Ion-induced electron emission – monitoring the structure transitions in graphite

The temperature dependence of ion-induced electron emission yield γ under 30 keV Ar⁺ ion impacts at incidence angles θ = 0−80° under dynamically steady-state conditions has been measured for polygranular graphite POCO-AXF-5Q. The fluencies were 10¹⁸–10¹⁹ ion/cm², the temperatures varied from the room temperature (RT) to 400 °C. The RHEED has shown that same diffraction patterns correspond to a high degree of disorder at RT. At high temperature (HT), some patterns have been found similar to those for the initial graphite surfaces. The dependence γ(T) has been found to be non-monotonic and for normal and near normal ion incidence manifests a step-like increase typical for a radiation induced phase transition. At oblique and grazing incidence (θ > 30°), a broad peak was found at T_p = 100 °C. An analysis based on the theory of kinetic ion-induced electron emission connects the behavior of γ(θ,T) to the dependence of both secondary electron path length λ and primary ion ionizing path length R_e on lattice structure that drastically changes due to damage annealing.     

Ion beam induced amorphization and recrystallization of Si/SiC/Si layer systems

Epitaxial, buried silicon carbide (SiC) layers have been fabricated in (100) and (111) silicon by ion beam synthesis (IBS). In order to study the ion beam induced epitaxial crystallization (IBIEC) of buried SiC layers, the resulting Si/SiC/Si layer systems were amorphized using 2 MeV Si²⁺ ion irradiation at 300 K. An unexpected high critical dose for the amorphization of the buried layers is observed. Buried, amorphous SiC layers were irradiated with 800 keV Si⁺ ions at 320 and 600°C, respectively, in order to achieve ion beam induced epitaxial crystallisation. It is demonstrated that IBIEC works well on buried layers and results in epitaxial recrystallization at considerably lower target temperatures than necessary for thermal annealing. The IBIEC process starts from both SiC/Si interfaces and may be accompanied by heterogenous nucleation of poly-SiC as well as interfacial layer-by-layer amorphization, depending on irradiation conditions. The structure of the recrystallized regions in dependence of dose, dose rate, temperature and crystal orientation is presented by means of TEM investigations.     

Influence of SHI irradiation on the formation of buried SiC

Silicon carbide (SiC) precipitates buried in Si(1 0 0) substrates were synthesized by ion implantation of 50 keV and 150 keV C⁺ ions at different fluences. Two sets of samples were subsequently annealed at 850 °C and 1000 °C for 30 min. Fourier transform infrared (FTIR) spectroscopy studies and X-ray diffraction (XRD) analysis confirmed formation of β-SiC precipitates in the samples. Ion irradiation with 100 MeV Ag⁷⁺ ions at room temperature does not induce significant change in the precipitates. It could be interpreted from the FTIR observations that ion irradiation may induce nucleation in Si + C solution created by ion implantation of C in Si. Modifications induced by swift heavy ion irradiation are found to be dependent on implantation energy of C⁺ ions.     

RBS studies of the lattice damage caused by 1 Me V Si implantation into Al0.3Ga0.7As/GaAs superlattices at elevated temperature

The lattice damage accumulation in GaAs and Al_0.3Ga_0.7As/GaAs superlattices by 1 MeV Si⁺irradiation at room temperature and 350°C has been studied. For irradiations at 350°C, at lower doses the samples were almost defect-free after irradiation, while a large density of accumulated defects was induced at a higher dose. The critical dose above which the damage accumulation is more efficient is estimated to be 2 × 10¹⁵ + Si/cm² for GaAs, and is 5 × 10¹⁵ Si/cm² for Al_0.8Ga_0.7As/GaAs superlattice for implantation with 1.0 MeV Si ions at 350°C. The damage accumulation rate for 1 MeV Si ion implantation in Al_0.3Ga_0.7As/GaAs superlattice is less than that in GaAs.     

Amorphization and recrystallization of the ABO3 oxides

Single crystals of the ABO₃ phases CaTiO₃, SrTiO₃, BaTiO₃, LiNbO₃, KNbO₃, LiTaO₃, and KTaO₃ were irradiated by 800 keV Kr⁺, Xe⁺, or Ne⁺ ions over the temperature range from 20 to 1100 K. The critical amorphization temperature, T_c, above which radiation-induced amorphization does not occur varied from approximately 450 K for the titanate compositions to more than 850 K for the tantalates. While the absolute ranking of increasing critical amorphization temperatures could not be explained by any simple physical parameter associated with the ABO₃ oxides, within each chemical group defined by the B-site cation (i.e., within the titanates, niobates, and tantalates), T_c tends to increase with increasing mass of the A-site cation. T_c was lower for the Ne⁺ irradiations as compared to Kr⁺, but it was approximately the same for the irradiations with Kr⁺ or Xe⁺. Thermal recrystallization experiments were performed on the ion-beam-amorphized thin sections in situ in the transmission electron microscope (TEM). In the high vacuum environment of the microscope, the titanates recrystallized epitaxially from the thick areas of the TEM specimens at temperatures of 800–850 K. The niobates and tantalates did not recrystallize epitaxially, but instead, new crystals nucleated and grew in the amorphous region in the temperature range 825–925 K. These new crystallites apparently retain some ‘memory' of the original crystal orientation prior to ion-beam amorphization.     

Damage production in GaAs during MeV ion implantation

The influence of the nuclear and electronic energy loss on the damage production in GaAs has been studied by Se⁺ ion implantation at T_I = 293 K with energies ranging from 2 MeV up to 20 MeV. The ion dose was varied between 5 × 10¹² /cm² and 1 × 10¹⁵ /cm². The damage production was investigated using RBS in channeling regime. Temperature and energy dependent backscattering measurements and TEM investigations were performed to study the kind of defects in more detail. The resulting defect profiles are compared with the depth distribution of the nuclear and electronic energy loss which were simulated by TRIM 87. The results show that the remaining defect concentration strongly decreases with increasing implantation energy even if the same energy density is deposited into nuclear processes. We suppose, that the electronic energy loss increases the defect transformation and annealing during implantation at T_I = 293 K. The defects in the samples implanted with energies greater than 5 MeV are characterized as point defects, point defect clusters and small dislocation loops; the kind of defects are the same over the whole implantation depth and the existence of amorphous zones can be widely excluded.     

X-ray yields from high-energy heavy ions channeled through a crystal: their crystal thickness and projectile dependences

X-rays emitted from Ar¹⁷⁺, Fe²⁴⁺ and Kr³⁵⁺ ions of about 400 MeV/u transmitting through a thin Si crystal of about 20 μm thickness have been measured in a planar channeling condition and compared with those in a random incident condition. We have found that the X-ray yield from Ar¹⁷⁺ ions is larger for the channeling condition than for the random incidence, while those from Fe²⁴⁺ and Kr³⁵⁺ ions are rather smaller. Such tendencies are explained by considering the projectile dependences of excitation and ionization probabilities together with X-ray emission rates. A crude simulation has qualitatively reproduced these experimental results. When the crystal thickness is small, the X-ray yield is smaller in the channeling condition than in the random incident condition, because excitation is depressed. However, for thicker crystals, the X-ray yield is larger, since the survived population of projectile-bound electrons is larger due to small ionization probabilities under the channeling condition. This inversion occurs at a specific crystal thickness depending on projectile species. Whether the thickness of the used crystal is smaller or larger than the inversion thickness determines enhancement or depression of the X-ray yield in the channeling condition.     

Ion beam enhanced etching of LiNbO3

Single crystals of z- and x-cut LiNbO₃ were irradiated at room temperature and 15 K using He⁺- and Ar⁺-ions with energies of 40 and 350 keV and ion fluences between 5 × 10¹² and 5 × 10¹⁶ cm⁻². The damage formation investigated with Rutherford backscattering spectrometry (RBS) channeling analysis depends on the irradiation temperature as well as the ion species. For instance, He⁺-irradiation of z-cut material at 300 K provokes complete amorphization at 2.0 dpa (displacements per target atom). In contrast, 0.4 dpa is sufficient to amorphize the LiNbO₃ in the case of Ar⁺-irradiation. Irradiation at 15 K reduces the number of displacements per atom necessary for amorphization. To study the etching behavior, 400 nm thick amorphous layers were generated via multiple irradiation with He⁺- and Ar⁺-ions of different energies and fluences. Etching was performed in a 3.6% hydrofluoric (HF) solution at 40 °C. Although the etching rate of the perfect crystal is negligible, that of the amorphized regions amounts to 80 nm min⁻¹. The influence of the ion species, the fluence, the irradiation temperature and subsequent thermal treatment on damage and etching of LiNbO₃ are discussed.     

Ion beam mixing of titanium films on stainless steel

The ion mixing of Ti-steel bilayers with N⁺, Ar⁺, Ti⁺, Kr⁺ and Xe⁺ ions was investigated by means of Rutherford backscattering spectroscopy (RBS). The mixing rates exhibit a linear scaling with the deposited damage energy f_D. No correlation between the properties of the mixing ion and the mixing efficiency was found. The results are compared with the predictions of ballistic and thermal-spike models.     

Ion beam synthesis and recrystallization of amorphous SiGe/SiC structures

Si_1−xGe_x amorphous layers implanted with different doses of carbon (between 5 × 10¹⁵ and 2 × 10¹⁷ cm⁻² and annealed at 700°C and 900°C have been analyzed by Raman and Infrared spectroscopies, electron microscopy and Auger electron spectroscopy. The obtained data show the synthesis of amorphous SiC by implanting at the highest doses. In these cases, recrystallization only occurs at the highest annealing temperature (900°C). The structure of the synthesized SiC strongly depends on the implantation dose, in addition to the anneal temperature. For the highest dose (2 × 10¹⁷ cm⁻²), crystalline β-SiC is formed. Finally, a strong migration of Ge towards the Si substrate is observed from the region where SiC precipitation occurs.     

Effect of forming gas anneals on the photoluminescence from nanocrystalline silicon formed by Si implantation into SiO2 matrix

The blue region of the room temperature photoluminescence spectrum from Si nanocrystallites formed in SiO₂ by Si⁺ ion implantation has been observed for the first time after annealing in a forming gas (10% H₂ + 90% N₂) ambient. Thermally grown SiO₂ on Si substrates were implanted with a dose of 2 × 10¹⁷ Si⁺ cm⁻² at energies of 200 keV and 400 keV. For reference purposes, quartz silica was implanted also with the same dose of 200 keV Si⁺ ions. The implanted samples were annealed in nitrogen and forming gas at 900°C for 3 to 180 min. Both the SiO₂ and quartz samples exhibited luminescence at about 380 nm which was weak, but detectable, before annealing. During extended anneals in forming gas, the intensity increased by a factor of about 2 above that recorded after a nitrogen anneal but the peak position was unchanged. The intensity was greater in samples annealed in forming gas which is due to the additional hydrogen. It would seem that this blue luminescence originates from new luminescent centres in the matrix caused by the Si⁺ ion implantation.     

Argon irradiation damage at a Cu/Al2O3 interface for different alumina structures

The evolution of damages at a Cu/Al₂O₃ device interface after Ar⁺ irradiation, depending on alumina structure, and the effect of surface roughness on sputtering have been studied. A polycrystalline Cu/Al₂O₃ bilayer and polycrystalline Cu on amorphous alumina were irradiated with 400 keV Ar⁺ ion beam at doses ranging from 5 × 10¹⁶ to 10¹⁷ Ar⁺/cm² at room temperature. The copper layer thicknesses were between 100 and 200 nm. RBS analysis was used to characterize the interface modification and to deduce the sputtering yield of copper. The SEM technique was used to control the surface topography. A RBS computer simulation program was used to reproduce experimental spectra and to follow the concentration profile evolutions of different elements before and after ion irradiation. A modified TRIM calculation program which takes into account the sputtering yield evolution as well as the concentration variation versus dose gives a satisfactory reproduction of the experimental argon distribution. The surface roughness effect on sputtering and the alumina structure influence at the interface on mixing mechanisms are discussed.     

Enthalpy and heat capacity of LiAlO2 between 298 and 1700 K by drop calorimetry

The enthalpy of γ-LiAlO₂ was measured between 403 and 1673 K by isothermal drop calorimetry. The smoothed enthalpy curve between 298 and 1700 K results in H⁰(T) − H⁰(298 K)=−37 396 + 93.143 · T + 0.00557 · T² + 2 725 221 · T⁻¹ J/mol. The standard deviation is 2.2%. The heat capacity was derived by differentiation of the enthalpy curve. The value extrapolated to 298 K is C_p,298=(65.8 ± 2.0) J/K mol.     

Surface morphology of the Ar ion-irradiated Ag/Si(1 1 1) system

In the present study, a 500 Å thin Ag film was deposited by thermal evaporation on 5% HF etched Si(1 1 1) substrate at a chamber pressure of 8×10⁻⁶ mbar. The films were irradiated with 100 keV Ar⁺ ions at room temperature (RT) and at elevated temperatures to a fluence of 1×10¹⁶ cm⁻² at a flux of 5.55×10¹² ions/cm²/s. Surface morphology of the Ar ion-irradiated Ag/Si(1 1 1) system was investigated using scanning electron microscopy (SEM). A percolation network pattern was observed when the film was irradiated at 200°C and 400°C. The fractal dimension of the percolated pattern was higher in the sample irradiated at 400°C compared to the one irradiated at 200°C. The percolation network is still observed in the film thermally annealed at 600°C with and without prior ion irradiation. The fractal dimension of the percolated pattern in the sample annealed at 600°C was lower than in the sample post-annealed (irradiated and then annealed) at 600°C. All these observations are explained in terms of self-diffusion of Ag atoms on the Si(1 1 1) substrate, inter-diffusion of Ag and Si and phase formations in Ag and Si due to Ar ion irradiation.     

Microstructural characterization of amorphized and recrystallized 6H-SiC

The mode of recrystallization of 6H-SiC implanted at 200 keV with a dose of 1 × 10¹⁵ Ge⁺ cm⁻² and subsequently annealed at 1500°C for 10 min, was studied by combined cross-section and planar view transmission electron microscopy techniques. The type of defects developed during recrystallization and their role in the 6H to 3C (cubic) transformation of the recrystallized zone is discussed. The instability of the 6H-SiC polytype and the domination of the 3C-SiC is attributed to the inability to apply the step-controlled growth mechanism, which is essential for the growth of 6H-SiC, in the amorphous zone.     

A comparative EPR study of ion implantation induced damage in Si, Si1−xGex (x ≠ 0) and SiC

Electron Paramagnetic Resonance (EPR) measurements have been made to investigate the build up of damage in silicon in relaxed crystalline Si_1−xGe_x (x = 0.04, 0.13, 0.24, 0.36) and in 6H-SiC as a result of increasing the ion dose from low levels (10¹² cm⁻²) up to values (10¹⁵ cm⁻²) sufficient to produce an amorphous layer. Si, Si_1−xGe_x (x ≠ 0) and SiC were implanted at room temperature with 1.5 MeV Si, 2 MeV Si and 0.2 MeV Ge ions respectively. A comparison is made between the ways in which the type and population of paramagnetic defects depend on ion dose for each material.     

Standard Gibbs energy of formation of Cs2CdI4

The vapor pressures of CdI₂ and Cs₂CdI₄ were measured below and above their melting points, employing the transpiration technique. The standard Gibbs energy of formation Δ_fG° of Cs₂CdI₄, derived from the partial pressure of CdI₂ in the vapor phase above and below the melting point of the compound could be represented by the equations Δ_fG°Cs₂CdI₄ (±6.7) kJ mol⁻¹=−1026.9+0.270 T (643 K≤T≤693 K) and Δ_fG°{Cs₂CdI₄} (±6.6) kJ mol⁻¹=−1001.8+0.233 T (713 K≤T≤749 K) respectively. The enthalpy of fusion of the title compound derived from these equations was found to be 25.1±10.0 kJ mol⁻¹ compared to 36.7 kJ mol⁻¹ reported in the literature from differential scanning calorimetry (DSC). The standard enthalpy of formation Δ_fH°_298.15 for Cs₂CdI₄ evaluated from these measurements was found to be −918.0±11.7 kJ mol⁻¹, in good agreement with the values −920.3±1.4 and −917.7±1.5 kJ mol⁻¹ reported in the literature from two independent calorimetric studies.     

Carbon ion-implanted optical waveguides in Nd:YLiF4 crystal: Refractive index profiles and thermal stability

We report on the optical planar waveguides in Nd:YLiF₄ laser crystals fabricated by 6.0 MeV C³⁺ ion implantation at doses of 1 × 10¹⁵ or 2.5 × 10¹⁵ ions/cm², respectively. The refractive index profiles, which are reconstructed according to the measured dark mode spectroscopy, show that the ordinary index had a positive change in the surface region, forming non-leaky waveguide structures. The extraordinary index is with a typical barrier-shaped distribution, which may be mainly due to the nuclear energy deposition of the incident ions into the substrate. In order to investigate the thermal stability of the waveguides, the samples are annealed at temperature of 200–300 °C in air. The results show that waveguide produced by higher-dose carbon implantation remains relatively stable with post-irradiation annealing treatment at 200 °C in air.     

Recrystallization of almost fully amorphous zircon under hydrothermal conditions: An infrared spectroscopic study

Hydrothermal experiments were carried out with powder from an almost fully amorphous, natural zircon under various P–T–t conditions mainly in a 0.1 N HCl solution. Powder infrared spectroscopic measurements on the experimental products reveal that first structural changes occurred at a fluid temperature as low as 75 °C. Significant recrystallization started at 200 °C, as indicated by an increase in the absorption intensity of the zircon fundamental IR bands and the formation of sharp OH stretching bands at 3385 and 3420 cm⁻¹. Although the powder has fully reacted at 400 °C, the zircon fundamental absorption bands are not fully recovered, indicating the occurrence of significant amounts of amorphous remnants. The experimental results in neutral to acidic solutions are consistent with the idea that water (H⁺ and possibly H₂O) diffuses into the amorphous network where it ‘catalyses’ solid state recrystallization. During this process, Zr and Si were leached from the amorphous network.     

Optical and structural behaviour of Mn implanted sapphire

Sapphire single crystals were implanted at room temperature with 180 keV manganese ions to fluences up to 1.8 × 10¹⁷ cm⁻². The samples were annealed at 1000 °C in oxidizing or reducing atmosphere. Surface damage was observed after implantation of low fluences, the amorphous phase being observed after implantation of 5 × 10¹⁶ cm⁻², as seen by Rutherford backscattering spectroscopy under channelling conditions. Thermal treatments in air annealed most of the implantation related defects and promoted the redistribution of the manganese ions, in a mixed oxide phase. X-ray diffraction studies revealed the presence of MnAl₂O₄. On the contrary, similar heat treatments in vacuum led to enhanced out diffusion of Mn while the matrix remained highly damaged. The analysis of laser induced luminescence performed after implantation showed the presence of an intense red emission.