Investigating the dissociation energies of niobium and vanadium oxide clusters synthesized by ion sputtering

The mass distributions and fragmentation routes of Nb _n O _m ⁺ and V _n N _m ⁺ clusters sputtered from an metal surfaces with Xe⁺ ions under O₂ pressure of P = 4?5 × 10^?3 Pa in a bombardment chamber are studied by means of secondary ion mass spectrometry. The spectra of kinetic energy release distribution (KERD) are measured for the most probable routes of the fragmentation of Nb _n O _m ⁺ and V _n N _m ⁺ and clusters, on the basis of which the activation energies of the decomposition (dissociation) of Nb _n O _m ⁺ and V _n N _m ⁺ clusters are determined within the model of evaporative ensemble and the theory of monomolecular reactions. The results show the closeness of the numerical values of dissociation energies derived using both models.     

Decay rate constants of sputtered vanadium oxide clusters

Results from studying the emission and fragmentation of V _n O _m ^± clusters sputtered from a vanadium surface by Xe⁺ ions at O₂ pressures of P = 4–5 × 10^?3 Pa are presented. The average decay rate constants of V _n O _m ^± clusters for major fragmentation channels are determined. It is shown that the decay rate constants for clusters of similar stoichiometry do not depend on their charge states.     

Mechanisms of oxidation-reduction processes on metal and oxide surfaces under ion bombardment

Surface oxidation occurs if metals are bombarded with low-energy (1–5 keV) ions of a chemically active gas (oxygen) in vacuum. It is ascertained that ion bombardment leads to the generation of lower, intermediate, and higher oxides. The composition and thickness of an oxidized layer depend on the metal reactivity and the dose and energy of oxygen ions. The mechanism underlying the ion-beam oxidation of metal surfaces is proposed. Surface reduction is observed if higher oxides are bombarded with low-energy (1–5 keV) ions of inert gases (argon and helium) in vacuum. It is revealed that ion bombardment not only generates intermediate and higher oxides but sometimes gives rise to surface metallization. The composition and thickness of the reduced layer are determined by the oxide type, the kind of inert gases, and the dose and energy of bombardment. The mechanism describing the ion-beam reduction of higher metal oxide surfaces is proposed.     

XPS study of vanadium surface oxidation by oxygen ion bombardment

Oxidation of vanadium metal surfaces at room temperature by low-energy oxygen ion beams is investigated by X-ray photoelectron spectroscopy (XPS). It is observed that ion-beam irradiation of clean V results in formation of thin oxide layer containing vanadium in oxidation states corresponding to VO, V₂O₃, VO₂ and V₂O₅ oxides. The composition of the products of ion-beam oxidation depends markedly on oxygen ion fluence. The results of angle-resolved XPS measurements are consistent with a structure of oxide film with the outermost part enriched in V₂O₅ and VO₂ oxides and with V₂O₃ and VO oxides located in the inner region of the oxide layer.     

Anisotropic energy distribution of sputtered atoms induced by low energy heavy ion bombardment

The theory of anisotropic sputtering published in Phys. Rev. B 71(2), 026101 (2005) and Radiat. Effects Defects Solids 159(5), 301 (2004) has been modified and used to calculate the sputtering yield energy distributions for copper, tungsten, and aluminum targets bombarded by low-energy argon ion. As usual, the electronic stopping is ignored in the analysis. The present theory (modified Sigmund’s theory) has been shown to fit the corresponding experimental results of sputtering yield energy distributions well, except for the cases where the larger ion incident angle and larger sputtering emission angles were considered. The larger discrepancy between the present theory and the experimental result in the latter cases is probably due to the influence of direct recoil atoms on the energy spectrum. Compared with Falcone’s analytical theory, the present theory can reproduce much better experimental results of sputtering phenomena. The fact clearly demonstrates the intrinsic relation between the ion–energy dependence of the total sputtering yield and the sputtering yield energy distribution and suggests the great importance of momentum deposited on the target surface in the physical sputtering     

氧化钒薄膜微观结构的研究

采用直流磁控反应溅射在Si(100)衬底上溅射得到(001)取向的V₂O₅薄膜.x射线衍射(XRD)、扫描电镜(SEM)和傅里叶变换红外光谱(FTIR)的结果表明，氧分压影响薄膜的成分和生长取向，在氧分压0.4Pa时溅射得到(001)取向的纳米V₂O₅薄膜，即沿c轴垂直衬底方向取向生长的薄膜.V₂O₅薄膜经过真空退火得到(001)取向的VO₂薄膜，晶体颗 关键词： 微观结构 氧化钒薄膜 择优取向 直流磁控溅射     

Multiple processes during the sputtering of materials by ion bombardment

A new method of statistical analysis dedicated to filling the gap between dynamic and thermodynamic theories of secondary-particle emission under ion bombardment is proposed. Expressions for the average number of emitted atomic particles and electrons are obtained, and the relationships between their yields are established.     

Low reflectance sputtered vanadium oxide thin films on silicon

Vanadium oxide thin films on silicon (Si) substrate are grown by pulsed radio frequency (RF) magnetron sputtering technique at RF power in the range of 100–700 W at room temperature. Deposited thin films are characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques to investigate microstructural, phase, electronic structure and oxide state characteristics. The reflectance and transmittance spectra of the films and the Si substrate are recorded at the solar region (200–2300 nm) of the spectral window. Substantial reduction in reflectance and increase in transmittance is observed for the films grown beyond 200 W. Further, optical constants viz. absorption coefficient, refractive index and extinction coefficient of the deposited vanadium oxide films are evaluated.     

Theoretical energy distributions of atoms sputtered from elastic collision spikes by monomer and dimer ion bombardment

The energy spectra of atoms sputtered from metal targets by bombardment with heavy monomer and dimer ions have been investigated on the basis of a standard model for elastic collision spikes. In particular we calculated the energy distributions for a Au sample bombarded by 4 keV I⁺ and 8 keV I ₂ ⁺ ions. The results were compared with the recent time of flight measurements performed by de Vries and coworkers. It was shown that the model described accurately most of the experimental observations: the count rates and the relative cascade to spike ratios for both I⁺ and I ₂ ⁺ projectiles, and the energy spectrum for dimer sputtering. The spectrum for monomer bombardment, however, was shifted towards lower energies in comparison to the experimental one. The possible source of this discrepancy is discussed.This work was supported by the Central Research Program CPBP 01.09     

Kinetic-energy release distributions and stability of niobium-carbon clusters sputtered from the surface of niobium carbide by xenon ions

The results of studying the emission and fragmentation of niobium-carbon clusters Nb _m C _n ⁺ synthesized upon sputtering a niobium carbide surface with Xe⁺ ions are presented. The fragmentation channels of Nb _m C _n ⁺ clusters are studied. We present the values of the dissociation energy of some Nb _m C _n ⁺ clusters (m = 1–7, n = 2–8) calculated within the context of the “evaporation ensemble” model and theory of unimolecular reactions based on performed measurements of the kinetic-energy spectra of fragment ions. The obtained results are compared with published data.     

Kinetic energy distributions of neutral In and In2 sputtered by polyatomic ion bombardment

Kinetic energy distributions of neutral In monomers and In₂ dimers sputtered from a polycrystalline indium surface under bombardment with 5 keV/atom Au₁⁻ and Au₂⁻ projectiles have been investigated by means of laser postionization time-of-flight mass spectrometry. Results show that 5 keV Au₁ bombardment leads to results in full compliance with linear cascade sputtering theory. For polyatomic ion bombardment, we find a clear transition to a collisional spike dominated emission process. The spike contribution appears as a low-energy part in the sputtered flux which increases with increasing projectile nuclearity and energy. We show that, the velocity spectrum associated with the low-energy contribution is virtually identical for sputtered monomers and dimers. This finding has important implications with respect to the particle emission mechanism under polyatomic projectile bombardment.     

Angular distributions of Au and Cu atoms sputtered from Au-Cu alloys by keV Ar+ ion bombardment

Angular distributions of Au and Cu atoms sputtered from Au-Cu alloys under 3 keV AR⁺ ion bombardment were measured to understand the preferential sputtering. The surface composition of sputter-deposited Au-Cu films on substrates mounted at different ejection angles was analyzed by Auger electron spectroscopy and electron probe microanalysis. Although the result indicated that the proportion of sputtered Cu atoms to the Au atoms in the Au-Cu alloy depends on the ejection angle, marked enhancement of the lighter component in the direction normal to the surface has not been observed in spite of the larger mass ratio of the constituent atoms of the Au-Cu alloy.     

Multiatomic clusters emerging from a metal surface under ion bombardment

[Ag _n ]^? ions emerging from a silver target under bombardment with energetic krypton ions have been measured forn ranging up to 60. The relative intensities of ions with odd numbers are strikingly favoured. The numbersn=8 and 20 mark minima in the abundance of ions with even numbers. The observations are briefly discussed.     

Effect of low-energy ion bombardment on the crystal structure and superconductivity of niobium films

The effect of ion bombardment on the growth of Nb films and their crystal structure is investigated. Epitaxial niobium films with the (001) orientation are grown on (01i2) Al₂O₃ substrates heated to 600°C and biased at ?20 V. Niobium films with pronounced axial texture in the [110] direction are grown on water-cooled Sitall (devitrified glass such as Pyroceram) substrates. In Nb films biased at ?50 V, which are in the superconducting state, the motion of individual magnetic vortices is observed with a magnetooptic indicator.     

Energy spectra of atoms sputtered by KeV light-ion bombardment

A calculation has been made for the sputtering of heavy targets by KeV light-ion bombardment. The calculation is based both on linear transport theory and on the assumption that only primary recoiling atoms are candidates for the sputtering process. The energy spectra calculation predicts the experimentally observed peak shift towards lower velocities than those obtained by standard linear cascade theory.     

Ripening of subsurface amorphous C clusters formed by low energy He ion bombardment of graphite

Surfaces of highly oriented pyrolytic graphite (HOPG) were bombarded with 100 eV and 500 eV He ions at ion doses of a few 10¹⁵ cm² and temperatures ranging from 300 K to 800 K. AFM images were recorded to investigate the topography of the surfaces after ion bombardment. Supplementary electron energy loss (EEL) and thermal desorption (TD) spectra were measured to determine the C sp² fraction of the bombarded surfaces and the amount of trapped He. The temperature at which He ion bombardment was performed had a drastic effect on the surface structure and topography of the targets on the angstrom-scale and micrometer-scale as well. At 300 K, limited defect atom transport revealed an amorphous but relatively flat HOPG surface. Bombardment at 400 K leads to a granular structure of small protrusions in micrometer-scale AFM images, however, without crystalline order on the surface. The protrusions are due to the formation of subsurface clusters of carbon formed by atoms displaced by ion irradiation. Towards higher temperatures during bombardment the clusters agglomerate and cause the surface layers to bend upwards in dome-like shapes. Simultaneously, the microscopic order of the graphite lattice recovers. At 800 K large areas of the top layer retain their order during bombardment, however, a small number of domes indicate that there still exist some subsurface C clusters. The cluster–cluster distance deduced from the dome distribution indicates that the clusters grow through a ripening process. Annealing of graphite at high temperatures subsequent to ion bombardment at low temperatures is much less effective for recovering the surface crystallinity than ion bombardment at high temperature.     

Spectroscopy of excited particles sputtered by ion bombardment of Zn,Cd, and chemical compounds of these metals

The main parameters of optical emission (spectra, excitation and population efficiencies of levels, and kinetic energies) of excited particles sputtered by a beam of Ar⁺ ions from the surfaces of Zn, Cd, and chemical compounds of these metals with electronegative elements (O, Te, Se, and S) are studied. It is shown that, upon ion bombardment of the compounds of the metals under investigation, an additional mechanism of formation of excited particles arises in comparison with the bombardment of pure Zn and Cd. This mechanism, related to the ionicity of chemical bonds, leads to inconsistency between the yield of excited particles and the sputtering coefficient of the corresponding material. The effect of the electronic structure of a solid on the yield of excited particles and their velocity distribution is also revealed.     

Molecular dynamics simulation of bipartite bimetallic clusters under low-energy argon ion bombardment

The evolution of bipartite bimetallic atomic clusters within 5 ps under bombardment with monoenergetic argon ions at the initial energy ranging from 1 eV to 1.4 keV has been simulated by the classical molecular dynamics method with a target obtained from Ni?Al and Cu?Au clusters consisting of 78 and 390 atoms, equally divided between the corresponding monometallic parts, the simulated pairs of which have different heats of intermixing. The changes in the potential energy and temperature, the sputtering yields, and the intensity of the ion-stimulated movement of atoms at the interface of the monometallic parts of clusters of both sizes have been determined as functions of the energy of the bombardment.     

Angular-distribution neutron-emission spectra of niobium following bombardment by fast neutrons

Neutron-emission spectra at ten angles between 20 and 160 degrees and incident neutron energies of 5.9, 7.1 and 8.4 MeV were measured relative to the neutron field emitted after spontaneous fission of ²⁵²Cf. The angular distribution of inelastically scattered neutrons appears to be essentially isotropic where it can be separated from the dominant elastic scattering peak. Above an excitation energy of 4 MeV the spectra are well described by a Maxwellian temperature distribution.