Study of silver diffusion in silicon carbide

Diffusion of silver in 6H-SiC and polycrystalline CVD-SiC was investigated using α-particle channeling spectroscopy and electron microscopy. Fluences of 2 × 10¹⁶ cm⁻² of ¹⁰⁹Ag⁺ were implanted with an energy of 360 keV at room temperature, at 350 °C and 600 °C, producing an atomic density of approximately 2% at the projected range of about 110 nm. The broadening of the implantation profile and the loss of silver through the front surface during vacuum annealing at temperatures up to 1600 °C was determined. Fairly strong silver diffusion was observed after an initial 10 h annealing period at 1300 °C in both polycrystalline and single crystalline SiC, which is mainly due to implant induced radiation damage. After further annealing at this temperature no additional diffusion took place in the 6H-SiC samples, while it was considerably reduced in the CVD-SiC. The latter was obviously due to grain boundary diffusion and could be described by the Fick diffusion equation. Isochronal annealing of CVD-SiC up to 1400 °C exhibited an Arrhenius type temperature dependence, from which a frequency factor D_o ∼ 4 × 10⁻¹² m² s⁻¹ and an activation energy E_a ∼ 4 × 10⁻¹⁹ J could be extracted. Annealing of 6H-SiC above 1400 °C shifted the silver profile without any broadening towards the surface, where most of the silver was released at 1600 °C. Electron microscopy revealed that this process was accompanied by significant re-structuring of the surface region. An upper limit of D < 10⁻²¹ m² s⁻¹ was estimated for 6H-SiC at 1300 °C.     

Sub-surface retention of Pb atoms in silicon after low-energy ion implantation and electron beam annealing

Low-energy Pb ion implantation into (1 0 0) Si and subsequent high-vacuum electron beam annealing was used to study the potential of sub-surface retention of Pb atoms after applying a high temperature annealing process. 7 keV Pb⁺ ions were implanted into p-type (1 0 0) Si at room temperature with a fluence of 4 × 10¹⁵ ions cm⁻². The implantation results in a Pb depth distribution that has a calculated Pb peak concentration of 23.9 at.% at a depth of 8.0 nm. The Pb implanted Si substrates were annealed with a high-current 20 keV electron beam at 200-700 °C for 15 s. The Pb loss by out-diffusion was measured with RBS. Key results are: (i) minimal Pb loss in samples annealed up to 400 °C, (ii) emerging out-diffusion above 400 °C, (iii) retention of Pb atoms in the near-surface region in samples annealed up to 700 °C. Comparison of the RBS data with the calculated evaporation rate of Pb under similar conditions reveals two distinctive temperature ranges in which the measured Pb loss of the implanted samples disagrees with the calculated Pb loss: (1) Pb atoms diffused out of the samples at a higher rate in the temperature range up to 400 °C and (2) the Pb atoms diffused out of the samples at a much slower rate above 450 °C. Both phenomena are attributed to the ion implantation process.     

Effect of annealing on structure and hardness of oxygen-implanted layer on Ti6Al4V by plasma-based ion implantation

Ti6Al4V was treated by oxygen plasma-based ion implantation at the voltage pulses of −30 and −50 kV with a constant fluency of 0.6 × 10¹⁷ O/cm². After implantation, the annealing in vacuum was applied to the implanted samples to control phase structure of the implanted layer. The higher voltage implantation forms nano-size rutile in the implanted layer, but the subsequent annealing at 600 °C induces the resolution of the previous rutile. Although, the lower voltage implantation does not lead to rutile, the annealing can precipitate anatase and rutile in the implanted layer. The higher voltage implantation results in a higher hardness of the implanted layer. The annealing at 500 °C leads to an apparent increase in hardness of the implanted layer, but the annealing at 600 °C induces a rapid decrease in hardness.     

Formation of InAs nanocrystals in Si by high-fluence ion implantation

We have studied the formation of InAs precipitates with dimensions of several nanometers in silicon by means of As (245 keV, 5 × 10¹⁶ cm⁻²) and In (350 keV, 4.5 × 10¹⁶ cm⁻²) implantation at 500 °C and subsequent annealing at 900 °C for 45 min. RBS, SIMS, TEM/TED, RS and PL techniques were used to characterize the implanted layers. The surface density of the precipitates has been found to be about 1.2 × 10¹¹ cm⁻². Most of the crystallites are from 3 nm to 6 nm large. A band at 1.3 μm has been registered in the low-temperature PL spectra of (As + In) implanted and annealed silicon crystals. The PL band position follows the quantum confinement model for InAs.     

N-TiO2 nanoparticles embedded in silica prepared by Ti ion implantation and annealing in nitrogen

Room-temperature Ti ion implantation and subsequent thermal annealing in N₂ ambience have been used to fabricate the anatase and rutile structured N-doped TiO₂ particles embedded in the surface region of fused silica. The Stopping and Range of Ions in Matter (SRIM) code simulation indicates a Gaussian distribution of implanted Ti, peaked at ∼75 nm with a full width at half maximum of ∼80 nm. However, the transmission electron microscopy image shows a much shallower distribution to depth of ∼70 nm. Significant sputtering loss of silica substrates has occurred during implantation. Nanoparticles with size of 10-20 nm in diameter have formed after implantation. X-ray photoelectron spectroscopy indicates the coexistence of TiO₂ and metallic Ti in the as-implanted samples. Metallic Ti is oxidized to anatase TiO₂ after annealing at 600 °C, while rutile TiO₂ forms by phase transformation after annealing at 900 °C. At the same time, N-Ti-O, Ti-O-N and/or Ti-N-O linkages have formed in the lattice of TiO₂. A red shift of 0.34 eV in the absorption edge is obtained for N-doped anatase TiO₂ after annealing at 600 °C for 6 h. The absorbance increases in the ultraviolet and visible waveband.     

Damage recovery and optical activity in europium implanted wide gap oxides

In this study we compare and discuss the defects and optical behaviour of sapphire and magnesium oxide single crystals implanted at room temperature with different fluences (1 × 10¹⁵-1 × 10¹⁶ cm⁻²) of europium ions.Rutherford backscattering channelling shows that for fluences above 5 × 10¹⁵ cm⁻² the surface disorder level in the Al-sublattice reaches the random level. Implantation damage recovers fast for annealing in oxidizing atmosphere but even for the highest fluence we recover almost completely all the damage after annealing at 1300 °C, independently of the annealing environment (reducing or oxidizing). Annealing above 1000 °C promotes the formation of Eu₂O₃ in the samples with higher concentration of Eu. The optical activation of the rare earth ions at room temperature was observed after annealing at 800 °C by photoluminescence and ionoluminescence. In Al₂O₃ lattice the highest intensity line of the Eu³⁺ ions corresponds to the forced electric dipole ⁵D₀ → ⁷F₂ transition that occurs ∼616 nm. For the MgO samples the Eu³⁺ optical activation was also achieved after implantation with different fluences. Here, the lanthanide recombination is dominated by the magnetic dipole ⁵D₀ → ⁷F₁ transition near by 590 nm commonly observed for samples were Eu³⁺ is placed in a high symmetry local site. The results clearly demonstrate the possibility to get Eu incorporated in optical active regular lattice sites in wide gap oxides.     

Surface exfoliation and defect structures in Si induced by 160 keV He and 110 keV H ion implantation

Cz n-type Si(100) wafers were implanted at room temperature with 160 keV He ions at a fluence of 5 × 10¹⁶/cm² and 110 keV H ions at a fluence of 1 × 10¹⁶/cm², singly or in combination. Surface phenomena and defect microstructures have been studied by various techniques, including scanning electron microscopy (SEM), atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM). Surface exfoliation and flaking phenomena were only observed on silicon by successive implantation of He and H ions after subsequent annealing at temperatures above 400 °C. The surface phenomena show strong dependence on the thermal budget. At annealing temperatures ranging from 500 to 700 °C, craters with size of about 10 μm were produced throughout the silicon surface. As increasing temperature to 800 °C, most of the implanted layer was sheared, leaving structures like islands on the surface. AFM observations have demonstrated that the implanted layer is mainly transfered at the depth around 960 nm, which is quite consistent with the range of the ions. XTEM observations have revealed that the additional low fluence H ion implantation could significantly influence thermal growth of He-cavities, which gives rise to a monolayer of cavities surrounded by a large amount of dislocations and strain. The surface exfoliation effects have been tentatively interpreted in combination of AFM and XTEM results.     

The improvement of low-resistance and high-transmission ohmic contact to p-GaN by Zn implantation

The electrical and optical characteristics of Zn⁺ ion-implanted Ni/Au ohmic contacts to p-GaN were investigated. After the preparation of Ni/Au electrode on the surface of p-GaN, the metal/p-GaN contact interface was doped by 35 keV Zn⁺ implantation with fluences of 5 × 10¹⁵-5 × 10¹⁶ cm⁻². Subsequent rapid thermal annealing of the implanted samples were carried in air at 200-400 °C for 5 min. Obvious improvements of the electrode contact characteristics were observed, i.e. the decrease of specific contact resistance and the increase of light transmittance. The lowest specific contact resistance of 5.46 × 10⁻⁵ Ω cm² was achieved by 1 × 10¹⁶ cm⁻² Zn⁺ implantation. The transmission enhancement of the electrodes was found as the annealing temperature rises. Together with the morphology and structure analyses of the contacts by scanning and transmission electron microscope, the corresponding mechanism for such an improvement was discussed.     

The annealing behavior of Cu nanoparticles in Ar-ion implanted spinel

Magnesium aluminate spinel crystals (MgAl₂O₄ (1 1 0)) deposited with 30 nm Cu film on surface were implanted with 110 keV Ar-ions to a fluence of 1.0 × 10¹⁷ ions/cm² at 350 °C, and then annealed in vacuum condition at the temperature of 500, 600, 700, 800 and 900 °C for 1 h, respectively. Ultraviolet-visible spectrometry (UV-VIS), scanning electron microscopy (SEM), Rutherford backscattering (RBS) and transmission electron microscopy (TEM) were adopted to analyze the specimens. After implantation, the appearance of surface plasmon resonance (SPR) absorbance peak in the UV-VIS spectrum indicated the formation of Cu nanoparticles, and the TEM results for 500 °C also confirmed the formation of Cu nanoparticles at near-surface region. In annealing process, The SPR absorbance intensity increased at 500 and 700 °C, decreased with a blue shift of the peak position at 600 and 800 °C, and the peak disappeared at 900 °C. The SPR absorbance intensity evolution with temperature was discussed combined with other measurement results (RBS, SEM and TEM).     

The range distribution and annealing behavior of Er ions implanted in silicon-on-insulator

The range distribution for energetic 400 keV Er ions implanted in silicon-on-insulator (SOI) at room temperature were measured by means of Rutherford backscattering followed by spectrum analysis. The damage distribution and annealing behavior of implanted Er ions in SOI at the energy of 400 keV with dose of 5 × 10¹⁵ cm⁻² were obtained by Rutherford backscattering technique. It has been found that the damage around the SOI surface had been almost removed after annealed in nitrogen atmosphere at 900 °C, and a lot of Er atoms segregate to the surface of sample with the recrystallization of surface Si of SOI sample after annealing at 900 °C.     

Dynamic annealing study of SiC epilayers implanted with Ni ions at different temperatures

SiC epilayers grown on 4H-SiC single crystals were implanted with 850 keV Ni⁺ ions with fluences in the 0.5-9 × 10¹⁶ Ni⁺/cm² range. Most of the samples were implanted at 450 °C, but for comparison some implantations were performed at room temperature (RT). In addition, a post-implantation annealing was performed in N₂ at 1100 °C in order to recover the implantation-induced structural damage. The disorder produced by the implantation at 450 °C and the effect of the post-implantation annealing on the recrystallization of the substrates have been studied as a function of the fluence by Backscattering Spectrometry in channeling geometry (BS/C) with a 3.45 MeV He²⁺ beam. RT as-implanted samples showed a completely amorphous region which extends until the surface when irradiated with the highest dose, whereas in the case of 450 °C implantation amorphization does not occur. In general, partial recovery of the crystal lattice quality was found for the less damaged samples, and the dynamic recovery of the crystalline structure increases with the irradiation temperature.     

Synthesis and characterization of SnO2 nanoparticles embedded in silica by ion implantation

Tin dioxide nanoparticles embedded in silica matrix were fabricated by ion implantation combined with thermal oxidation. Silica substrate was implanted with a 150 keV Sn⁺ ions beam with a fluence of 1.0 × 10¹⁷ ions/cm². The sample was annealed for 1 h in a conventional furnace at a temperature of 800 °C under flowing O₂ gas. According to the structural characterization performed by X-ray diffraction and transmission electron microscopy techniques, metallic tetragonal tin nanoparticles with a volume average size of 12.8 nm were formed in the as-implanted sample. The annealing in oxidizing atmosphere promotes the total oxidation of the tin nanoparticles into tin dioxide nanoparticles with a preferential migration toward the surface of the matrix, where large and coalesced nanoparticles were observed, and a small diffusion toward the bulk, where smaller nanoparticles were found.     

The interdiffusion and solid-state reaction of low-energy copper ions implanted in silicon

At room temperature, single-crystal silicon was implanted with Cu⁺ ions at an energy of 80 keV using two doses of 5 × 10¹⁵ and 1 × 10¹⁷ Cu⁺ cm⁻². The samples were heat treated by conventional thermal annealing at different temperatures: 200 °C, 230 °C, 350 °C, 450 °C and 500 °C. The interdiffusion and solid-state reactions between the as-implanted samples and the as-annealed samples were investigated by means of Rutherford backscattering spectrometry (RBS) and X-ray diffraction (XRD). After annealing at 230 °C, the XRD results of the samples (subject to two different doses) showed formation of Cu₃Si. According to RBS, the interdiffusion between Cu and Si atoms after annealing was very insignificant. The reason may be that the formation of Cu₃Si after annealing at 230 °C suppressed further interdiffusion between Si and Cu atoms.     

Caesium isothermal migration behaviour in sintered titanium nitride: New data and comparison with previous results on iodine and xenon

Titanium nitride has been proposed as a fission product barrier in fuel structures for gas cooled fast reactor (GFR) systems. The thermal migration of Cs was studied by implanting 800 keV ¹³³Cs⁺⁺ ions into sintered samples of TiN at an ion fluence of 5 × 10¹⁵ cm⁻². Thermal treatments at temperatures ranging from 1500 to 1650 °C were performed under a secondary vacuum. Concentration profiles were determined by 2.5 MeV ⁴He⁺ elastic backscattering. The results reveal that the global mobility of caesium in the host matrix is low compared to xenon and iodine implanted in the same conditions. Nevertheless, the evolution of caesium depth profile during thermal treatment presents similarities with that of xenon. Both species are homogeneously transported towards the surface and the transport rate increases with the temperature. In comparison, iodine exhibits singular migration behaviour. Several assumptions are proposed to explain the better retention of caesium in comparison with both other species. The potential role played by the oxidation is underlined since even a slight modification of the surface stoichiometry may modify species mobility. More generally, the apparition of square-like shapes on the surface of the samples after implantations and thermal treatments is discussed.     

Lateral straggling and its influence on lateral diffusion in implantation with a focused ion beam

Parallel stripes of nanostructures on an n-type Si substrate have been fabricated by implanting 30 keV Ga⁺ ions from a focused ion beam (FIB) source at three different fluences: 1 × 10¹⁵, 2 × 10¹⁵ and 5 × 10¹⁵ ions/cm². Two sets of implantation were carried out. In one case, during implantation the substrate was held at room temperature and in the other case at 400 °C. Photoemission electron microscopy (PEEM) measurements were carried out on these samples. The implanted parallel stripes, each with a nominal dimension of 4000 × 100 nm², appear as bright regions in the PEEM image. Line scans of the intensities from PEEM images were recorded along and across these stripes. Intensity profile at the edges of a line scan is broader for the implantation carried out at 400 °C compared to room temperature. From the analysis of this intensity profile lateral diffusion coefficient of Ga in silicon was estimated assuming that the PEEM intensity is proportional to Ga concentration. The diffusion coefficient at 400 °C has been estimated to be ∼10⁻¹⁵ m²/s. No significant dependence of diffusion coefficient on ion fluence was observed in the fluence range investigated here. Radiation enhanced diffusion has been discussed in the light of the associated defect distribution due to lateral straggling of the implanted ions.     

Channeling study of thermal decomposition of III-N compound semiconductors

GaN thermal stability is the limiting factor of the growth rate for epitaxially grown films and of the thermal annealing of defects. As a consequence, this issue has been extensively studied for more than one decade. There are, however, substantial differences in the reported kinetics and presumed mechanisms of decomposition, which are primarily related to the reactor design thus, reflecting the complexity of chemical reactions involved. We report here on the use of 1.7 MeV He-ion RBS/channeling for the study of thermal decomposition of MOVPE grown GaN and Al_xGa_1−xN (x = 0.05-0.5) layers. These layers with thickness of 320 nm were grown on sapphire substrates with 20 nm AlN nucleation layer. Prior to annealing samples were characterized by RBS/channeling, selected samples were also studied by SEM. Thermal treatment was performed in the MOVPE reactor in the temperature range 900-1200 °C in the N₂ atmosphere. RBS/channeling analysis provided data on layer thickness, composition and evolution of ingrown defects. GaN decomposition starts at 900 °C and results in the reduction of the layer thickness without observable changes of the film composition. The presence of large density of GaN hillocks on the surface was revealed by SEM after annealing at 1000-1050 °C. Remarkable stability of Al_xGa_1−xN was observed, this alloy remains unchanged upon annealing at 1200 °C/6 h even for x as low as 0.05.     

Structural and magnetic characterization of cobalt implanted GaN films

Cobalt ions were implanted into GaN films with multiple energies between 50 keV and 380 keV with two total fluences, 1.25 × 10¹⁶ and 1.25 × 10¹⁷ cm⁻², followed by annealing at temperatures between 600 and 850 °C. The crystal quality and surface morphology of as-implanted and subsequently annealed films were investigated by X-ray diffraction (XRD) 2θ scans, ω-rocking curve measurements and atomic force microscopy (AFM). The profiles of impurities and defects were analyzed by Rutherford backscattering spectrometry (RBS) in random and channeling configurations. The virgin GaN films have an excellent crystal quantity (χ_min = 1.4%) and in the implanted samples 60% disorder induced by ion implantation was recovered after annealing. The annealed sample become ferromagnetic, with a spontaneous magnetization of 0.1 emu/g and a coercive magnetic field of 100 Oe at 10 K, and the Curie point was found to be higher than room temperature.     

Temperature dependence of lattice disorder in Ar-irradiated (1 0 0), (1 1 0) and (1 1 1) MgO single crystals

To better appreciate dynamic annealing processes in ion irradiated MgO single crystals of three low-index crystallographic orientations, lattice damage variation with irradiation temperature was investigated. Irradiations were performed with 100 keV Ar ions to a fluence of 1 × 10¹⁵ Ar/cm² in a temperature interval from −150 to 1100 °C. Rutherford backscattering spectroscopy combined with ion channeling was used to analyze lattice damage. Damage recovery with increasing irradiation temperature proceeded via two characteristic stages separated by 200 °C. Strong radiation damage anisotropy was observed at temperatures below 200 °C, with (1 1 0) MgO being the most radiation damage tolerant. Above 200 °C damage recovery was isotropic and almost complete recovery was reached at 1100 °C. We attributed this orientation dependence to a variation of dynamic annealing mechanisms with irradiation temperature.     

First temperature stage evolution of irradiation-induced defects in tungsten studied by positron annihilation spectroscopy

The behaviour of vacancy like implantation-induced defects created in the track region of 800 keV ³He ions in polycrystalline tungsten was studied by Doppler broadening spectroscopy as a function of annealing temperature. A slow positron beam, coupled with a Doppler broadening spectrometer, was used to measure the low- and high-momentum annihilation fractions, S and W, respectively, as a function of positron energy in tungsten samples implanted at different fluences from 10¹⁴ to 5 × 10¹⁶ cm⁻². The behaviour of the S(E), W(E) and S(W) plots with the annealing temperature clearly indicates that the irradiation-induced vacancy like defects begin to evolve between 523 and 573 K, whatever the implantation fluence. This first temperature stage evolution corresponds to the migration of the monovacancies created during implantation to form larger vacancy like defects of which depth profile is different from the initial radiation-induced defects one.     

Nuclear reaction analysis of helium migration in silicon carbide

4H-SiC and 6H-SiC single crystals were implanted at room temperature with 3-MeV ³He ions at a fluence of 1 × 10¹⁶ cm⁻². Analysis of helium migration was carried out with the ³He(d, p)⁴He nuclear reaction. No clear thermally-activated migration in the end-of-range (EOR) region is found below 1100 °C, meaning that helium is strongly trapped probably in helium-vacancy clusters. At 1100 °C and above, a fraction of ³He atoms remains trapped in the clusters, but a significant fraction is detrapped into a broad distribution, which is slightly shifted towards the sample surface. Helium detrapping from the EOR region increases with increasing annealing time and temperature. Moreover, the helium content is not conserved, since a significant fraction of ³He atoms is released out of the sample. Helium out-gassing actually increases with increasing annealing time and temperature, up to about 40% at 1150 °C. No clear difference is found between the 4H-SiC and 6H-SiC polytypes.