Ion implantation induced by Cu ablation at high laser fluence

High energy laser plasma-produced Cu ions have been implanted in silicon substrates placed at different distances and angles with respect to the normal to the surface of the ablated target. The implanted samples have been produced using the iodine high power Prague Asterix Laser System (PALS) using 438 nm wavelength irradiating in vacuum a Cu target. The high laser pulse energy (up to 230 J) and the short pulse duration (400 ps) produced a non-equilibrium plasma expanding mainly along the normal to the Cu target surface. Time-of-flight (TOF) technique was employed, through an electrostatic ion energy analyzer (IEA) placed along the target normal, in order to measure the ion energy, the ion charge state, the energy distribution and the charge state distribution. Ions had a Boltzmann energy distributions with an energy increasing with the charge state. At a laser fluence of the order of 6 × 10⁶ J/cm², the maximum ion energy was about 600 keV and the maximum charge state was about 27+.In order to investigate the implantation processes, Cu depth profiles have been performed with Rutherford backscattering spectrometry (RBS) of 1.5 MeV helium ions, Auger electron spectroscopy (AES) with 3 keV electron beam and 1 keV Ar sputtering ions in combination with scanning electron microscopy (SEM). Surface analysis results indicate that Cu ions are implanted within the first surface layers and that the ion penetration ranges are in agreement with the ion energy measured with IEA analysis.     

Characteristics of laser-produced Ge ion fluxes used for modification of semiconductor materials

This paper describes the laser generation of Ge ion fluxes and their application to the modification of semiconductor materials by ion implantation. The Ge ions were produced by ablating solid targets using the PALS high-power iodine laser system at the PALS Research Centre in Prague, operating at its third harmonic frequency (438 nm wavelength) and producing 0.4 ns pulses with energy up to 0.25 kJ (intensity≤10¹⁵ W/cm²). The goal of these investigations was optimisation of the implantation of low and medium energy laser-generated Ge ion fluxes and they were carried out as part of the project PALS000929. Recently, a new repetitive pulse laser system at IPPLM in Warsaw, with a wavelength of 1.06 μm, energy of ～0.8 J in a 3.5 ns-pulse, repetition rate of up to 10 Hz, and intensity on target of up to 10¹¹ W/cm², has also been employed to produce Ge ions by irradiating solid targets. The laser-generated ions were investigated with diagnostics based on the time-of-flight method: various ion collectors and an electrostatic ion-energy analyzer. The Ge ion fluxes were implanted into Si and SiO₂ substrates located at distances of 10–30 cm from the target. The SiO₂ films were prepared on single crystal Si substrates and were implanted with Ge ions with different properties. The properties of the Ge-implanted layers, in particular, the depth distributions of implanted Ge ions, were characterised using Rutherford backscattering and other material surface diagnostic methods.     

Effect of N ion implantation on the optical properties of an organometallic complex—Zinc cadmium thiocyanate single crystal

A highly efficient non-linear optical organometallic compound zinc cadmium thiocyanate (ZCTC) single crystal was grown by solvent evaporation method. The as grown single crystals were implanted with 45 keV N⁵⁺ ions having energy at various fluencies of 1 × 10¹⁵, 5 × 10¹⁵, 1 × 10¹⁶ and 5 × 10¹⁶ ions/cm². The surface modification induced by the ion implantation was studied using scanning electron microscopy. The UV spectrum shows an increase in absorbance with the increase in the dosage of the ions implanted. There is a red shift in the cut off wavelength due to implantation which may be attributed to the lattice damage produced during implantation. From the Raman spectra, it is observed that there is no shift in the peak positions or any extra peaks due to implantation confirming that the nitrogen ions are not substituted into the lattice. The FWHM, area and intensity of the Raman peak corresponding to CN stretching vibration were calculated and the influence of ion implantation on these parameters was discussed. The effect of implantation on the PL spectra was analysed and discussed in detail. The change in refractive index of the sample due to implantation was reported.     

Modification of medical metals by ion implantation of copper

The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10¹⁷ to 4 × 10¹⁷ ions/cm² at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.     

Chemical surface composition of the polyethylene implanted by Ag ions studied by phase imaging atomic force microscopy

High density polyethylene (HDPE) has been modified by Ag⁺ ion implantation with the energy of 60 keV. The total amount of implanted silver ions was 1, 5 and 12 × 10¹⁵ ions/cm². The surface topography was observed by atomic force microscopy (AFM), while the surface composition changes were detected using phase imaging AFM. Surface topography changes were studied in detail using 3D surface parameters analyses. The average roughness decreased for the implanted HDPE indicating the flattening of the surface. Phase AFM images indicated the homogenization of the polyethylene during ion implantation, while histogram analyses confirmed the change in surface composition.     

Ferromagnetism in ZnO doped with Co by ion implantation

The importance of doping ZnO with magnetic ions is associated with the fact that this oxide is a good candidate for the formation of a magnetic-diluted semiconductor. Most of the studies reported in Co-doped ZnO were carried out in thin films, but the understanding of the modification of the magnetic behaviour due to doping demands the study of single-crystalline samples. In this work, ZnO single crystals were doped at room temperature with Co by ion implantation with fluences ranging between 2×10¹⁶ and 1×10¹⁷ ions cm⁻² and implantation energy of 100 keV. As implanted samples show a superparamagnetic behaviour attributed to the formation of Co clusters, room temperature ferromagnetism is attained after annealing at 800 °C, but no magnetoresistance was detected in the temperature range from 10 to 300 K.     

Optical reflectivity study of silicon ion implanted poly(methyl methacrylate)

The optical reflectivity (both specular and off-specular) of poly(methyl methacrylate) (PMMA) implanted with silicon ions (Si⁺) at energy of 50 keV, is studied in the spectral range 0.25-25 μm. The effect from the Si⁺ implantation on the reflectivity of two PMMA materials is examined in the dose range from 10¹⁴ to 10¹⁷ ions/cm² and is linked to the structure formed in this ion implanted plastic. As compared to the pristine PMMA, an enhancement of the reflectivity of Si⁺ implanted PMMA is observed, that is attributed to the modification of the subsurface region of PMMA upon the ion implantation. The ion-produced subsurface organic interface is also probed by laser-induced thermo-lens.     

Change of sheet resistance of high purity alumina ceramics implanted by Cu and Ti ions

High purity alumina ceramics (99% Al₂O₃) was implanted by copper ion and titanium ion in a metal vapour vacuum arc (MEVVA) implanter, respectively. The influence of implantation parameters was studied varying ion fluence. The samples were implanted by 68 keV Cu ion and 82 keV Ti ion with fluences from 1 × 10¹⁵ to 1 × 10¹⁸ ions/cm², respectively. The as-implanted samples were investigated by scanning electron microscopy (SEM), glancing X-ray diffraction (GXRD), scanning Auger microscopy (SAM), and four-probe method. Different morphologies were observed on the surfaces of the as-implanted samples and clearly related to implantation parameters. For both ion implantations, the sheet resistances of the alumina samples implanted with Cu and Ti ion fluences of 1 × 10¹⁸ ions/cm², respectively, reached the corresponding minimum values because of the surface metallization. The experimental results indicate that the high-fluence ion implantation resulted in conductive layer on the surface of the as-implanted high purity alumina ceramics.     

Damage formation in Ge during Ar and He implantation at 15 K

Ar⁺ and He⁺ ions were implanted into Ge samples with (1 0 0), (1 1 0), (1 1 1) and (1 1 2) orientations at 15 K with fluences ranging from 1×10¹¹ to 1×10¹⁴ cm⁻² for the Ar⁺ ions and fluences ranging from 1×10¹² to 6×10¹⁵ cm⁻² for the He⁺ ions. The Rutherford backscattering (RBS) technique in the channelling orientation was used to study the damage built-up in situ. Implantation and RBS measurements were performed without changing the target temperature. The samples were mounted on a four axis goniometer cooled by a close cycle He cryostat. The implantations were performed with the surface being tilt 7° off the ion beam direction to prevent channelling effects. After each 300 keV Ar⁺ and 40 keV He⁺ implantation, RBS analysis was performed with 1.4 MeV He⁺ ions.For both the implantation ions, there is about no difference between the values found for the damage efficiency per ion for the four different orientations. This together with the high value (around 5 times higher than that found in Si), gives rise to the assumption of amorphous pocket formation per incident ion, i.e. direct impact amorphization, already at low implantation fluences. At higher fluences, when collision cascades overlap, there is a growth of the already amorphized regions.     

Implantation-caused open volume defects in Ge after flash lamp annealing (FLA) probed by slow positron implantation spectroscopy (SPIS)

B⁺ and P⁺ ions were implanted into Ge wafers covered with a pre-amorphised surface layer of 150 nm. After this, flash lamp annealing (FLA) in Ar atmosphere was used as post-implantation heat treatment. Radiation with Xenon flash lamps, having a spectrum in the visible range of light and a pulse length of 3 ms or 20 ms, allowed an ultra-short heating up of the near surface region. In this way, a modification of the structure of the as-implanted amorphous Ge layer was possible. Depth profiles of defects, especially those of the vacancy-type, were investigated by slow positron implantation spectroscopy (SPIS) before and after FLA.It was found that the remaining vacancy-type defect structure depends on the parameters of the process of heat treatment, and that these defects could not be completely removed by FLA.Results are compared with such from SRIM 2006 calculations (stopping and range of ions in matter) and Rutherford backscattering spectrometry (RBS).     

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.     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

Room temperature magnetic properties of Fe and C implanted ZnO films

ZnO films prepared by radio frequency magnetron sputtering were singly or sequentially implanted with 120 keV Fe ions at a fluence of 5 × 10¹⁶ ions/cm² and 20 keV C ions at a fluence of 3 × 10¹⁵ ions/cm². Magnetic and optical properties as well as structures of the films have been investigated using various techniques. Magnetic measurements show that the as-deposited ZnO film presents room temperature ferromagnetism. Single Fe or C ion implantation has no contribution to enhancement in the film magnetism, while magnetic moment increases distinctly in the Fe and C ions sequentially implanted film. Results from structural measurements reveal that Fe nanoparticles are formed in the Fe singly implanted ZnO film. The post C implantation induces dissolution of Fe nanoparticles and promotes Fe atoms to substitute Zn atoms in the lattice. Based on the structural results, the effect of magnetic enhancement has been tentatively interpreted.     

Luminescence properties of Ge implanted SiO2:Ge and GeO2:Ge films

We have investigated cathodeluminescence (CL) of Ge implanted SiO₂:Ge and GeO₂:Ge films. The GeO₂ films were grown by oxidation of Ge substrate at 550 °C for 3 h in O₂ gas flow. The GeO₂ films on Ge substrate and SiO₂ films on Si substrate were implanted with Ge-negative ions. The implanted Ge atom concentrations in the films were ranging from 0.1 to 6.0 at%. To produce Ge nanoparticles the SiO₂:Ge films were thermally annealed at various temperatures of 600-900 °C for 1 h in N₂ gas flow. An XPS analysis has shown that the implanted Ge atoms were partly oxidized. CL was observed at wavelengths around 400 nm from the GeO₂ films before and after Ge⁻-implantation as well as from SiO₂:Ge films. After Ge⁻-implantation of about 0.5 at% the CL intensity has increased by about four times. However, the CL intensity from the GeO₂:Ge films was several orders of magnitude smaller than the intensity from the 800 °C-annealed SiO₂:Ge films with 0.5 at% of Ge atomic concentration. These results suggested that the luminescence was generated due to oxidation of Ge nanoparticles in the SiO₂:Ge films.     

Surface morphology of Mn implanted Ge(1 0 0): A systematic investigation as a function of the implantation substrate temperature

Ge (1 0 0) wafers were implanted with 100 keV Mn⁺ ions with a dose of 2 × 10¹⁶ ions/cm² at different temperatures, ranging from 300 to 573 K. The surface morphology of implanted samples, analyzed with scanning electron microscopy and atomic force microscopy measurements, reveals for the 300-463 K implant temperature range the formation of a surface swelled and porous film, containing sponge-like structures. On the contrary, samples implanted in the 513-573 K temperature range present an atomically flat surface, with a roughness less than 1 nm, indicating that crystalline order has been preserved. X-ray photoemission spectroscopy depth profiling measurements indicate the presence of adsorbed oxygen in the porous layer of lower-temperature implanted samples, as well the presence of a large Mn concentration below the expected end of range for impinging ions. Mn and O concentrations at anomalously great depths are maximum in the 413 K implanted sample, indicating that the phenomenon of ion beam induced porosity is best favored at a well defined temperature.     

Synthesis of molybdenum silicide by both ion implantation and ion beam assisted deposition

Two groups of Mo/Si films were deposited on surface of Si(1 0 0) crystal. The first group of the samples was prepared by both ion beam assisted deposition (IBAD) and metal vapor vacuum arc (MEVVA) ion implantation technologies under temperatures from 200 to 400 °C. The deposited species of IBAD were Mo and Si, and different sputtering Ar ion densities were selected. The mixed Mo/Si films were implanted by Mo ion with energy of 94 keV, and fluence of Mo ion was 5 × 10¹⁶ ions/cm². The second group of the samples was prepared only by IBAD under the same test temperature range. The Mo/Si samples were analyzed by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), sheet resistance, nanohardness, and modulus of the Mo/Si films were also measured. For the Mo/Si films implanted with Mo ion, XRD results indicate that phase of the Mo/Si films prepared at 400 and 300 °C was pure MoSi₂. Sheet resistance of the Mo/Si films implanted with Mo ion was less than that of the Mo/Si films prepared without ion implantation. Nanohardness and modulus of the Mo/Si films were obviously affected by test parameters.     

Optical waveguide with homogeneous refractive index profile in LiNbO3 by double-low-energy Oxygen ion implantation

We report on the formation of the planar waveguide by 550 keV O ion followed by 250 keV O ion implantation in lithium niobate (LiNbO₃), at fluences of 6 × 10¹⁴ ions/cm² and 3 × 10¹⁴ ions/cm², respectively. The Rutherford backscattering/channeling spectra have shown the atomic displacements in the damage region before and after annealing. A broad and nearly homogeneous damage layer has been formed by double-energy ion implantation after annealing. Both the dark mode spectra and the data of refractive index profile verified that the extraordinary refractive index was enhanced in the ion implanted region of LiNbO₃. A homogeneous near-field intensity profile was obtained by double-low-energy ion implantation. There is a reasonable agreement between the simulated modal intensity profile and the experimental data. The estimated propagation loss is about 0.5 dB/cm.     

Surface nano-structural modifications and characteristics in nitrogen ion implanted W as a function of temperature and N energy

The surface modifications of tungsten 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 tungsten samples for 1600 s at different temperatures. XRD patterns clearly showed WN₂ (0 1 8) (rhombohedral) very close to W (2 0 0) line. Crystallite sizes (coherently diffracting domains) 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. Similar morphological changes to that has been observed for thin films by increasing substrate temperature (i.e., structure zone model (SZM)), is obtained. The surface roughness variation with temperature generally showed a decrease with increasing temperature. The density of implanted nitrogen ions and the depth of nitrogen ion implantation in W studied by SIMS showed a minimum for N⁺ density as well as a minimum for penetration depth of N⁺ ions in W at certain temperatures, which are both consistent with XRD results (i.e., I_{W (2 0 0)}/I_{W (2 1 1)}) for W (bcc). Hence, showing a correlation between XRD and SIMS results.     

XPS study of silicon surface after ultra-low-energy ion implantation

Ultra-low-energy ion implantation of silicon with a hydrogen-terminated (0 0 1) surface was carried out using a mass-separated ³¹P⁺ ion beam. The ion energy was 30 eV, the displacement energy of silicon, and the ion doses were 6 × 10¹³ ions/cm². Annealing after the implantation was not carried out. The effects of ion implantation on the surface electrical state of silicon were investigated using X-ray photoelectron spectroscopy (XPS). The Si 2p peak position using XPS depends on the doping conditions because the Fermi level of the hydrogen-terminated silicon surface is unpinned. The Si 2p peak position of the specimen after ion implantation at a vacuum pressure of 3 × 10⁻⁷ Pa was shifted to the higher energy region. It suggested the possibility of phosphorus doping in silicon without annealing. In the case of ion implantation at 5 × 10⁻⁵ Pa, the Si 2p peak position was not shifted, and the peak was broadened because of the damage by the fast neutrals. Ultra-low-energy ion doping can be achieved at ultra-high-vacuum conditions.     

Influence of titanium ions implantation on corrosion behavior of zirconium in 1 M H2SO4

In order to study the effect of titanium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with titanium ions with fluence ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc (MEVVA) source at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with titanium ions. The larger the fluence, the better is the corrosion resistance of implanted sample. Finally, the mechanism of the corrosion behavior of titanium-implanted zirconium was discussed.