumes still a significant fraction of an IBA scientist’s working time. SimNRA offers therefore the opportunity to partially fit layer thicknesses and/or elemental ratios for a given layer within a certain region of a spectrum. WINDF goes a step further and implements an automated spectrum fitting based on a simulated annealing algorithm. However, it takes the user quite some time to set up the boundary conditions and fit parameters until the actual fit procedure can be initiated. Furthermore, the outcome of the fit procedure in some cases contains non-physical artifacts and requires multiple re-adjustments of the boundary conditions / fit parameters.

An approach that came up in the past (and is still being applied for particular tasks) is the application of artificial neural networks (ANN) to derive sample information from IBA spectra [3,4]. In a nut-shell this method basically trains an algorithm how the shape of a spectrum is correlated to the sample’s target model without introducing any physics (numerical calculations) to the code. Therefore, the ANN is fed with many (typically several 10 thousand) training spectra with a known target model. After this training procedure (which can be quite time consuming) the ANN spits out the target model of any unknown spectra in almost zero time. However, the spectra must be of the same type as all the training spectra since an ANN can only interpolate and not extrapolate, which is for sure one of the mayor drawbacks of this approach. However, all these efforts are justified in some special scenarios e.g. if a large series of spectra of similar type has to be evaluated.

In this contribution, we present a new approach of automated IBA spectra fitting applying an evolutionary algorithm (EA). We show that EA is well suited and robust for complete and fast IBA spectrum fitting with minimum input of boundary conditions. The benefits of this algorithm and the particular differences to simulated annealing and ANN are pointed out. Special emphasis is put on the adoption of this algorithm to the analysis of MEIS spectra, since there is a couple of differences to classical IBA methods that needs to be considered.

Based on this algorithm a platform independent software package has been developed that comprises a clean and easy-to-use graphical user interface. We will introduce this software in a basic overview.

Keywords: Ion beam analysis; evaluation software; evolutionary algorithm

  • Invited lecture (Conferences)
    9th International Workshop on High-Resolution Depth Profiling (HRDP-9), 25.-29.06.2018, Uppsala, Schweden

Structural and magnetic properties of epitaxial Mn–Ge films grown on Ir/Cr buffered MgO(0 0 1)

Dash, S.; Schleicher, B.; Schwabe, S.; Reichel, L.; Heller, R.; Fähler, S.; Neu, V.; Patra, A. K.

Epitaxial Mn–Ge films with varying composition have been prepared on Ir/Cr buffered MgO(0 0 1) substrates using DC magnetron sputtering. The effect of composition on phase formation, texture and magnetic properties of Mn–Ge films has been investigated. These films grow epitaxially on Ir/Cr buffered MgO(0 0 1) with a tetragonal D022 type structure. From the pole figure analysis the epitaxial relationship is determined to be: D022 Mn–Ge [1 0 0] (0 0 1)||Ir [1 0 0] (0 0 1)||Cr [1 1 0] (0 0 1)||MgO [1 0 0] (0 0 1). Mn–Ge films close to stoichiometric composition (Mn77.5Ge22.5) exhibit perpendicular magnetic anisotropy with crystallographic c-axis being the easy axis of magnetization. The room temperature measured values of coercivity µ 0 H c, saturation magnetization M S and anisotropy field µ 0 H A for Mn77.5Ge22.5 are 2.86 T, 90 kA m−1 and 9.6 T, respectively. Mn–Ge films with low and high Mn concentration possess high coercivity but extremely low magnetization and that can be ascribed to the presence of secondary phases of non-magnetic/low magnetic nature, possible interdiffusion, and especially partial substitution of excess Mn atoms into the Ge site.

Keywords: epitaxial growth; magnetron sputtering; ion beam analysis; Mn; Ge; magnetic propoerties

Interaction of hydrogen with hafnium dioxide grown on silicon dioxide by the atomic layer deposition technique

Kolkovsky, V.; Scholz, S.; Kolkovsky, V.; Schmidt, J. U.; Heller, R.

The electrical and structural properties of thin hafnia films grown by the atomic layer deposition technique were investigated before and after different annealing steps as well as after a dc H plasma treatment. By using the nuclear reaction analysis, the authors demonstrated that high concentrations of hydrogen (about 1–2 at. %) could be observed even in as-grown hafnia layers. An additional hydrogenation of the samples with atomic H led to a significant shift of the flatband voltage. This shift could be explained by the introduction of positively charged H-related defects which were found to be stable at room temperature. By comparing the experimental findings with the theory and the data from muon spin spectroscopy, they tentatively ascribed these defects to interstitial H in HfO2.

Keywords: hafnium oxide; ion beam analysis; nuclear reaction analysis; hydrogen depth profiling

Zr and Mo thin films with reduced residual impurities’ uptake under high vacuum conditions at room temperature

Meško, M.; Bohovičová, J.; Munnik, F.; Grenzer, J.; Hübner, R.; Čaplovič, Ľ.; Čaplovičová, M.; Vančo, Ľ.; Vretenár, V.; Krause, M.

In recent years, transition (refractory) metals such molybdenum (Mo) and zirconium (Zr) have been studied as infrared (IR) reflector in solar absorber applications. The sputter process parameters are very important for depositing a high quality thin film achieving the necessary low emittance. IR reflectance of the metal film is influenced by the film microstructure, presence of residual impurities and surface roughness. The main objective of the present study is to prepare Mo and Zr metallic thin films with improved optical properties by high power impulse magnetron sputtering at room temperature under high vacuum conditions. In comparison to the Mo and Zr thin films deposited by direct current magnetron at the same average power, thin films deposited by HiPIMS exhibits dense microstructure without voids, grown preferentially along c-axis, have smooth surface and are free of residual contaminants. Compared to the dcMS films we observed an element specific reduction of impurities measured by elastic recoil detection analysis (ERDA) by a factor 4/8 for N, 3/4 for H and 9/14 for O for Mo/Zr thin films respectively. The compositional effects are correlated with differences in the film morphology microstructure revealed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis.

  • Poster
    16th International Conference on Plasma Surface Engineering, 16.-21.09.2018, Garmisch-Partenkirchen, Deutschland

Physical and electrical properties of nitrogen-doped hydrogenated amorphous carbon films

Fenker, M.; Julin, J.; Petrikowski, K.; Richter, A.

Nitrogen-doped hydrogenated amorphous carbon films (a-C:H:N) have been prepared by a plasma-activated chemical vapor deposition technique (PACVD) by using a plasma beam source (PBS). The properties of the a-C:H:N films were changed by varying the total pressure, the substrate temperature (100 °C, 300 °C) and nitrogen partial pressure p(N₂) by adding nitrogen to the precursor acetylene (C₂H₂). For the investigations, a-C:H:N films have been deposited onto glass slides and doped silicon wafers. The deposition rate decreased with increasing nitrogen content in the N₂/C₂H₂ gas mixture and with decreasing total pressure. The elemental composition of two sample series (300 °C) has been analyzed with Elastic Recoil Detection Analysis (ERDA). The highest N content and N/C ratio was estimated to be 16 at.% and 0.25 at the highest p(N₂), respectively. Microhardness measurements showed that the hardness decreased with increasing p(N₂). Electrical resistance of the a-C:H:N films was measured by 4-point probe. Electrically conductive coatings have been obtained by nitrogen-doped a-C:H films at higher substrate temperature (300 °C). The electrical resistance of the a-C:H:N films also decreases with ecreasing total pressure, with the lowest value being about 1 Ohm cm. The film density was determined by means of X-ray reflectometry (XRR).

Keywords: PACVD; DLC; carbon films; carbon nitride films; XRR; electrical conductivity

Structural Properties of Al–O Monolayers in SiO₂ on Silicon and the Maximization of their Negative Fixed Charge Density

Hiller, D.; Göttlicher, J.; Steininger, R.; Huthwelker, T.; Julin, J.; Munnik, F.; Wahl, M.; Bock, W.; Schoenaers, B.; Stesmans, A.; König, D.

Al₂O₃ on Si is known to form an ultra-thin interfacial SiO₂ during deposition and subsequent annealing, which creates a negative fixed charge (Qfᵢₓ) that enables field-effect passivation and low surface recombination velocities in Si solar cells. Various concepts were suggested to explain the origin of this negative Qfᵢₓ. In this study we investigate Al–O monolayers (MLs) from atomic layer deposition (ALD) sandwiched between deliberately grown/deposited SiO₂ films. We show that the Al-atoms have an ultra-low diffusion coefficient (~4×10⁻¹⁸ cm²/s at 1000°C), are deposited at a constant rate of ~5×10¹⁴ Al-atoms/cm²/cycle from the first ALD-cycle on, and are tetrahedral O-coordinated, since the adjacent SiO₂ imprints its tetrahedral near-order and bond length into the Al–O MLs. By variation of the tunnel-SiO₂ thickness and the number of Al–O MLs, we demonstrate that the tetrahedral coordination alone is not sufficient for the formation of Qfᵢₓ but that a SiO₂ /Al₂O₃ interface within a tunneling distance from the substrate must be present. The Al-induced acceptor states at these interfaces have energy levels slightly below the Si valence band edge and require charging by electrons from either the Si substrate or from Si/SiO₂ dangling bonds to create the negative Qfᵢₓ. Hence, tunneling imposes limitations for the SiO₂ and Al₂O₃ layer thicknesses. In addition, Coulomb repulsion between the charged acceptor states results in an optimum number of Al–O MLs, i.e., separation of both interfaces. We achieve maximum negative Qfᵢₓ of ~5×10¹² cm⁻² (comparable to thick ALD-Al₂O₃ on Si) with ~1.7 nm tunnel-SiO₂ and just 7 ALD-Al₂O₃ cycles (~8 Å) after optimized annealing at 850°C for 30 s. The findings are discussed in the context of a passivating, hole-selective tunnel contact for high-efficiency Si solar cells.

Keywords: atomic layer deposition; aluminum oxide; silicon oxide; negative fixed charge; silicon surface passivation; hole-selective contact

Evolution of structure and residual stress of a fcc/hex-AlCrN multi-layered system upon thermal loading revealed by cross-sectional X-ray nano-diffraction

Jäger, N.; Klima, S.; Hruby, H.; Julin, J.; Keckes, J. F.; Mitterer, C.; Daniel, R.

Understanding the influence of process conditions and coating architecture on the microstructure and residual stress state of multi-layered coatings is essential for the development of novel thermally and mechanically stable coatings and requires advanced depth resolving characterization techniques. In this work, an arc-evaporated multi-layered coating, consisting of alternating Al₇₀Cr₃₀N and Al₉₀Cr₁₀N sublayers with an individual layer thickness between 120 nm and 380 nm, was investigated. The as-deposited state of the multi-layered coating and the state after vacuum annealing at 1000 ◦C for 30 min was studied along its cross-section by synchrotron X-ray nano-diraction using a beam with a diameter of 50 nm. The results revealed sublayers with alternating cubic and hexagonal phase, causing repeated interruption of the grain growth at the interfaces. The in-plane residual stress depth distribution across the coating thickness could be tuned in a wide range between pronounced compressive and slight tensile stress by combining the effects of the coating architecture and the modulated incident particle energy controlled by the substrate bias voltage ranging from −30 V to −250 V . This resulted in an oscillatory stress profile fluctuating between −2 GPa and −4.5 GPa or pronounced stress gradients with values between −4 GPa and 0.5 GPa. Finally, the decomposition routes of the metastable cubic Al₇₀Cr₃₀N phase could be controlled by the Al₉₀Cr₁₀N sublayers which acted as nucleation sites and governed the texture of the decomposition products as Cr₂N. The results demonstrate that the cross sectional combinatorial approach, relying on a sophisticated multi-layer architecture combining various materials synthesized under tailored conditions, allowed for resolving structural variations and stress proles in the individual layers within the complex architecture and pioneers the path for knowledge-based development of multi-layered coatings with predefined microstructure and a dedicated stress design.

Keywords: Coating; Multilayers; Microstructure design; Residual stress; X-ray nano-diffraction

A versatile ion beam spectrometer for studies of ion interaction with 2D materials

Schwestka, J.; Melinc, D.; Heller, R.; Niggas, A.; Leonhartsberger, L.; Winter, H.; Facsko, S.; Aumayr, F.; Wilhelm, R. A.

We present an ultra-high vacuum setup for ion spectroscopy of freestanding two-dimensional solid targets. An ion beam of different ion species (e.g. Xe with charge states from 1 to 44 and Ar with charge states from 1 to 18) and kinetic energies ranging from a few 10 eV to 400 keV is produced in an electron beam ion source. Ions are detected after their transmission through the 2D target with a position sensitive microchannel plate detector allowing the determination of the ions exit charge state as well as the scattering angle with a resolution of approx. 0.04◦. Further, the spectrometer is mounted on a swiveling frame covering a scattering angle of ±8° with respect to the incoming beam direction. By utilizing a beam chopper we measure the time-of-flight of the projectiles and determine the energy loss when passing a 2D target with an energy uncertainty of about 2%. Additional detectors are mounted close to the target to observe emitted secondary particles and are read-out in coincidence with the position and time information of the ion detector. A signal in these detectors can also be used as a start trigger for time-of-flight measurements, which then yield an energy resolution of 1% and an approx. 1000-fold larger duty cycle. First results on the interaction of slow Xe30+ ions with a freestanding single layer of graphene obtained with the new setup are compared to recently published data where charge exchange and energy were measured by means of an electrostatic analyzer.

Keywords: slow highly charged ions; 2D materials; ion spectrometer; single layer graphene


Recent experiments on plasma immersion ion implantation (and deposition) using discharges inside metal tubes

Ueda, M.; Silva, C.; Marcondes, A. R.; Reuther, H.; de Souza, G. B.

Plasma immersion ion implantation (PIII) of nitrogen inside metallic tubes of different diameters and configurations were attempted recently. PIII tests in practical size metallic tubes of SS304, ranging from 1.1 to 16 cm∅ and length of 20 cm, were carried out as a continued effort in our lab, to explore PIII inside tubes. Tubes in laying down positions and configurations including metallic lid in one side or both sides open were used, as well as, plane sample support placed 10 cm far from the tube mouth and without bias, taking advantage of plasma flowing out the tube. In particular, nitrogen and argon PIIIs were tested for tube inner wall sputtering and deposition studies, running the PIII system in the last configuration of sample support detached from the tube. During the nitrogen ion implantation runs in other cases, it was found that the final temperature of the tubes and the plasma turn-on voltages were both inversely proportional to the dimensions of the tubes, except for the smallest tube tested. High voltage glow and hollow cathode discharges were produced inside the tubes, either alternately, during the pulse or independently, depending on the tube geometry and pulser used (LIITS, a current controlled source or RUP-4, a voltage controlled one). In the case of smallest diameter of 1.1 cm∅, a suspended tube of SS304 was tested using lower power pulser (RUP-4), at its near maximum capability of 1.2 kW. In this case also, very bright plasmas were formed, mainly inside the tube and resulted in high temperature there (~700 °C). Nitrogen uptake was superior for higher temperature PIII treatments (>700 °C), combining ion implantation and thermal diffusion, which allowed the formation of TiN and Ti2N on the Ti alloy samples inside tubes with diameters ≤4 cm. In this paper, detailed discussion of results of above cited PIII tests with diversified tubes and configurations are presented, together with the analysis of the corresponding treated surfaces of the samples inside, outside and on the support detached from the tube.

Keywords: Plasma immersion ion implantation; Sputtering and deposition inside metallic tubes; TiN and Ti2N in high temperature PIII; Tubes with different dimensions and configurations

Comparison of mechanical properties and composition of magnetron sputter and plasma enhanced atomic layer deposition aluminum nitride films

Sippola, P.; Pyymaki Perros, A.; Ylivaara, O. M. E.; Ronkainen, H.; Julin, J.; Liu, X.; Sajavaara, T.; Etula, J.; Lipsanen, H.; Puurunen, R. L.

Comparative study of mechanical properties and elemental and structural composition was made for aluminum nitride thin films deposited with reactive magnetron sputtering and plasma enhanced atomic layer deposition (PEALD). The sputtered films were deposited on Si (100), Mo (110) and Al (111) oriented substrates to study the effect of substrate texture to the film properties. For the PEALD trimethylaluminum-ammonia (TMA/NH3) films, the effects of process parameters such as temperature, bias voltage, and plasma gas (NH3 vs. N2/H2) on the AlN properties were studied. All the AlN films had a nominal thickness of 100 nm. Time-of-flight elastic recoil detection analysis (ToF-ERDA) showed the sputtered films to have lower impurity concentration with an Al/N ratio of 0.95, while the Al/N ratio for the PEALD films was 0.81-0.90. The mass densities were ~3.10 g/cm3 and ~2.70 g/cm3 for sputtered and PEALD AlN, respectively. Only the sputtered films were crystalline, as determined by x-ray diffraction (XRD). Nanoindentation experiments showed the elastic modulus and hardness to be 250 GPa and 22 GPa, respectively, for sputtered AlN on (110) substrate, whereas with PEALD AlN, values of 180 GPa and 19 GPa, respectively, were obtained. The sputtered films were under tensile residual stress (61 to 421 MPa) whereas PEALD films had a residual stress ranging from tensile to compressive (846 to -47 MPa) and high plasma bias resulted in compressive films. The adhesion of both films was good on Si, although sputtered films showed more inconsistent critical load behaviour. Also, the substrate underneath the sputtered AlN did not withstand as high wear forces as with the PEALD AlN. The coefficient of friction was determined to be ~0.2 for both AlN types and their wear characteristics were almost identical.

Analysis of the Electric-Double-Layer formation by in-situ Rutherford Backscattering Spectrometry

Baghban Khojasteh Mohammadi, N.; Heller, R.; Bergmann, U.; Apelt, S.

A setup for in-situ Rutherford Backscattering Spectrometry (RBS) has been installed at the 2 MV Van-de-Graaff accelerator at the Ion Beam Center (IBC) of the Helmholtz-Zentrum Dresden-Rossendorf (HZDR). Online analysis of solid-liquid interfaces as well as electro-chemistry experiments are conducted by this technique. A Si3N4 window separates the liquid from the vacuum in the RBS chamber. A He+ beam (E = 1.7 MeV) is utilized for the RBS measurements. RBS as well as Particle Induced X-Ray Emission Spectroscopy (PIXE) spectra are recorded simultaneously to increase the sensitivity for trace elements. The technique was employed for direct measurements of the Electric-Double-Layer (EDL) formation on Si3N4. Investigations of the EDL formation at solid-liquid interfaces are of great significance due to the various valuable applications such as super-capacitors that can be utilized to provide a backup power supply or applied in various other fields [1-3]. In our preliminary experiments, the specific adsorption of Barium ions from a 1mM BaCl2 solution with various pH values was observed in a direct and quantitative manner. Sensitivity of the technique reaches the ppm range and areal densities can be measured down to 0.1 atomic monolayer.
[1]Kötz et al., (2002). The 12th International Seminar on Double Layer Capacitors and Similar Energy Storage Devices, Dec, USA.
[2]Faggioli et al., (1999). J. Power Sources, 84(2): 261.
[3]Simon et al., (2008). Nature materials, 7(11): 845.

Keywords: in-situ RBS; Electric-Double-Layer

  • Lecture (Conference)
    Workshop on Ion and Particle Beams (Ionenstrahl Workshop), 24.-25.04.2018, Darmstadt, Germany

Evolutionary Algorithm for Automated IBA Spectra Fitting

Heller, R.

In order to extract chemical compositions and layer thicknesses of layered samples from IBA spectra (RBS, ERD, etc.) experimentalists usually have to take the following approach: Simulation of a theoretical spectrum for an initial target configuration and comparison to the measured data followed by the successive adjustment of the target model iteratively until simulation result and experimental spectrum fit together. For multi-layer samples this procedure can get rather time consuming, especially when a series of similar samples with varying layer thickness and/or stoichiometry has to be analyzed.
Although modern IBA spectrum simulation software like SimNRA[1] or WINDF[2] have become quite powerful and handy tools, the analysis of IBA spectra consumes still a significant fraction of an IBA scientist’s working time. SimNRA offers therefore the opportunity to partially fit layer thicknesses and/or elemental ratios for a given layer within a certain region of a spectrum. WINDF goes a step further and has an automated spectrum fitting included which is based on a simulated annealing algorithm. However, it takes the user quite some time to set up the boundary conditions and fit parameters until the actual fit procedure can be initiated. Furthermore, the outcome of the fit procedure in some cases requires multiple re-adjustments of the boundary conditions / fit parameters.
In the present contribution, we present a new approach for automated IBA spectra fitting by implementing an evolutionary algorithm. We will show that this powerful algorithm is very well suited and robust for complete and fast IBA spectrum fitting with minimum input of boundary conditions. Furthermore, the benefits of this algorithm over other ones and the particular differences to simulated annealing are pointed out.
Based on this algorithm a software package has been developed, written in the programming language Java that is platform independent and comprises a clean and easy-to-use graphical user interface. We will introduce this software in a basic overview.

Keywords: IBA Fit routine evolutionary algorithm

  • Poster
    Ion Beam Analysis, 08.-13.10.2017, Shanghai, China

Chemical analysis of solid-liquid interfaces by in-situ Rutherford Backscattering Spectrometry

Baghban Khojasteh Mohammadi, N.; Heller, R.

Solid-liquid interfaces are important locations for various reactions to occur in biological, chemical and physical processes [1-3]. Recently, an experimental setup for in-situ Rutherford Backscattering Spectrometry (RBS) technique has been installed at the 2 MV Van-de-Graaff accelerator at Ion Beam Center (IBC) of the Helmholtz-Zentrum Dresden-Rossendorf to analyze solid-liquid interfaces as well as to conduct electro-chemistry experiments. The focus of the project is to perform experiments in different fields utilizing this quantitative, non-destructive and standard free ion beam analysis technique for solid-liquid interfaces. A Si3N4 window separates the liquid in the cell from vacuum in the beam line. He+ beam with E = 1.7 MeV is employed to bombard the samples. For feasibility tests, the cell was filled with air, Ne, He, Xe and DIH2O respectively and RBS and Particle Induced X-Ray Emission Spectroscopy (PIXE) spectra were recorded. To examine the efficiency of the technique, ion backscattering studies of the solid-liquid using 0.1M solutions of Cu(NO3) and AgNO3 have been performed and are compared to the literature [4].
[1] Kötz et al., Electrochimica acta. 31 (1986) 169.
[2] Morita et al., Radiation Physics and Chemistry. 49 (1997) 603.
[3] Hodnik et al., Accounts of chemical research. 49 (2016) 2015.
[4] Forster et al., Nuclear Instruments and Methods in Physics Research Section B. 28 (1987) 385.

Keywords: solid-liquid; interface analysis; in-situ RBS

  • Poster
    DPG Spring Meeting of the Condensed Matter Section (SKM), 11.-16.03.2018, Berlin, Deutschland

Nitrogen redistribution in annealed LaFeOxNy thin films investigated by FTIR spectroscopy and EELS mapping

Haye, E.; Pierron, V.; Barrat, S.; Capon, F.; Munnik, F.; Bruyère, S.

LaFeOxNy thin films have been deposited by magnetron sputtering in Ar/O2/N2 gas mixture at 800°C. Such oxynitride perovskites present an uncommon infrared vibration mode position at 2040cm-1, due to presence of nitrogen, which disappears with heating in air. The evolution of this vibration mode with temperature has been studied and permit to determine an activation energy of thermal degradation of LaFeOxNy. The quantification of nitrogen by Elastic Recoil Detection Analysis (ERDA) before and after heating exhibits the same nitrogen content, indicating a redistribution of nitrogen. Such nitrogen redistribution is observed by Electron Energy Loss Spectroscopy (EELS) mapping, showing migration of nitrogen into grain boundaries, in association with film oxidation.

Keywords: Oxynitride perovskite; Thermal stability; EELS mapping; FTIR

Enhancing Charge Carrier Lifetime in Metal Oxide Photoelectrodes through Mild Hydrogen Treatment

Jang, J.; Friedrich, D.; Müller, S.; Lamers, M.; Hempel, H.; Lardhi, S.; Cao, Z.; Harb, M.; Cavallo, L.; Heller, R.; Eichberger, R.; van de Krol, R.; Abdi, F. F.

Widespread application of solar water splitting for energy conversion is largely dependent on the progress in developing not only efficient but also cheap and scalable photoelectrodes. Metal oxides, which can be deposited with scalable techniques and are relatively cheap, are particularly interesting, but high efficiency is still hindered by the poor carrier transport properties (i.e., carrier mobility and lifetime). In this paper, a mild hydrogen treatment is introduced to bismuth vanadate (BiVO4), which is one of the most promising metal oxide photoelectrodes, as a method to overcome the carrier transport limitations. Time-resolved microwave and terahertz conductivity measurements reveal more than twofold enhancement of the carrier lifetime for the hydrogen-treated BiVO4, without significantly affecting the carrier mobility. This is in contrast to the case of tungsten-doped BiVO4, although hydrogen is also shown to be a donor type dopant in BiVO4. The enhancement in carrier lifetime is found to be caused by significant reduction of trap-assisted recombination, either via passivation of deep trap states or reduction of trap state density, which can be related to vanadium antisite on bismuth or vanadium interstitials according to density functional theory calculations. Overall, these findings provide further insights on the interplay between defect modulation and carrier transport in metal oxide photoelectrodes, which will benefit the development of low-cost, highly efficient solar energy conversion devices.

Hydrogen calibration of GD-spectrometer using Zr-1Nb alloy

Mikhaylov, A. A.; Priamushko, T. S.; Babikhina, M. N.; Kudiiarov, V. N.; Heller, R.; Laptev, R. S.; Lider, A. M.

To study the hydrogen distribution in Zr-1Nb alloy (E(cyrillic)110 alloy) GD-OES was applied in this work. Qualitative analysis needs the standard samples with hydrogen. However, the standard samples with high concentrations of hydrogen in the zirconium alloy which would meet the requirements of the shape, size are absent. In this work method of Zr + H calibration samples production was performed at the first time. Automated Complex Gas Reaction Controller was used for samples hydrogenation. To calculate the parameters of post-hydrogenation incubation of the samples in an inert gas atmosphere the diffusion equations were used. Absolute hydrogen concentrations in the samples were determined by melting in the inert gas atmosphere using RHEN602 analyzer (LECO Company). Hydrogen distribution was studied using nuclear reaction analysis (HZDR, Dresden, Germany). RF GD-OES was used for calibration. The depth of the craters was measured with the help of a Hommel-Etamic profilometer by Jenoptik, Germany. © 2017.

Keywords: Calibration; Glow discharge optical emission spectroscopy (GD-OES); Hydrogen; Standard samples; Zirconium alloy

Nanorattles with tailored electric field enhancement

Schnepf, M. J.; Mayer, M.; Kuttner, C.; Tebbe, M.; Wolf, D.; Dulle, M.; Altantzis, T.; Formanek, P.; Förster, S.; Bals, S.; König, T. A. F.; Fery, A.

Nanorattles are metallic core-shell particles with core and shell separated by a dielectric spacer. These nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions and commensurate variations in enhancement factor. We present a novel synthetic approach for the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy (STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic applications where a defined and robust unit cell is crucial.

LaFeOxNy perovskite thin films: Nitrogen location and its effect on morphological, optical and structural properties

Haye, E.; Bruyère, S.; André, E.; Boulet, P.; Barrat, S.; Capon, F.; Miska, P.; Migot, S.; Carteret, C.; Coustel, R.; Gendarme, C.; Munnik, F.

This paper reports on the first study of chemical, optical, and structural properties of lanthanum ferrite oxynitride thin films deposited by reactive magnetron sputtering. Thin films were deposited in a Ar/O2/N2 mixture as reactive plasma, from two elemental La and Fe targets, at room and high temperature (25 and 800°C). Films deposited at room temperature are amorphous and have been flash annealed to crystallize the perovskite. Oxynitride properties were investigated and compared to oxide films deposited in Ar/O2 gas mixture. All oxide and oxynitride films present an orthorhombic structure. However, nitrogen doping limited to 1-1.5% leads to lattice expansion (4%), bandgap narrowing, a lower electrical resistivity in range [25-350°C] , and modification of Infrared and Raman spectra. Electron Energy Loss Spectroscopy measurements clearly show the presence of two nitrogen sites with an “active” intra-granular nitrogen associated to an enhancement of the physical properties.

Keywords: Oxynitride perovskite; Thin film; LaFeO3; Nitrogen doping

Advanced Data Processing for Full-Field PIXE Imaging

Buchriegler, J.; Klingner, N.; Hanf, D.; Munnik, F.; Nowak, S. H.; Scharf, O.; Ziegenrücker, R.; Renno, A. D.; von Borany, J.

The combination of a pnCCD-based detector with a poly-capillary X-ray optics was installed and examined at HZDR [1]. The set-up is intended for PIXE imaging with protons (2-4 MeV) to survey large, polished geological samples with respect to their trace elemental composition. The X-ray optics is used to guide the emitted photons towards the pnCCD-chip divided into nearly 70000 pixels with dimensions of 48 × 48 µm². By applying a dedicated sub-pixel algorithm to recalculate the footprint of the photon’s electron cloud in the chip [2], this limitation can be bypassed and the resolution is then mainly determined by the capillary’s diameter of 20 µm.
Nevertheless, all images gathered with this kind of set-up from are superimposed by patterns of the X-ray optics. The optics’ capillaries are grouped in hexagonal bundles during the fabrication process and these bundles are grouped together again. This process results in a reduced efficiency in the regions where the bundles are joined making the hexagonal pattern visible. This influence can be removed by the technique of multi-frame super-resolution combining several short measurements with slightly shifted positions. The optics pattern is averaged out and in addition the shifting allows further increase of the lateral resolution. The total measurement time can be kept similar by dividing the single measurement time by the number of “shots” without reducing the sampling size.
This approach of multi-frame super-resolution in combination with a sub-pixel correction algorithm will be illustrated and shown on experimental data. Additionally, a flat-field correction attempt is shown to remove general imaging inhomogeneity. Descriptive image-sets will be presented to demonstrate the potential of such techniques for full-field PIXE imaging [3].
[1] D. Hanf, J. Buchriegler, A. D. Renno, S. Merchel, F. Munnik, R. Ziegenrücker, O. Scharf, S. H. Nowak, J. von Borany, NIM B 377, pp. 17-24 (2016).
[2] S. H. Nowak, A. Bjeoumikhov, J. von Borany, J. Buchriegler, F. Munnik, M. Petric, A. D. Renno, M. Radtke, U. Reinholz, O. Scharf, L. Strüder, R. Wedell, R. Ziegenrücker, X-ray Spectrometry 44 (3), pp. 135-140 (2015).
[3] J. Buchriegler, N. Klingner, D. Hanf, F. Munnik, S. H. Nowak, O. Scharf, R. Ziegenrücker, A. D. Renno, J. von Borany, submitted to Journal of Analytical Atomic Spectrometry (2017)

This work has been supported by BMBF (INTRA r3 033R070) and by Marie Curie Actions - Initial Training Network (ITN) as an Integrating Activity Supporting Postgraduate Research with Internships in Industry and Training Excellence (SPRITE) under EC contract no. 317169.

  • Poster
    23rd International Conference on Ion Beam Analysis IBA-2017, 08.-13.10.2017, Shanghai, China

Road to micron resolution with a color X-ray camera – polycapillary optics characterization

Nowak, S. H.; Petric, M.; Buchriegler, J.; Bjeoumikhov, A.; Bjeoumikhov, Z.; von Borany, J.; Munnik, F.; Radtke, M.; Renno, A. D.; Reinholz, U.; Scharf, O.; Tilgner, J.; Wedell, R.

In a color X-ray camera spatial resolution is achieved by means of a polycapillary optic conducting X-ray photons from small regions on a sample to distinct energy dispersive pixels on a CCD matrix. At present, the resolution limit of color X-ray camera systems can go down to several microns and is mainly restricted by pixel dimensions. The recent development of an efficient subpixel resolution algorithm allows a release from pixel size, limiting the resolution only to the quality of the optics. In this work polycapillary properties that influence the spatial resolution are systematized and assessed both theoretically and experimentally. It is demonstrated that with the current technological level reaching one micron resolution is challenging, but possible.

Keywords: color X-ray camera; polycapillary optics; lateral resolution

Time-of-Flight Telescope for ERDA at the HZDR

Julin, J.; Heller, R.

Elastic Recoil Detection Analysis (ERDA) is a near-surface heavy ion beam based elemental characterization technique, known especially for its suitability for light element analysis of thin films. The elemental composition of an unknown sample can be determined quantitatively in a single measurement, without resorting to the use of standards or information from additional measurements or models.

In the Ion Beam Center (IBC) of the Helmholtz-Zentrum Dresden-Rossendorf a Bragg Ionization Chamber (BIC) based ERDA setup has been operated successfully for many years. In the past there has also been a time-of-flight telescope installed in the same chamber. During 2017 this instrument will be upgraded with new detectors, bringing it up to date with latest experimental developments in the field.

The goal for the project is first and foremost to construct a user-friendly instrument, which can be operated reliably. Special emphasis will be put to the achievable depth resolution, without sacrificing performance in other areas. The instrument can be operated with a relatively broad energy range, with lower incident beam energy (< 10 MeV) enabling high depth resolution (2 nm) near the surface and higher energies, e.g. 20 MeV, enable excellent mass separation and better probing depth for thicker films.

In this contribution we will present the basic idea of the new setup and give some particular details on the design, expected performance and a realization time line.

  • Poster
    Workshop Ionenstrahlphysik, 13.-15.02.2017, Göttingen, Deutschland

P1608 - Ionenmikroskopievorrichtung

Klingner, N.; Heller, R.; Hlawacek, G.; Facsko, S.; von Borany, J.; Wilhelm, R. A.

Die Erfindung betrifft eine Ionenmikroskopievorrichtung mit einer Ionenquelle zum Erzeugen eines Ionenstrahls, einem Detektor, einer Spannungsquelle und einem Photonenpuls-Generator, wobei die Ionenmikroskopievorrichtung zum Bestrahlen eines Objekts mit dem Ionenstrahl unter Erzeugung von Wechselwirkungsteilchen ausgebildet ist, wobei die Ionenquelle eine Gasionisationskammer, eine in derselben angeordnete spitzenförmige Elektrode und eine Gegenelektrode aufweist, der Detektor zum Erfassen der Wechselwirkungsteilchen dient, die Spannungsquelle zum Anlegen einer elektrischen Spannung zwischen die Elektrode und die Gegenelektrode dient, und der Photonenpuls-Generator zum Erzeugen von in die Ionisationskammer gerichteten Photonenpulsen dient.

  • Patent
    DE102016112328 - Erteilung: 05.01.2017

Upgrade of the microprobe at Dresden-Rossendorf

Munnik, F.; Hanf, D.; Heller, R.

The nuclear microprobe that was in operation until 2104 at the Ion Beam Center of the Helmholtz-Zentrum Dresden-Rossendorf was installed in 1994 [1]. It has been in operation since then with only minor changes. This necessitated an upgrade to bring the setup up to current standards of technology and good working practice. This study presents the details of the upgrade and modernization process we have undertaken.
The major drawbacks of the old system were the poor resolution and low contrast and brightness of the optical microscope. However, a good optical image is essential to localise the areas of interest on, for example, large geological samples.
On the other hand, the main investigative tool is the focused beam of high-energy ions and the corresponding detectors. Any other system such as an optical microscope has to be designed around this equipment. A new custom-designed microscope has been installed for which the first light-collecting lens is mounted in the sample chamber at only a few centimetres from the sample. The light is then guided over large mirrors and focussed on a CCD camera outside the sample chamber. Also the illumination is fed in through the lenses instead of using a separate light source as in the old system. The lens system can also serve as a basis for a possible ionoluminescence detector.
Other improvements concern the beam deflection system, the control of the scanning system and the control and monitoring of all relevant parameters for the experiment. The control of the scanning system is done by custom-designed hardware to guarantee the real-time execution of the scanning without the need for a computer with a real-time operating system. This makes it possible to use a standard Windows based computer with commercial software for the data acquisition. A new channeltron has also been installed to detect secondary electrons that can be used to obtain a quick overview of an measurement area.
Technical details and first test measurements with the new system are presented.

[1] F. Herrmann, D. Grambole, Nucl. Instr. Meth. B 104 (1995) 26.

Keywords: PIXE; nuclear microprobe

  • Poster
    15th International Conference on Particle Induced X-ray Emission, 02.-07.04.2017, Split, Kroatien

Full-field PIXE imaging: Multi-frame super-resolution to overcome optics pattern and imaging-based resolution limitations

Buchriegler, J.; Klingner, N.; Munnik, F.; Nowak, S. H.; von Borany, J.; Ziegenrücker, R.

The combination of a pnCCD-based detector (264 x 264 pixels) with a polycapillary X-ray optics was installed and examined at HZDR [1]. The set-up is intended for PIXE imaging with protons (2-4 MeV) to survey large, flat/polished geological samples with respect to their (trace) elemental composition. In the standard configuration a 1:1 polycapillary X-ray optics (78 mm length, 20 µm capillary diameter) is used to guide the emitted photons towards the pnCCD-chip divided into nearly 70000 pixels. Their dimensions of 48 x 48 µm² cause a native lateral resolution of about 100 µm. By applying dedicated sub-pixel algorithms to recalculate the footprint of the photon’s electron cloud in the chip [2], this limitation can be bypassed and the lateral resolution is then mainly determined by the capillary’s diameter.
Nevertheless, all images gathered with this kind of set-up from a single measurement are superimposed by the optics pattern. The optics’ capillaries are grouped in hexagonal bundles during the fabrication process and these bundles are grouped together again. This process results in a reduced transparency in the regions where the bundles are joint making the hexagonal pattern visible. This influence can be (largely) removed by combining several short measurements with slightly shifted positions. The optics pattern is averaged out and in addition the lateral information (shift-lengths) can be used to further improve the resolution limit beyond the pixels’/capillaries’ dimensions. The total measurement time can be kept almost similar by dividing the single measurement time by the number of “shots” without losing statistics/sensitivity.
Results from descriptive image-sets of first test-measurements will be shown to demonstrate the potential of this technique for full-field PIXE imaging.

[1] D. Hanf et al., NIM B, Vol. 377, pp. 17-24 (2016).
[2] S.H. Nowak et al., X-ray Spec., Vol. 44 (3), pp. 135-140 (2015).

Keywords: full-field imaging; capillary optics; super resolution

  • Lecture (Conference)
    15th International Conference on Particle Induced X-ray Emission, 02.-07.04.2017, Split, Croatia

Upgrade of the nuclear microprobe at the Ion Beam Center at HZDR

Munnik, F.; Hanf., D.; Heller, R.

The nuclear microprobe that was installed in 1994 at the Ion Beam Center of the Helmholtz-Zentrum Dresden-Rossendorf [1], has been in operation up to 2014 with only minor changes. After 20 years it became necessary to make an upgrade to replace old components and bring the setup up to current standards of technology and good working practice.
The major drawback of the old system was the optical microscope, especially the poor resolution and low contrast and brightness. However, a good optical image is essential to localise the areas of interest on, for example, large geological samples. Since the focused beam of MeV ions and the corresponding detectors is the principal investigative tool, any other equipment such as an optical microscope has to be designed around this device. A new microscope has been installed for which the first light-collecting lens is mounted directly into the chamber at only a few centimetres from the sample. The light is then guided over large mirrors and focussed on a CCD camera outside the sample chamber. The illuminating light is fed in through the lenses instead of using an external light source as in the old system. In addition, there is also a light source opposite to the microscope, allowing transmission illumination including through a polarising filter making polarised imaging possible.
Other improvements concern the control of the scanning system as well as the control and monitoring of all relevant experimental parameters. The control of the scan magnets is done by custom-designed hardware to guarantee real-time execution of the scanning without the need for a computer running a real-time operating system. Controlling and monitoring of the experiment are implemented to facilitate easy and secure operation of the microprobe by the user with special emphasis on operation by un-experienced users, since the device is part of the user facility IBC. All standard IBA techniques like PIXE, PIGE, RBS, NRA, ERDA and STIM are available and, in addition, a Channeltron detector has been installed to detect secondary electrons that allow quick imaging of the measurement area.
Technical details and first test measurements with the new system are presented.

[1] F. Herrmann, D. Grambole, Nucl. Instr. Meth. B 104 (1995) 26.

  • Poster
    Ionentreffen (Teil der Serie Workshop Ionenstrahlphysik), 13.-15.02.2017, Göttingen, Deutschland

New possibilities of plasma immersion ion implantation (PIII) and deposition (PIII&D) in industrial components using metal tube fixtures

Ueda, M.; Silva, A. R.; Pillaca, E. J. D. M.; Mariano, S. F. M.; Rossi, J. O.; Oliveira, R. M.; Pichon, L.; Reuther, H.

New possibilities of Plasma Immersion Ion Implantation (PIII) and deposition (PIII&D) for treating industrial components in the batch mode have been explored. A metal tubular fixture is used to allocate the components inside around and along the tube, exposing to the plasma only the parts of each component that will be implanted. Hollow cathode- like plasma is generated only inside the tube filled with the desired gas, by applying high negative voltage pulses to the hollow cylindrical metal fixture which is insulated from the vacuum chamber walls. The metal tube (Me-tube) loaded with workpieces can be set-up inside the vacuum chamber in the standing-up, upside down or lying down arrangements. PIII tests were also run with and without metal sheet lids on the tube as well as with and without the components. Sputtering deposition and carbonitriding are also possible in this scheme by placing carbon tapes inside the tube and running the process with nitrogen PIII. Relatively clean DLC (Diamond Like Carbon) PIII&D deposition is possible by this method also since the plasma occupies mainly the Me-tube interior and not the whole chamber. Furthermore, operating high density PIII and PIII&D systems without additional plasma source, using only the high voltage pulser, is now possible to treat three dimensional parts. These methods are very convenient for batch processing of industrial parts by ion implantation and by ion implantation and deposition, in which a large number of small to medium size components can be treated by PIII and PIII&D, very quickly, efficiently and also at low cost.


Dr. René Heller

Head Ion Beam Analysis
Phone: +49 351 260 3617