Effect of the ion current density on the temperature dependences of ion-induced electron emission from carbon-based materials

The effect of ion current density j on the temperature dependences of the ion-induced electron emission yield γ(T) of carbon-based materials (polycrystalline graphite MPG-8, highly oriented pyrolytic graphite UPV-1T, and some glassy carbons) under irradiation by atomic and molecular nitrogen ions with energies of several tens of keV has been experimentally studied. The most significant effect of the density j on the dependences γ(T) is observed for low-temperature glassy carbons.     

Effect of temperature on the physical sputtering of highly oriented pyrolytic graphite

The results of experimentally investigating the sputtering and erosion of the basal plane of highly oriented pyrographite UPV-1T under irradiation with 30-keV Ar⁺ in the range from room temperature to 400°C are presented. It has been found that ion-induced surface-relief evolution at higher temperatures results in a two-fold increase in the sputtering yield (Y = 2) in comparison with sputtering of a surface with a nanosized relief at temperatures less than that of the texture transition T _t ≈ 150°C. Sputtering simulation using the OKSANA code for a surface with a sinusoidal nanorelief, which reflects the instability of the basal plane of UPV-1T under ion irradiation, permits to estimate the ratio of the amplitude to the relief period at T < T _t.     

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.     

Influence of the magnetic phase transition on secondary ion emission from disordered Ni-Pd compounds of various compositions

Variations in secondary ion emission (SIE) from polycrystals of ferromagnetic disordered Ni-Pd compounds irradiated by argon ions with energy of 10 keV are studied experimentally. A considerable reduction in Ni⁺ and Pd⁺ ion emission upon transitioning from the ferromagnetic to the paramagnetic state is revealed for the following Ni-Pd compounds with various Curie points T _C: NiPd (T _C = 190°C), Ni₅Pd (T _C = 315°C), and NiPd₅ (T _C = 110°C). The observed reduction in SIE is attributed to variations in the surface binding energy and the density of electron states near the Fermi level.     

A search for a thermal spike effect in sputtering

The temperature dependence of the sputtering yield was measured for lOOkeV per atom bombardment of silver with molecular and atomic antimony ions. No exponential increase of the yield was found in the temperature range from 25° to 775 °C, although a pronounced nonlinear effect is observed when the yield of these projectiles is compared,Y(Sb ₂ ⁺ )≈ 1.5×[2Y(Sb⁺)]. We conclude that there is no influence of the lattice temperature on collision spikes.     

Specific features of electrical properties of porous biocarbons prepared from beech wood and wood artificial fiberboards

This paper reports on comparative investigations of the structural and electrical properties of biomorphic carbons prepared from natural beech wood, as well as medium-density and high-density fiberboards, by means of carbonization at different temperatures T _carb in the range 650–1000°C. It has been demonstrated using X-ray diffraction analysis that biocarbons prepared from medium-density and high-density fiberboards at all temperatures T _carb contain a nanocrystalline graphite component, namely, three-dimensional crystallites 11–14 Å in size. An increase in the carbonization temperature T _carb to 1000°C leads to the appearance of a noticeable fraction of two-dimensional graphene particles with the same sizes. The temperature dependences of the electrical resistivity ρ of the biomorphic carbons have been measured and analyzed in the temperature range 1.8–300 K. For all types of carbons under investigation, an increase in the carbonization temperature T _carb from 600 to 900°C leads to a change in the electrical resistivity at T = 300 K by five or six orders of magnitude. The dependences ρ(T) for these materials are adequately described by the Mott law for the variable-range hopping conduction. It has been revealed that the temperature dependence of the electrical resistivity exhibits a hysteresis, which has been attributed to thermomechanical stresses in an inhomogeneous structure of the biocarbon prepared at a low carbonization temperature T _carb. The crossover to the conductivity characteristic of disordered metal systems is observed at T _carb ? 1000°C.     

Fast lithium-ion transport in composites containing lithium-bromide dihydrate

Composites containing lithium-bromide dihydrates and a second phase, either the monohydrate or dispersed Al₂O₃ particles, exhibit an abrupt increase in the electrical conductivity at thedihydrate melting temperature T_m = 43°C. Although the conductivity at T >62 T_m is characteristic of a good liquid electrolyte -σ ≈ 0.1 mho cm^-1 at 130°C with an activation energy E_A = 13 kJ/mol and a Li⁺-ion transport number 0.9 ± 0.2, the composite pellet may be handled as a solid; it is brittle at 100°C. The possible significance of this finding for the design of high-power battery electrodes is indicated.     

Spectroscopic diagnostics of R.F. discharges at moderate pressure and chemical applications—I. Pure nitrogen

A vibro-rotational analysis has been performed of the second positive system (SPS) of N₂ and of the first negative system (FNS) of N⁺₂ emitted by 35 MHz discharges in flowing nitrogen operated at pressures of 5–50 torr and power densities of the order of 1–10 W-cm^-3. The distributions of the vibrational and of the rotational levels follow Boltzmann's law in both the SPS and the FNS with T_v = 4000°K and T_R = 2800°K for the N₂(C³Π_u) state and T_v = 5100°K and T_R = 5800°K for the N⁺₂(B²Σ⁺_g) state and independent of pressure. Kinetic gas temperatures are between 1200 and 2000°K and increase with pressure; electron temperatures are in the range 15,000–9,500°K. The reversal of line intensities of the SPS and of the FNS observed with increasing pressure has been tentatively interpreted. Possible chemical implications of these results have been examined.     

35Cl NQR study of the low temperature transition in ferroelectric (CH3NH3)HgCl3

In addition to the paraelectric-ferroelectric phase transition at T_c = + 62°C there is another low T phase transition in the −152 to −165°C range associated with a sudden change in the NQR spectra.The three ³⁵Cl NQR lines observed in the P3₂ ferroelectric phase of (CH₃NH₃)HgCl₃ below T_c = 62°C suddenly disappear on cooling below −152°C. No lines could be observed between 152 and −165°C. Below this temperature five ³⁵Cl NQR lines appear and remain down to liquid nitrogen temperature.     

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.     

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.     

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 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.     

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.     

Synthesis,characterisation, luminescence and defect centres in solution combustion synthesised CaZrO3:Tb3+ phosphor

Tb³⁺ doped CaZrO₃ has been prepared by an easy solution combustion synthesis method. The combustion derived powder was investigated by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy techniques. A room temperature photoluminescence study showed that the phosphors can be efficiently excited by 251 nm light with a weak emission in the blue and orange region and a strong emission in green light region. CaZrO₃:Tb³⁺ exhibits three thermoluminescence (TL) glow peaks at 126 °C, 200 °C and 480 °C. Electron Spin Resonance (ESR) studies were carried out to study the defect centres induced in the phosphor by gamma irradiation and also to identify the centres responsible for the TL peaks. The room temperature ESR spectrum of irradiated phosphor appears to be a superposition of two distinct centres. One of the centres (centre I) with principal g-value 2.0233 is identified as an O^? ion. Centre II with an axial symmetric g-tensor with principal values g_=1.9986 and g_?=2.0023 is assigned to an F⁺ centre (singly ionised oxygen vacancy). An additional defect centre is observed during thermal annealing experiments and this centre (assigned to F⁺ centre) seems to originate from an F centre (oxygen vacancy with two electrons). The F centre and also the F⁺ centre appear to correlate with the observed high temperature TL peak in CaZrO₃:Tb³⁺ phosphor.     

Effect of electron irradiation on the paramagnetic state of La0.67Ca0.33MnO3

The effect of point defects on the magnetic properties of La_0.67Ca_0.33MnO₃ polycrystals and single crystals has been studied. The magnetic susceptibility χ _dc of the initial samples and samples irradiated by electrons to the maximum dose F = 9 × 10¹⁸ cm^?2 has been measured in the temperature region 80 K < T < 650 K. Local variations of Mn-O-Mn bond angles and lengths result in a nonmonotonic dose dependence of the Curie temperature T _C. At high doses of electron irradiation, F ≥ 5 × 10¹⁸ cm^?2, the temperature of the transition from the ferromagnetic to polaron state in a single crystal is found to increase. In the paramagnetic region close to T _C, ferromagnetically ordered polarons are observed to exist, while at T > 1.2T _C, localization of e _g electrons initiates formation of paramagnetic polarons with a higher magnetic moment. Electron irradiation stimulates persistence of magnetic polarons up to higher temperatures T > 2T _C.     

Electric field gradients at Zr sites and phase transition in the Nasicon-type compound Na5Zr(PO4)3

The quadrupole coupling parameters of the ¹⁸¹Ta probe placed in substitution for zirconium were measured by Perturbed Angular Correlation (PAC) Spectroscopy in a polycrystalline sample of the Na₅Zr(PO₄)₃ composition between R · T and 400°C. The PAC spectra indicate the existence of a transition which spreads out over a rather large temperature range between 90 and 130°C. The results are coherent with the X-ray diffraction data previously reported on this compound. Spin relaxation phenomena are observed, which give evidence that the phase transition induces important modifications on the local motions of Na⁺-ions.     

Influence of argon ion bombardment on the formation of intermetallic compounds in the nickel-aluminum system

The formation of Ni _x Al _y intermetallic compounds in two-layer (Ni/Al) structures (nickel films deposited on aluminum substrates in vacuum) under bombardment by Ar⁺ ions has been studied experimentally. The method based on Rutherford backscattering of He⁺ ions is used to demonstrate that argon ion bombardment causes the formation of intermetallic compounds in the near-surface layer. The thickness of the intermetallic layer formed in the near-surface region substantially exceeds the projective ion path. The composition and thickness of the intermetallic layer depend mainly on the implantation dose and the substrate temperature, rather than on the ion current density. In the intermetallic layer, the content of nickel increases with increasing temperature. It has been established that, in the absence of bombardment, intermetallic phases are not observed at temperatures lower than T = 400°C and that, in the presence of bombardment, the Ni₃Al intermetallic layer arises at a temperature of 320°C.     

Radiation-induced defects in annealed carbonate-containing hydroxyapatite

The effect of preliminary (before irradiation) annealing of synthetic carbonate-containing hydroxyapatite powders on the formation of paramagnetic centers under γ-ray and ultraviolet irradiation has been investigated. Annealing of the samples has been performed in the temperature range from 100 to 700°C. It has been found that electron paramagnetic resonance spectra of radiation-induced defects depend substantially on the annealing temperature. The paramagnetic centers CO ₂ ^? dominate in the samples annealed to 250°C (γ-ray irradiation) and 500°C (ultraviolet irradiation). In the samples annealed above 400°C, other defects, in particular, the O^? and CO ₃ ^3? centers, play a significant role. Annealing at some temperatures leads to an increase in the radiation sensitivity of the material. The observed effects can be associated with the escape of molecular water from the annealed hydroxyapatite samples and with the corresponding transformation of the defect subsystem of the material.     

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.