Structural characterization of amorphous Fe–Si and its recrystallized layers

We have synthesized amorphous Fe–Si thin layers and investigated their microstructure using transmission electron microscopy (TEM). Si single crystals with (1 1 1) orientation were irradiated with 120 keV Fe⁺ ions to a fluence of 4.0 × 10¹⁷ cm⁻² at cryogenic temperature (120 K), followed by thermal annealing at 1073 K for 2 h. A continuous amorphous layer with a bilayered structure was formed on the topmost layer of the Si substrate in the as-implanted specimen: the upper layer was an amorphous Fe–Si, while the lower one was an amorphous Si. After annealing, the amorphous bilayer crystallized into a continuous β-FeSi₂ thin layer.     

Effect of Si implantation on the microstructure of silicon nanocrystals and surrounding SiO2 layer

Si nanocrystals (Si-nc) embedded in a SiO₂ layer have been characterized by means of transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). For local Si concentration in excess  8 × 10²¹ Si⁺/cm³, the size of the Si-nc was found to be 3 nm and comparatively homogeneous throughout the whole implanted layer. For local Si concentration in excess of 2.4 × 10²² Si⁺/cm³, the Si-nc diameter ranges from 2 to 12 nm in the sample, the Si-nc in the middle region of the implanted layer being bigger than those near the surface and the bottom of the layer. Also, Si-nc are visible deeper than the implanted depth. Characterization by XPS shows that a large quantity of oxygen was depleted from the first 25 nm in this sample (also visible on TEM image) and most of the SiO₂ bonds have been replaced by Si–O bonds. Experimental and simulation results suggest that a local Si concentration in excess of 3 × 10²¹ Si/cm³ is required for the production of Si-nc.     

Channeled ion beam synthesis: a new technique for forming high-quality rare-earth silicides

High dose ¹⁶⁶Er or ¹⁶⁰Gd implantations are used to form rare-earth (RE) silicides in Si. After implanting 0.8−2.0 × 10¹⁷ at./cm² with 90 keV into Si(111) substrates kept at 450 to 530°C, we found that using conventional non-channeled implantation (tilted over 7°), it is impossible to form a continuous RESi_1.7 layer. On the contrary, using channeled implantation, a continuous epitaxial ErSi_1.7 layer with very good crystalline quality can be synthesized; a lowest χ_min value of 1.5% for a surface ErSi_1.7 layer is obtained. This different behaviour is explained using a model based on the difference in implantation depth, defect density and sputtering yield between random and channeled implantation, and the results are compared with Monte Carlo simulations. Such a high-quality RESi_1.7/Si system offers a rare opportunity to study the structure, orientation and strain comprehensively using Rutherford backscattering and channeling spectrometry, X-ray diffraction and TEM. We found that the azimuthal orientation of the hexagonal RESi_1.7 layer to the cubic Si substrate is RESi_1.7[0001]/t|Si[111] and RESi_1.7{11 0}/t|Si{110}. It is further observed that the ErSi_1.7 epilayer is compre strained and quasi-pseudomorphic. In the case of GdSi_1.7, the most difficult rare-earth silicide to form, and enhanced stabilization of the hexagonal over the orthorhombic phase is observed.     

Heavy ion irradiation effects in the rare-earth sesquioxide Dy2O3

Polycrystalline pellets of the rare-earth sesquioxide Dy₂O₃ with cubic C-type rare-earth structure were irradiated with 300 keV Kr²⁺ ions at fluences up to 5 × 10²⁰ Kr/m² at cryogenic temperature. Irradiation-induced microstructural evolution is characterized using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). In previous work, we found a phase transformation from a cubic, C-type to a monoclinic, B-type (C2/m) rare-earth structure in Dy₂O₃ during Kr²⁺ ion irradiation at a fluence of less than 1 × 10²⁰ Kr/m². In this study, we find that the crystal structure of the top and middle regions of the implanted layer transform to a hexagonal, H-type (P6₃/mmc) rare-earth structure when the irradiation fluence is increased to 5 × 10²⁰ Kr/m²; the bottom of the implanted layer, on the other hand, remains in a monoclinic phase. The irradiation dose dependence of the C-to-B-to-H phase transformation observed in Dy₂O₃ appears to be closely related to the temperature and pressure dependence of the phases observed in the phase diagram. These transformations are also accompanied by a decrease in molecular volume (or density increase) of approximately 9% and 8%, respectively, which is an unusual radiation damage behavior.     

Molecular dynamics simulation of fluorine ion etching of silicon

Formation of precursors and desorption of etching products by fluorine ion irradiation were studied using molecular dynamics (MD) simulation. When F atoms impact sequentially on a Si substrate, a mixed layer of F and Si atoms is formed on the surface. When the incident energy is below 30 eV, the fluorine coverage reaches steady state after 1.0×10¹⁶ atoms/cm² irradiation. The ratio of F to Si in the mixed layer is about 1:1. At an incident energy of 15 eV, the mixed layer at steady state consists of 4.5 ML of fluorine with a depth of 20 Å and the main etching products are SiF₃ and SiF₄. At 30 eV incident energy, the mixed layer at steady state is 6.5 ML with a depth of 40 Å and the main etching products are SiF₂ and SiF₃. When F atoms were irradiated onto a Si substrate heated at 1000 K, a significant reduction of F coverage was observed due to diffusion of F atoms.     

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.     

Neutron-irradiation effect in ceramics evaluated from macroscopic property changes in as-irradiated and annealed specimens

Macroscopic length (linear swelling) and thermal diffusivity changes were measured for heavily neutron-irradiated -Al₂O₃, AlN, β-Si₃N₄ and β-SiC that were irradiated under the same capsule to compare the difference between these materials. And in addition, several capsules were irradiated under different temperatures (646–1039 K) and to different neutron doses (0.4–8.0 × 10²⁶ n/m²) in the Japanese experimental fast reactor JOYO. The swelling and the thermal diffusivity of as-irradiated specimens showed some dependence on the neutron-irradiation dose and the irradiation temperature, and that indicates stability under neutron-irradiation environments. Alpha-Al₂O₃ and AlN showed relatively large swelling and degradation of thermal diffusivity than β-Si₃N₄ and β-SiC. This difference is related to the crystal structure of each material. The dependence of swelling on irradiation dose, that is, -Al₂O₃ showed linear inclination but β-Si₃N₄ and β-SiC showed saturation, supports the model of defect structures. In addition, annealing behaviors of swelling and thermal diffusivity were compared to analyze the behavior of defects at higher temperature.     

Characterization of extended defects in SiGe alloys formed by high dose Ge implantation into Si

The synthesis of SiGe/Si heterostructures by Ge⁺ ion implantation is reported. 400 keV Ge⁺ ions were implanted at doses ranging from 3 × 10¹⁶ to 10 × 10¹⁶ ions/cm² into (001) Si wafers, followed by Si⁺ amorphisation and low temperature Solid Phase Epitaxial Regrowth (SPER). TEM investigations show that strained alloys can be fabricated if the elastic strain energy (E_el) of the SiGe layer does not exceed a critical value (E′_el) of about 300 mJ/m², which is independent of the implantation energy. Our analysis also suggests that “hairpin” dislocations are formed as strain relieving defects in relaxed structures. A “strain relaxation” model is proposed to explain their formation.     

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.     

Standard molar Gibbs free energy of formation of PbO(s) over a wide temperature range from EMF measurements

The EMF of the following galvanic cells,

(render)

Kanthal,Re,Pb,PbOCSZO₂ (1 atm.),Pt

(render)

Kanthal,Re,Pb,PbOCSZO₂(1 atm.),RuO₂,Pt

were measured as a function of temperature. With O₂ (1 atm.), RuO₂ as the reference electrode, measurements were possible at low temperatures close to the melting point of Pb. Standard Gibbs energy of formation, Δ_fG⁰_mβ-PbO was calculated from the emf measurements made over a wide range of temperature (612–1111 K) and is given by the expression: Δ_fG⁰_mβ-PbO±0.10 kJ=−218.98+0.09963T. A third law treatment of the data yielded a value of −218.08 ± 0.07 kJ mol⁻¹ for the enthalpy of formation of PbO(s) at 298.15 K, Δ_fH⁰_mβ-PbO which is in excellent agreement with second law estimate of −218.07 ± 0.07 kJ mol⁻¹.     

Neutralization rate for slow Ar ions in front of KCl(0 0 1)

Charge state distributions of reflected ions are measured when 5 keV Ar^q+(q = 0−2) ions are incident on a clean KCl(0 0 1) surface at grazing angle, θ_i. Although the charge state distribution does not depend on the incident charge state at larger θ_i, significant dependence of the charge state distribution on incident charge state is observed at smaller θ_i. The ionization of Ar⁰ is completely suppressed at θ_i < 20 mrad, while large neutralization probability is observed for Ar⁺ incidence. These features allow us to derive the position-dependent neutralization rate of Ar⁺ in front of KCl(0 0 1). The obtained neutralization rate decreases exponentially with distance from the surface as it is usually assumed.     

Loop formation by ion irradiation in yttria stabilized zirconia

Yttria stabilized zirconia (YSZ) is a candidate material focused as optical and insulating materials in nuclear reactors. Therefore, it is useful to investigate defect formation during irradiation, in order to assess YSZ resistance to radiation damage. In the present study, in situ transmission electron microscopy (TEM) observations were performed on YSZ during 30 keV Ne⁺ ion irradiation in the temperature range of 723–1123 K (using 100 K intervals). Results revealed that damage evolution morphology depends on irradiation temperature. For irradiations below 1023 K, defect clusters and bubbles were formed simultaneously. On the other hand, at 1123 K, only bubbles were formed in the initial stage of irradiation. Loops formed later following the bubble formation. It was also observed that, in the early stage of irradiation above 923 K, larger bubbles were formed along the loop planes compared with other areas.

TEM observations indicated that dislocation loops formed on three kinds of crystallographic planes: namely, {1 0 0}, {1 1 1} and {1 1 2} planes.     

High resolution channeling contrast microscopy and channeling analysis of SiGe quantum well structures

High resolution channeling contrast microscopy (CCM) and channeling measurements were carried out to characterize SiGe quantum well structures on micron thick graded layers (i.e. virtual substrates). The virtual substrates were grown by gas source molecular beam epitaxy at a pressure of 10⁻⁵ mbar and low pressure chemical vapor deposition at 10⁻² mbar on boron doped Si(0 0 1) substrates respectively. A homoepitaxial silicon buffer layer was grown prior to the deposition. The nominal structure is a 20 nm Si_0.75Ge_0.25 layer at the surface, followed by 10 nm pure Si, 500 nm Si_0.75Ge_0.25 and a 1000 nm thick graded SiGe (0–26%) layer. RBS was used to measure the depth profiles, and angular scans around the (1 0 0) axis were carried out to assess crystal and interface quality. CCM was used to acquire depth resolved images of micron-sized lateral inhomogenities (‘cross-hatch') present on both samples.     

A TEM study of D -implanted Cu following Ar-ion milling: Microstructure and epitaxial Cu2O formation

In examining the microstructure of TEM specimens prepared from D⁺-implanted Cu for the presence of bubbles it was found that cuprous oxide (Cu₂O) layers had formed over large areas of the specimen surfaces. The Cu was irradiated at normal incidence with 200 keV D⁺ ions at a temperature of 120 K to a dose of ˜2 × 10²¹ D⁺/m². Ar⁺ ion milling at 330 K was used to erode irradiated surfaces to various depths prior to chemical back-thinning in a jet electropolishing bath. There was no evidence for the formation in the Cu of bubbles of either deuterium or argon, but dislocations at high density and planar defects were evident. Lattice fringes from {110}, {111} and {200} planes in Cu₂O and moiré patterns formed by double diffraction in the Cu and overlaid Cu₂O film were obvious features in bright-field micrographs. The moiré patterns include examples of magnified images of lattice defects.     

Effects of 160 MeV Ni ion irradiation on polypyrrole conducting polymer electrode materials for all polymer redox supercapacitor

Electronically conducting polymers are suitable electrode materials for high performance supercapacitors, for their high specific capacitance and high dc conductivity in the charged state. Supercapacitors and batteries are energy storage and conversion systems which satisfies the requirements of high specific power and energy in a complementary way. Ion beam {energy > 1 MeV} irradiation on the polymer is a novel technique to enhance or alter the properties like conductivity, density, chain length and solubility.

Conducting polymer polypyrrole thin films doped with LiClO₄ are synthesized electrochemically on ITO coated glass substrate and are irradiated with 160 MeV Ni¹²⁺ ions at different fluence 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². Dc conductivity measurement of the irradiated films showed 50–60% increase in conductivity which is may be due to increase of carrier concentration in the polymer film as observed in UV–Vis spectroscopy and other effects like cross-linking of polymer chain, bond breaking and creation of defects sites. X-ray diffractogram study shows that the degree of crystallinity of polypyrrole increases in SHI irradiation and is proportionate to ion fluence. The capacitance of the irradiated films is lowered but the capacitance of the supercapacitors with irradiated films showed enhanced stability compared to the devices with unirradiated films while characterized for cycle life up to 10,000 cycles.     

Thermochemical study of vaporization of LiTiO by a mass spectrometric Knudsen effusion method

The vaporization of Li₄TiO₄ has been studied by a mass spectrometric Knudsen effusion method in the temperature range 1082–1582 K. Identified vapors are Li(g), LiO(g), Li₂O(g) and Li₃O(g). When the vaporization proceeds, the content of Li₂O in the Li₄TiO₄ sample decreases and the condensed phase of the sample changes to β-Li₄TiO₄ plus l-Li₂TiO₃ below 1323 K, to β-Li₄TiO₄ plus h-Li₂TiO₃ in the range 1323–1473 K and to h-Li₂TiO₃ plus liquid above 1473 K. On the basis of the partial pressure data, the enthalpies of formation for β-Li₄TiO₄ from elements and from constituent oxides have been determined to be ΔH_f,298^°(β-Li₄TiO₄,s) = −2247.8 ± 14.3 kJ mol⁻¹ and Δ_fox,298^°(β-Li₄TiO₄, s) = −107.3 ± 14.3 kJ mol⁻¹, respectively.     

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.     

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.     

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.