Characteristics of surface nano-structural modifications in nitrogen ion implanted W as a function of temperature

The surface modifications of tungsten massive samples (0.5 mm foils) made by nitrogen ion (30 keV; 1 × 10¹⁸ N⁺ cm⁻²) implantation are studied by XRD, AFM, and SIMS. XRD patterns clearly showed WN₂ (0 1 8) (rhombohedral) very close to W (2 0 0) line. Crystallite sizes obtained from WN₂ (0 1 8) line, showed an increase with substrate temperature. AFM images showed the formation of grains on W samples, which grew in size with temperature. These morphological changes are similar to those observed for thin films by increasing substrate temperature (i.e. structure zone model (SZM)). Surface roughness variation with temperature, showed a decrease with increasing temperature. The density of implanted nitrogen ions, and the depth of nitrogen ion implantation in W are studied by SIMS. The results show a minimum for N⁺ density at a certain temperature consistent with XRD results (i.e. I_W (2 0 0)/I_W (2 1 1)). This minimum in XRD results is again similar to that obtained for different thin films by Savaloni et al. [Physica B, 349 (2004) 44; Vacuum, 77 (2005) 245] and Shi and Player [Vacuum, 49 (1998) 257].     

Dependence of surface nano-structural modifications of Ti implanted by N ions on temperature

The surface modification of titanium thin foil/sheet samples (0.5 mm) implanted by nitrogen ions of 30 keV energy and a fluence of 1 × 10¹⁸ N⁺ cm⁻² at different temperatures is studied using XRD, AFM, SEM, and SIMS. XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, while the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 654 K showed the formation of grains, that after initial sputtering of the grain boundary at 728 K temperature, the morphology of the surface changed from small grains to a bimodal distribution of grains at 793 K which consisted of larger grains with bright hillocks within them. This was considered to be due to phase transformation/compositional changes, explained by correlating XRD and SIMS results. The SIMS results showed a maximum at about 730 K and a minimum at about 790 K for both N⁺ density and depth of N⁺ penetration in the Ti sample. The variation of these results with temperature was explained on the basis of the residual gas, substrate temperature, dissociation of water in the chamber and the gettering property of titanium.     

Synergetic effect between ion energy and sample temperature in the formation of distinct dot pattern on Si(1 1 0) by ion-sputter erosion

We observed a synergetic effect between ion energy and sample temperature in the formation of distinct dot pattern on Si(1 1 0) by Ar⁺ ion sputtering. The ion flux was 20 μA/cm², a value smaller than those used in preceding reports by one or two orders of magnitude. In experiments, the ion energy was from 1 to 5 keV, and the temperature from room temperature to 800 °C. A phase diagram indicating the ranges of ion energy and temperature within which distinct dot patterns can be achieved has been obtained. Data analyses and simulation results reveal that the synergetic effect is consistent with the effect of the Ehrlich-Schwoebel step-edge barrier, rather than the Bradley-Harper model.     

An electrostatic force microscope study of Si nanostructures on Si(1 0 0) as a function of post-annealing temperature and time

The evolution of Si nanostructures induced by Ar⁺ ion sputtering on Si(1 0 0) was studied with electrostatic force microscopy (EFM) as a function of post-annealing temperature (T = room temperature-800 °C) and time (t = 0-160 min). The post-annealing of the nanostructure was conducted in vacuum. It was found that with T increasing, the EFM contrast degraded steadily and became nearly undetectable at T = 800 °C; with t increasing at T = 800 °C, the EFM contrast fell down steadily as well. However, the surface morphology and roughness were much less affected after annealing. The results suggest that the as-formed Si nanostructures may not be epitaxially grown on Si(1 0 0) substrate as claimed before. A plane capacitance model supported this conclusion.     

Using time-of-flight secondary ion mass spectrometry and multivariate statistical analysis to detect and image octabenzyl-polyhedral oligomeric silsesquioxane in polycarbonate

Silsesquioxane, with an empirical formula of RSiO_3/2, has the potential to combine the mechanical properties of plastics with the oxidative stability of ceramics in one material [D.W. Scott, J. Am. Chem. Soc. 68 (1946) 356; K.J. Shea, D.A. Loy, Acc. Chem. Res. 34 (2001) 707; K.-M. Kim, D.-K. Keum, Y. Chujo, Macromolecules 36 (2003) 867; M.J. Abad, L. Barral, D.P. Fasce, R.J.J. William, Macromolecules 36 (2003) 3128]. The high sensitivity, surface specificity, and ability to detect and image high mass additives make time-of-flight secondary ion mass spectrometry (ToF-SIMS) a powerful surface analytical instrument for the characterization of polymer composite surfaces in an analytical laboratory [J.C. Vickerman, D. Briggs (Eds.), ToF-SIMS Surface Analysis by Mass Spectrometry, Surface Spectra/IMPublications, UK, 2001; X. Vanden Eynde, P. Bertand, Surf. Interface Anal. 27 (1999) 157; P.M. Thompson, Anal. Chem. 63 (1991) 2447; S.J. Simko, S.R. Bryan, D.P. Griffis, R.W. Murray, R.W. Linton, Anal. Chem. 57 (1985) 1198; S. Affrossman, S.A. O’Neill, M. Stamm, Macromolecules 31 (1998) 6280]. In this paper, we compare ToF-SIMS spectra of control samples with spectra generated from polymer nano-composites based on octabenzyl-polyhedral oligomeric silsesquioxane (BnPOSS) as well as spectra (and images) generated from multivariate statistical analysis (MVSA) of the entire spectral image. We will demonstrate that ToF-SIMS is able to detect and image low concentrations of BnPOSS in polycarbonate. We emphasize the use of MVSA tools for converting the massive amount of data contained in a ToF-SIMS spectral image into a smaller number of useful chemical components (spectra and images) that fully describe the ToF-SIMS measurement.     

A refined Ehrlich-Schwoebel effect on the modification of Si surface nanostructures by post ion milling

A modeling work has been conducted on a phenomenon called post ion milling (PIM), a post-treatment of Ar⁺ ion sputtering to modify nanostructures on solid surface. It was found by experiments that for PIM with a sufficiently low ion flux, both the average dot size and the surface roughness of Si nanodot arrays on Si(1 0 0) decline steadily against milling time. However, the usually adopted Kuramoto-Sivashinsky (KS) model involving the Bradley-Harper (BH) theory failed to explain the experimental results, nor the KS model that combines both the BH and Ehrlich-Schwoebel (ES) effects. We reexamined the ES term in the KS equation, and derived new terms reflecting the ES contribution. With such a modification, the KS model involving both the BH and the refined ES effects finally gave a qualitative explanation to the PIM result.     

SIMS investigation of gettering centres produced by phosphorus MeV ion implantation

The ion implantation is a well-known standard procedure in electronic device technology for precise and controlled introduction of dopants into silicon. Damages caused by implantation act as effective gettering zones, collecting unwanted metal impurities. In this work, the consequences of high-energy ion implantation into silicon and of subsequently annealing were analysed by means of secondary ion mass spectrometry (SIMS). The differences in impurities gettering behaviour were studied in dependence of the implantation dose and annealing time at T = 900 °C.     

Nano- and micro-scale patterning of Si (1 0 0) under keV ion irradiation

Evolution of Si (1 0 0) surface under 100 keV Ar⁺ ion irradiation at oblique incidence has been studied. The dynamics of surface erosion by ion beam is investigated using detailed analysis of atomic force microscopy (AFM) measurements. During an early stage of sputtering, formation of almost uniformly distributed nano-dots occurs on Si surface. However, the late stage morphology is characterized by self-organization of surface into a regular ripple pattern. Existing theories of ripple formation have been invoked to provide an insight into surface rippling.     

Effect of gas residence time on the morphology of silicon surface etched in SF6 plasmas

This paper describes the effect of the SF₆ gas residence time on the morphology of silicon (1 0 0) samples etched in a reactive ion etching system. Profilometry and atomic force microscopy techniques were used to characterize the etching process focusing attention on the evolution of the surface morphology. Under the condition of variable pressure and gas flow rate, the decrease of the residence time leads to an increase of the silicon etch rate concomitantly with an increase of the surface roughness. Contrary fact is observed when the gas flow is fixed and the pressure is varied. Here, the increasing of residence time leads to a constant increase of silicon etch rate with small variations in final surface roughness. To better understanding this resident time effect, mass spectrometry analyses were realized during the discharge for both gas flow conditions.     

Characterization of ion species of silicon oxide films using positive and negative secondary ion mass spectra

Secondary ion species of silicon oxide films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Characterization of thermally grown SiO₂ films on silicon has been performed. A diagram showing secondary ion spectra of SiO₂ films in both positive and negative polarities indicates the pattern of change in polarities and intensities of ion species from SiO⁺ to Si₅O₁₁⁻. The ions mostly change from positive to negative polarity between Si_nO_2n−1 and Si_nO_2n. Ion peaks with the strongest intensities in the respective cluster ions correspond to the Si_nO_2n+1 negative ion. Intensities of ion species of Si_nO_2n+2 appear negligibly small. Ion species of Si₃O⁺, Si₃O₂⁺ and Si₃O₃⁺ have been found at the interface between silicon and SiO₂ films. The intensity patterns of these ion species compared to those of SiO₂ films indicate that most of these species are not emitted from the SiO₂ films, but likely from the SiO structures.     

Low energy RBS and SIMS analysis of the SiGe quantum well

The Ge concentration in a MBE grown SiGe and the depth of the quantum well has been quantitatively analysed by means of low energy Rutherford backscattering (RBS) and secondary ion mass spectrometry (SIMS). The concentrations of Si and Ge were supposed to be constant, except for the quantum well, where the nominal germanium concentration was at 5%. Quantitative information was deduced out of raw data by comparison to SIMNRA simulated spectra. With the knowledge of the response function of the SIMS instrument (germanium delta (δ) layer) and using the model of forward convolution (point to point convolution) it is possible to determine the germanium concentration and the thickness of the analysed quantum well out of raw SIMS data.     

Evolution of surface morphology of NiO thin films under swift heavy ion irradiation

NiO nanoparticle thin films grown on Si substrates were irradiated by 107 MeV Ag⁸⁺ ions. The films were characterized by glancing angle X-ray diffraction and atomic force microscopy. Ag ion irradiation was found to influence the shape and size of the nanoparticles. The pristine NiO film consisted of uniform size (∼100 nm along major axis and ∼55 nm along minor axis) elliptical particles, which changed to also of uniform size (∼63 nm) circular shape particles on irradiation at a fluence of 3 × 10¹³ ions cm⁻². Comparison of XRD line width analysis and AFM data revealed that the particles in the pristine films are single crystalline, which turn to polycrystalline on irradiation with 107 MeV Ag ions.     

Range evaluation in SIMS depth profiles of Er-implantations in silicon

In the last decade ion implantation of common dopants in silicon has been almost full characterised. However, data of inner transition elements are based on few measurements or even extrapolations. Our investigations focus on erbium, an upcoming dopant in photonic applications. Some of us have previously found errors of 20% in the projected range of Er in Si and SiO₂ when comparing the range profiles measured with SIMS and simulations using SRIM, T2D, and our own binary collision simulator IMSIL. Because of the far-reaching consequences, we have performed additional, more precise experiments to confirm our previous results.Equal doses of Er has been implanted into SIMOX wafers with energies of 100, 200, 300, 400, 500, and 600 keV. Profiles have been measured with secondary ion mass spectrometry (SIMS). Relative sensitivity factors (RSF) were gathered from low-energy implantations, remaining within the Si top layer. We used the Si/SiO₂ interface at exactly 217.7 nm to calibrate the depth scale of all profiles. In addition dynamical Monte-Carlo simulations of the sputter process were taken to correct the depth scale and the interface position.     

Surface nanostructural modifications of Ti implanted by N+ ions as a function of energy

The surface modification of titanium foil/sheet samples (0.5?mm thickness) implanted by nitrogen ions of different energy and fluence of 1?×?10^18?N^+?cm^?2 was studied using X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy and secondary-ion mass spectrometry (SIMS). XRD patterns showed the development of titanium nitride with different compositions in the implanted samples, and the presence of different titanium compositions such as titanium oxides was also observed. AFM images at 16 and 20?keV showed the formation of grains, which were attributed to the initial sputtering of grain boundaries. The morphology of the surface changed at 25?keV showing granular structure with an almost uniform background and lowest surface roughness relative to lower and higher implantation energies. A correlation was obtained between all results for XRD, SIMS and AFM except the titanium nitride maximum intensity at 25?keV N⁺ implantation. In order to achieve more detailed information about the role of N⁺ energy in this kind of work it is proposed that a further investigation is needed on both N⁺ energy and substrate temperature as well as some theoretical studies.     

Thermal stability of nanoscale silver metallization in Ag/W/Co/Si(1 0 0) multilayer

In this work, we have studied thermal stability of nanoscale Ag metallization and its contact with CoSi₂ in heat-treated Ag(50 nm)/W(10 nm)/Co(10 nm)/Si(1 0 0) multilayer fabricated by sputtering method. To evaluate thermal stability of the systems, heat-treatment was performed from 300 to 900 °C in an N₂ ambient for 30 min. All the samples were analyzed by four-point-probe sheet resistance measurement (R_s), Rutherford backscattering spectrometry (RBS), X-ray diffractometry (XRD), and atomic force microscopy (AFM). Based on our data analysis, no interdiffiusion, phase formation, and R_s variation was observed up to 500 °C in which the Ag layer showed a (1 1 1) preferred crystallographic orientation with a smooth surface and R_s of about 1 Ω/□. At 600 °C, a sharp increase of R_s value was occurred due to initiation of surface agglomeration, WSi₂ formation, and interdiffusion between the layers. Using XRD spectra, CoSi₂ formed at the Co/Si interface preventing W silicide formation at 750 and 800 °C. Meantime, RBS analysis showed that in this temperature range, the W acts as a cap layer, so that we have obtained a W encapsulated Ag/CoSi₂ contact with a smooth surface. At 900 °C, the CoSi₂ layer decomposed and the layers totally mixed. Therefore, we have shown that in Ag/W/Co/Si(1 0 0) multilayer, the Ag nano-layer is thermally stable up to 500 °C, and formation of W-capped Ag/CoSi₂ contact with R_s of 2 Ω/□ has been occurred at 750-800 °C.     

Measurement and Analysis of Composition and Depth Profile of H in Amorphous Si1-xCx:H Films

Composition in amorphous Si1-xCx：H heteroepitaxial thin films on Si （100） by plasma enhanced chemical vapour deposition （PECVD） is analysed. The unknown x （0.45-3.57） and the depth profile of hydrogen in the thin films are characterized by Rutherford backscattering spectrum （RBS）, resonance-nuclear reaction analysis （R-NRA） and elastic recoil detection （ERD）, respectively. In addition, the depth profile of hydrogen in the unannealed thin films is compared to that of the annealed thin films with rapid thermal annealing （RTA） or laser spike annealing （LSA） in nitrogen atmosphere. The results indicate that the stoichiometric amorphous SiC can be produced by PECVD when the ratio of CH4/SiH4 is approximately equal to 25. The content of hydrogen decreases suddenly from 35% to 1% after 1150℃ annealing. RTA can reduce hydrogen in SiC films effectively than LSA.     

Temperature and N energy dependence on nano-structural modifications and characteristics of Mo surface

The surface modifications of Mo massive samples (0.5 mm foils) made by nitrogen ion implantation are studied by SEM, XRD, AFM, and SIMS. Nitrogen ions in the energy range of 16-30 keV with a fluence of 1 × 10¹⁸ N⁺ cm⁻² were implanted in molybdenum samples for 1600 s at different temperatures. XRD patterns clearly showed MoN (0 3 1) (hcp) very close to Mo (2 0 0) line. Crystallite sizes (coherently diffracting domains) obtained from MoN (0 3 1) line, showed an increase with substrate temperature. AFM images showed the formation of grains on Mo samples, which grew in size with temperature. Similar morphological changes to that has been observed for thin films by increasing substrate temperature (i.e., structure zone model (SZM)), is obtained. The density of implanted nitrogen ions and the depth of nitrogen ion implantation in Mo studied by SIMS showed a minimum for N⁺ density as well as a minimum for penetration depth of N⁺ ions in Mo at certain temperatures, which are both consistent with XRD results (i.e., I_{Mo (2 0 0)}/I_{Mo (2 1 1)}) for Mo (bcc). Hence, showing a correlation between XRD and SIMS results. This phenomenon is explained on the basis of residual gas, substrate temperature, dissociation of water in the chamber and the ion energy.     

Evolution of dislocations in perylene films with thickness and deposition rate

The growth of perylene films on an amorphous oxide bottom layer is investigated. The perylene films show clear spiral growth and formation of screw dislocations. As a function of deposition rate and film thickness the densities of screw dislocations, grains as well as the roughness and the lateral correlation length are determined from AFM images. The evolution of microstrain as calculated from an XRD peak profile analysis corresponds to the dislocation density. The simultaneous decrease of grain density and dislocation density with film thickness is explained by considering the overgrowth of grains due to loss of dislocations acting as growth spirals. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

     

Influence of substrate temperature on the chemical and microstructural properties of MO-CVD ZrTiO<Subscript>4</Subscript> thin films

In the last few years, intensive research activity has been focused on the development of suitable synthesis methods for high-permittivity materials, used for the realization of next-generation microdevices able to fulfil the previsions of the Technology Roadmap of Semiconductors. The use of high-permittivity materials can overcome the difficulties concerning the production of SiO₂-based ultra-thin dielectrics, such as the generation of pinholes and the non-uniformity of the film, which may result in a malfunction in high-density systems. Recently, zirconium titanate thin films were discovered to have very interesting dielectric properties, which suggests a use for them in microwave integrated systems, such as receivers or DRAMs, since they are monophasic, have little dissipation and show a good thermal stability and a high value for the dielectric constant, independent of frequency in the range from kilohertz to a few gigahertz. Real application is possible only in strict connection with the development of a suitable preparation method which allows production with controlled and reproducible characteristics. In this work, the synthesis and characterization of Zr_xTi_1-xO₄ (ZT) thin films grown via MO-CVD is described, studying the influence of growth parameters on their structural, chemical and physical properties. Received: 17 June 2002 / Accepted: 24 June 2002 / Published online: 4 November 2002 RID="*" ID="*"Corresponding author. Fax: +39-06/9067-2445, E-mail: Pad@mlib.cnr.it     

Dynamic secondary ion mass spectrometry and X-ray photoelectron spectroscopy on artistic bronze and copper artificial patinas

To prevent the natural processes of decay and to develop and improve the treatments of conservation and restoration of artistic bronzes meaning statues and sculptures, it is important understanding the patination processes and the knowledge of artificially corroded surfaces. Chemical and physical characterization of artificial patinas obtained on artistic bronzes and coppers by using the 19th century Western traditional patination techniques and recipes by means of SEM-EDS, light microscopy and ATR/FT-IR has been done in previous studies [I.Z. Balta, L. Robbiola, Characterization of artificial black patinas on artistic cast bronze and pure copper by using SEM-EDS and light microscopy, in: Proceedings of the 13th European Microscopy Congress, 22-27 August 2004, Antwerp, Belgium, EMC 2004 CD-Rom Conference Preprints; I.Z. Balta, L. Robbiola, Traditional artificial artistic bronze and copper patinas—an investigation by SEM-EDS and ATR/FT-IR, in: Proceedings of the 8th International Conference on Non Destructive Investigations and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage, 15-19 May 2005, Lecce, Italy, ART’05 CD-Rom Conference Preprints]. Differences in morphology (structure, thickness, porosity, adherence, compactity, uniformity, homogeneity) and also in composition, on both artistic cast bronze and pure copper patinas, were clearly evidenced. Further in-depth investigation is required to be carried out in order to better understand the patinas mechanisms of formation and the layers kinetics of growth. The elemental and chemical analysis, either on a surface monolayer or in a depth profile, by using the Secondary Ion Mass Spectrometry (SIMS) and X-ray Photoelectron Spectroscopy (XPS) techniques, can provide this kind of information, unique at trace-level sensitivity. SIMS has proved to be a suitable analytical technique for analyzing small amounts of material with high atomic sensitivity (ppm or even ppb) and high depth/lateral resolution in the micron and sub-micron range [R.G. Wilson, F.A. Stevie, C.W. Magee, Secondary Ion Mass Spectrometry: A Practical Handbook for Depth Profiling and Bulk Impurity Analysis, Wiley & Sons, New York, 1989; M. Dowsett, A. Adriaens, The role of SIMS in cultural heritage studies, Nucl. Instr. Meth. Phys. Res. B 226 (2004) 38-52]. XPS has the ability to provide detailed chemical information on virtually each kind of solid sample, and elemental identification is therefore possible due to the core level photoemission. The most important advantage is the high surface sensitivity of the chemical information (a few monolayers) [E. Ciliberto, G. Spoto, Modern Analytical Methods in Art and Archaeology, John Wiley & Sons, Inc., New York, 2000]. In addition elements’ relative abundance can be made semi-quantitative or quantitative and information on chemical bonds can be derived.The aim of the present work is to highlight the advantages and the limits of XPS and Dynamic SIMS surface analytical techniques for the characterization of artistic bronze and copper artificial patinas. The results obtained on the analyzed samples allowed the distribution of the main elements in the corrosion patinas layers and the contribution of each elements present in bronze matrix to the color of the resulting patinas to be precisely revealed. This information could be used for comparative studies between artificial and natural patinas, and also for provenience and authentication studies for artistic and archaeological bronzes.