Study of carbon material surface layers modified by nitrogen and argon ion irradiation

We present the results of the study of the elemental composition and defects of the electronic structure of the surface layer modified by high-dose irradiation (10¹⁸–10¹⁹ ion/cm²) of highly oriented pyrolytic graphite (UPV-1T) by 30-keV N ₂ ⁺ and Ar⁺ ions in the temperature range from 180 to 400°C. The EPR spectra observed during irradiation with argon ions at high temperatures and with nitrogen ions at temperatures near the liquid-nitrogen temperature T = 77 K exhibit anomalously narrow lines which probably result from the exchange interaction inside paramagnetic clusters of displaced carbon atoms. During nitrogen ion irradiation at room and higher temperatures, paramagnetic defects typical of many carbon materials (single EPR lines with g = 2.0027–2.0029) and belonging to carbon atoms bound to one or three nitrogen atoms were detected.     

Sputtering of highly oriented pyrolytic graphite with 30 keV Argon ions

The influence of the incidence angle of 30 keV Ar⁺ ions, ion fluence and target temperature on the sputtering yield and surface microgeometry of highly oriented pyrolytic graphite (UPV-1T) samples was experimentally studied. It was found that at fluences more than 5 × 10¹⁹ ion cm^?2 the sputtering yield at room temperature in the range of the ion incidence angle from 0° to 80° is twice as small as the corresponding experimental data for both polycrystalline graphite and glassy carbon. The analysis of ion-induced relief permits us to suppose the topographical suppression mechanism of highly oriented pyrolytic graphite sputtering.     

Temperature dependences of the ion-electron emission of glassy carbons under 30-keV argon ion irradiation

The temperature dependences (?200°C < T ≤ 350°C) of the ion-induced electron emission yield γ and the structures of modified surface layers have been studied experimentally for SU-850, SU-1000, SU-1300, SU-2000, and SU-2500 glassy carbons under high-dose 30-keV Ar⁺ and N ₂ ⁺ ion irradiation. Glassy carbons manufactured using a relatively high heat-treatment temperature T _ht exhibit a stepwise increase in the electron yield at certain annealing temperatures T _a. The same behavior is observed for graphitized carbon materials. For low-temperature glassy carbons, the electron yield exhibits a monotonic increase with increasing irradiation temperature. The observed differences are related to the occurrence of different structural types of fullerene-like nanoparticles in the low-and high-temperature glassy carbons.     

Sputtering of metals at ion-electron irradiation

It has been found that, in contrast to the commonly accepted opinion, simultaneous irradiation by 15-keV Ar⁺ ions and 2.5-keV electrons at temperatures above 0.5T _m (T _m is the melting temperature) induces much larger sputtering of metallic copper, nickel, and steel than irradiation only by Ar⁺ ions. The effect increases with the temperature. At T = 0.7T _m, the sputtering coefficients in the case of ion-electron irradiation are more than twice as large as the sputtering coefficients in the case of irradiation by Ar⁺ ions. The experiments on the sublimation of copper show that the sublimation rate in the case of the heating of a sample by an electron beam is higher than that in the case of heating in an electric vacuum oven. The revealed effects are explained by the electron-induced excitation of adatoms (atoms stuck over the surface, which appear owing to ion bombardment). Excited adatoms have a smaller binding energy with the surface and are sputtered more easily.     

Characterization of silicon doped with sodium upon high-voltage implantation

The depth distribution profiles of sodium atoms in silicon upon high-voltage implantation (ion energy, 300 keV; implantation dose, 5 × 10¹⁴ and 3 × 10¹⁵ cm ^?2) are investigated before and after annealing at temperatures in the range T _ann = 300–900°C (t _ann = 30 min). Ion implantation is performed with the use of a high-resistivity p-Si (ρ= 3–5 kΩ cm) grown by floating-zone melting. After implantation, the depth distribution profiles are characterized by an intense tail attributed to the incorporation of sodium atoms into channels upon their scattering from displaced silicon atoms. At an implantation dose of 3 × 10¹⁵ ions/cm², which is higher than the amorphization threshold of silicon, a segregation peak is observed on the left slope of the diffusion profile in the vicinity of the maximum after annealing at a temperature T _ann = 600°C. At an implantation dose of 5 × 10¹⁴ ions/cm², which is insufficient for silicon amorphization, no similar peak is observed. Annealing at a temperature T _ann = 700°C leads to a shift of the profile toward the surface of the sample. Annealing performed at temperatures T _ann ≥ 800°C results in a considerable loss of sodium atoms due to their diffusion toward the surface of the sample and subsequent evaporation. After annealing, only a small number of implanted atoms that are located far from the region of the most severe damages remain electrically active. It is demonstrated that, owing to the larger distance between the diffusion source and the surface of the sample, the superficial density of electrically active atoms in the diffusion layer upon high-voltage implantation of sodium ions is almost one order of magnitude higher than the corresponding density observed upon low-voltage implantation (50–70 keV). In this case, the volume concentration of donors near the surface of the sample increases by a factor of 5–10. The measured values of the effective diffusion parameters of sodium at annealing temperatures in the range T _ann = 525–900°C are as follows: D ₀ = 0.018 cm²/s and E _a = 1.29 eV/kT. These parameters are almost identical to those previously obtained in the case of low-voltage implantation.     

Kossel lines in angular distribution of X-rays excited by protons in pyrolytic graphite quasi-crystal

Kossel line profiles were experimentally studied upon 1.5-MeV proton excitation of characteristic K _α radiation of argon atoms implanted into an UPV-1T graphite quasi-crystal. It was found that Kossel line profiles depend on argon ion implantation conditions, i.e., the lines generated in crystals implanted at temperatures of 150 and 200°C exhibit different widths and contrasts. In addition to the main Kossel cone line, a second cone line was detected caused by an additional texture component in the UPV-1T pyrolytic graphite quasi-crystal.     

Variety of LaSrMnO structures induced by growth conditions and laser irradiation

Crystallographic phase transitions in perovskite-like LaSrMnO metallic oxides are studied. The transitions are induced when internal stresses generated during film synthesis (at temperatures between 450 and 730°C) vary (decrease or increase) upon subsequent irradiation by a KrF laser emitting in the UV range. As the synthesis temperature T _s grows, the rhombohedral-to-orthorhombic phase transition occurs at 650–670°C. The resistivity is shown to be either temperature-independent, ρ(T)=const, at T<T _crit, or varies and reaches a maximum, ρ(T)=ρ_max, at the Curie temperature T _c. Optical transmission spectra taken at photon energies ℏω=0.5–2.5 eV exhibit both a high (0.8–0.9) and low (0.1–0.3) transmission coefficient t, depending on the synthesis temperature. As follows from X-ray diffraction data, the laser irradiation causes a phase transition only in LaSrMnO films grown at T _s<650°C. Phases of different size scales appear: the long-range-order orthorhombic matrix and mesoscopic-range-order rhombohedral clusters are observed in the films grown at T _s=450–550°C and the rhombohedral matrix with orthorhombic clusters, in the films grown at T _s=550–650°C.     

Structural and Morphological Changes of Carbon Fiber Surfaces,Produced via Sputtering by Noble Gas Ions

SEM, laser goniophotometry, and Raman spectroscopy are used to analyze a modification of the carbon PAN fiber shell of KUP-VM composite upon irradiation with 30 keV Ne⁺ and Ar⁺ ions at normal incidence and temperatures of RT to 600°C. It is found that the formation of corrugated submicron structures in the composite upon irradiation at elevated temperatures (≥125°C for neon and ≥250°C for argon) displays certain features at temperatures of 400–500°C. The corrugated faces’ angles of inclination and the fraction of the corrugated structure on the fiber surface at these temperatures are minimal. Together with regularities established earlier, the observed patterns allow us to relate ion-induced corrugation to anisotropic radiation- induced plastic processes of dimensional changes in carbon materials affected by ion sputtering of their surfaces.     

Graphitization of a Polycrystalline Diamond under High-Fluence Irradiation with Noble Gas and Nitrogen Ions

To analyze the process of the ion-induced graphitization of a polycrystalline diamond, the surfacelayer conductivity and microstructure are studied experimentally after high-fluence irradiation with Ne⁺, Ar⁺, N⁺, and ions with energies of 20–30 keV at irradiation and heat-treatment temperatures ranging from 30 to 720°R in vacuum. After irradiation with argon ions at room temperature and subsequent heat treatment, the resistivity ? of a modified layer decreases exponentially with increasing treatment temperature T _ht and reaches the graphite value ? at Tht = 700°R. Such a temperature T _ht is insufficient for surface-layer graphitization by nitrogen ions. The increase in the diamond temperature under irradiation leads to a decrease in the ion-induced thermal graphitization temperature T _g by several hundred degrees. It is found that the temperature T _g is almost coincident with the corresponding temperature T_a of the dynamic annealing of radiation-induced damage in graphite. Analysis of the irradiated layer using Raman spectroscopy reveals the heterogeneous structure of the modified layer containing graphite and amorphous phases, the ratio between which correlates with the layer resistivity. Under argon-ion irradiation at diamond temperatures of 500°R or more, an increase in ? of the irradiated layer is observed, which is related to the formation of nanocrystalline graphite. This effect is not observed under nitrogen-ion irradiation.     

Relation between surface structures and sputtering ratios of copper single crystals

Polished (100) Cu crystals have been bombarded at target temperatures of 204 K, 294 K and 456 K by 10 and 20 keV Ne⁺ ions up to a total dose of 1.7 × 10¹⁹ ions/cm². The plane of incidence was chosen to be a {100} plane perpendicular to the surface. Measurements have been performed for incident angles between 36° and 44° with respect to the surface normal. In this angular interval the sputtering ratio and the surface structure have been studied by weightloss and replica electron microscope techniques respectively. At target temperatures of 204 K and 294 K an anomaly was observed in the curve of the sputtering ratio versus angle of incidence. A small peak appears where the curve slopes towards the 〈110〉 minimum. The position and height of the peak is a function of target temperature and ion energy.

This sputtering submaximum is accompanied by the formation of {100} orientated furrows perpendicular to the ion beam. The nucleation of this relief is tentatively discussed in terms of local deviations from perfection of the surface, which might be due to a singularity in the production of focusing collisions influencing the damage structure. The growth of the furrows and the submaximum in the sputtering ratio are discussed in terms of the angle between the ion beam and the characteristic {110} side of the furrows.

These sputtering and faceting phenomena have not been observed at 20 keV Ar⁺ ion bombardment nor generally under bombardment at a target temperature of 456 K.     

Nitrogen 1s electron binding energy assignment in carbon nitride thin films with different structures

Carbon nitride thin films deposited by dc unbalanced magnetron sputtering have been analyzed by high-resolution X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The XPS data show that N 1s binding states depend on substrate temperature (T_s). By comparison with the Raman spectra, N 1s binding states are assigned in which nitrogen atoms are mainly bound to sp² and sp³ carbon atoms at T_s = 100°C, whereas at T_s = 500°C nitrogen atoms are mainly bonded to sp², sp³ and sp¹ carbon atoms.     

Structure-mediated transition in the behavior of elastic and inelastic properties of beach tree bio-carbon

Microstructural characteristics and amplitude dependences of the Young modulus E and of internal friction (logarithmic decrement δ) of bio-carbon matrices prepared from beech tree wood at different carbonization temperatures T _carb ranging from 600 to 1600°C have been studied. The dependences E(T _carb) and δ(T _carb) thus obtained revealed two linear regions of increase of the Young modulus and of decrease of the decrement with increasing carbonization temperature, namely, ΔE ～ AΔT _carb and Δδ ～ BΔT _carb, with A ≈ 13.4 MPa/K and B ≈ ?2.2 × 10^?6 K^?1 for T _carb < 1000°C and A ≈ 2.5 MPa/K and B ≈ ?3.0 × 10^?7 K^?1 for T _carb > 1000°C. The transition observed in the behavior of E(T _carb) and δ(T _carb) at T _carb = 900–1000°C can be assigned to a change of sample microstructure, more specifically, a change in the ratio of the fractions of the amorphous matrix and of the nanocrystalline phase. For T _carb < 1000°C, the elastic properties are governed primarily by the amorphous matrix, whereas for T _carb > 1000°C the nanocrystalline phase plays the dominant part. The structurally induced transition in the behavior of the elastic and microplastic characteristics at a temperature close to 1000°C correlates with the variation of the physical properties, such as electrical conductivity, thermal conductivity, and thermopower, reported in the literature.     

Study of near surface layer of graphite produced by nitrogen ion bombardment at high doses

To study the modified surface layers of graphites and deposited films of sputtered material, the dependences of sputtering yield Y , and ion-electron emission coefficient γ on ion incidence angle and target temperature under high dose 30 keV N⁺ ₂ ion irradiation have been measured. In the angular range θ=0-80° Y and γ increase approximately as inverse cosθ, Y of POCO-AXF-5Q are 1.5 times larger than of MPG-LT. The dependences of γ (T) manifests a step-like behaviour typical for the radiation induced phase transitions. EPR analysis shows that at near room temperatures the point electron defects are typical of carbon and the defects due to carbon atoms interacting with 14 N nuclei. At elevated temperatures (≥ 300°C) there are the defects typical of graphite-like structures. The films deposited on glass collectors shows for cold targets only the defects typical of carbon, for the heated graphites - also the defects associated with C-¹⁴N nuclei interaction.     

Vortex structure and anisotropy of electric resistance in Bi2Sr1.65La0.35CuO6 + δ single crystals

The vortex structure of Bi₂Sr_1.65La_0.35CuO_6+δ single crystals in tilted magnetic fields has been studied by the decoration method. From the observed pattern of vortex chains in the basal plane, the parameter of anisotropy in the superconducting state has been estimated as γ_S = 460 ± 40. The electric resistance of Bi₂Sr_1.65La_0.35CuO_6+δ single crystals has been studied in a broad range of temperatures (T _c < T < 300 K) and magnetic fields (up to 16 T). The ratio of resistivities in the direction perpendicular to the basal plane and in plane near the critical temperature T _c amounted to ρ⊥/ρ‖ = 3.2 × 10⁵. A possible relationship between the anisotropy in the normal and superconducting states is discussed.     

Anomalous thermoelastic behaviour of cubic potassium cyanide

The temperature dependence of all elastic constants of cubic potassium cyanide has been measured by ultrasonic methods in the range from -105.4 to 181°C. Until about 180°C all elastic wave velocities increase with higher temperatures. The behaviour of the shear constant c₄₄ is given by c₄₄ = a · logT/T₀ with a = 0.219 · 10¹¹dyn.cm^?2 and T₀ = 153.7°K with a good approximation. These unusual effects are assigned to the librational vibrations and orientational jumping processes of the CN-ions. The phase transition at -105.5°C is a consequence of the low c₄₄ value.     

Superconductivity of niobium nitride single crystals after implantation of carbon and nitrogen

Single crystals of δ-NbN_0.85 with a superconducting transition temperature T_c of 14.3 K were implanted with nitrogen and carbon ions at room temperature and subsequently annealed at high temperatures. Implantation was also performed at high substrate temperatures. After implantation at about 920°C maximum T_c-values of 16.5 and 17.8 K were obtained with N- and C-ions respectively. Disorder observed after room temperature implantation consisted of displaced Nb-atoms which could not be completely annealed in an isochromous annealing process up to 1000°C. For annealing temperatures above 1100°C nitrogen diffusion out of the implanted layers resulted in a reduction of T_c.     

The effects of irradiation temperature and preinjected gases on voids in aluminum

Voids in high purity aluminum irradiated to a fast (E>1 MeV) fluence of 4 × 10²⁰ n/cm² at 125 (0.43T _m) and 150°C (0.45T _m) are fewer in number but very much larger in size than those in material irradiated at 55°C (0.35T _m). Additionally, at 125 and 150°C, the voids adopt a variety of shapes including plates, ribbons, cylinders and more equiaxed polyhedra, and are frequently associated with particles of transmutation-produced silicon. At the higher temperatures voids are larger near grain boundaries than in grain interiors. Injection of hydrogen or helium prior to irradiation causes an increase in the number of voids and a corresponding decrease in size in specimens irradiated at 150°C; 3 at. ppm He is more effective than either 3 or 9 at. ppm H. The gases do not appear to influence swelling.

A commercial purity (99 per cent) aluminum subjected to the same irradiation treatments did not develop voids whether preinjected with gases or not; the visible radiation damage consisted solely of small loops on or near grown-in dislocations.     

Metal-insulator transition in a radiation-disordered La<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> manganite

The temperature dependences of the electrical resistivity ρ(T) and the ac magnetic susceptibility χ(T, H = 0) are thoroughly investigated for a perovskite-like lanthanum manganite, namely, La_0.85Sr_0.15MnO₃, which is preliminarily exposed to neutron irradiation with a fluence _F = 2 × 10¹⁹ cm^?2 and then annealed at different temperatures ranging from 200 to 1000°C. The results of the electrical resistance measurements demonstrate that neutron irradiation of the samples leads to the disappearance of the low-temperature insulating phase. As the annealing temperature increases, the insulating phase is not restored and the manganite undergoes a transformation into a metallic phase. Analysis of the magnetic properties shows that, under irradiation, the ferromagnet-paramagnet phase transition temperature T_C decreases and the magnetic susceptibility is reduced significantly. With an increase in the annealing temperature, the phase transition temperature T_C and magnetic susceptibility χ(_{T, H} = 0) increase and gradually approach values close to those for an unirradiated sample. This striking difference in the behavior of the electrical and magnetic properties of the radiation-disordered La_0.85Sr_0.15MnO₃ manganite is explained qualitatively.     

Effect of pre-annealing on NO32- centers in synthetic hydroxyapatite

Effect of pre-annealing of synthetic hydroxyapatite (HAP) on properties of γ- and UV- induced NO₃^2- centers was studied by electron paramagnetic resonance (EPR). Nitrate-containing hydroxyapatite powders ((N)HAP)) and the powders with an admixture of carbonate and nitrate ions ((C,N)HAP) were annealed in the temperature range T_ann = 20 °C ? 600 °C before irradiation. It was found that pre-annealing of (N)HAP samples changes the parameters of NO₃^2- centers while no changes took place in (C,N)HAP. Moreover, at the pre-annealing temperatures T_ann > 200 °C two new NO₃^2- centers were observed in (N)HAP samples; they are characterized by larger value of A_⊥ (3.67 and 4.41 mT) as compared to the known centers. It was also found that the dependence of NO₃^2- centers amount on T_ann is non-monotonous in both types of samples. Presumably this is caused by the escape of water molecules from HAP during the annealing and essential modification of the defect subsystem of HAP.     

Phase transition to anticlinic texture in free-standing smectic c films

Experimental data on the optical reflectance of free-standing smectic C films were analyzed within the framework of a phenomenological Landau approach. At a certain temperature T _0N (determined from experimental data), which exceeds the known temperature T _c of the volume phase transition from smectic A to smectic C state, a surface phase transition takes place whereby molecules in the surface layer become sloped relative to the normal of the smectic layers. The transition temperatures T _0N ^s,a for N-layer films possessing synclinic (symmetric) and anticlinic (antisymmetric) textures of the order parameter (tilt angle θ) were determined. A comparison of the theoretical and experimental data allowed all parameters of the model to be determined (including critical indices of the correlation length and the surface order parameter). Three possible models of the transition from the state with transverse polarization (perpendicular to the molecular tilt plane) to the state with longitudinal polarization (parallel to this plane) are analyzed. The transition takes place at low (°–°) values of the order parameter θ in the middle layer of the film.