A spectroscopic study of CNx formation by the keV N2 irradiation of highly oriented pyrolytic graphite surfaces

Amorphous carbon nitride (CN_x) thin layer, formed by the keV N₂⁺ irradiation of highly oriented pyrolytic graphite, has been investigated using X-ray photoelectron and raman spectroscopies, and time-of-flight secondary ion mass spectrometry. C1s X-ray photoelectron spectroscopy (XPS) peak separations indicate that C-N bonds form over and above the graphite fragmentation previously obtained on Ar⁺ irradiation. N1s XPS peak separations indicate three components. Their attributions, and the resultant CN_x structure, are confirmed by angle-resolved XPS and TOF-SIMS analyses.     

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.     

Specific features of steady-state implantation of crystalline silicon with a molecular oxygen-nitrogen beam: Si <Emphasis Type="Italic">L</Emphasis><Subscript>2, 3</Subscript> x-ray emission spectra

The local electronic structure of 〈111〉 n-silicon single-crystal samples is studied using Si L _{2, 3} x-ray emission spectroscopy. The Si _x O _y N _z system is formed by implanting the samples with an ¹⁶O ₂ ⁺ and ¹⁴N ₂ ⁺ ion molecular beam (the oxygen/nitrogen ratio in the molecular beam is 1:1, the implantation energy is 30 keV, the irradiation fluences vary from 2.0 × 10¹⁷ to 1.5 × 10¹⁸ cm^?2, the samples after the implantation are subjected to rapid thermal annealing in nitrogen at 800°C for 5 min). A comparison of the recorded Si L spectra with the spectra of the reference samples reveals clear correlations between the specific features of the electronic structure of the silicon oxynitride formed upon implantation and the ion fluence. It is shown that the implantation at fluences of 2 × 10¹⁷ and 1 × 10¹⁸ cm^?2 results in the predominant formation of Si₃N₄, whereas the implantation at a fluence of 1.5 × 10¹⁸ cm^?2 leads primarily to the formation of SiO₂ layers in single-crystal silicon. The most probable factors and mechanisms accounting for such implantation of ¹⁶O ₂ ⁺ and ¹⁴N ₂ ⁺ into the samples under study are discussed. The experimental data obtained are compared with ab initio full-potential linearized augmented plane wave calculations of the band structure.     

Investigation of the EPR g factors and defect structure for the Cu-VNa center in the X-irradiated NaCl: Cu crystal

The g factors of a tetragonally-compressed Cu²⁺ center in NaCl: Cu⁺ crystal X-irradiated at room temperature are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, the contribution to g factors from both crystal-field (CF) and charge-transfer (CT) mechanisms are included. The calculations are based on the defect model that the tetragonally-compressed Cu²⁺center is assigned to the Cu²⁺ ion (which is caused by Cu⁺ ion (at the Na⁺ site) irradiated by X-ray) associated with a nearest Na⁺ ion vacancy V_Na along C₄ axis due to charge compensation. From the calculations, the g factors g_|| and g_⊥ are explained and the defect structure (charactering by the displacement ΔZ of the Cl⁻ ion intervening in Cu²⁺ and V_Na) of the Cu²⁺ (or Cu²⁺-V_Na) center is obtained. The results are discussed.     

Desorption of cluster ions from adsorbed methane under cryogenic condition by low-energy ion irradiation

We have investigated ion desorption from adsorbed methane following keV He⁺ ion irradiation. The thickness of the adsorbed layer was precisely controlled. For mono-layered methane, only monomer ions (CH_x⁺) were desorbed by 1 keV He⁺ ion irradiation. On the other hand, a large number of cluster ions (C_nH_x⁺) up to n = 20 were desorbed from multi-layered film. Among cluster ions, molecular ions with CC bonds were found, which indicates that chemical bonds are newly formed by ion irradiation. Based on the results for thickness dependences of the mass spectral patterns, it was elucidated that the monomer ions are desorbed from the top surface layer through single electron excitation. While the cluster ions are formed mainly in the inside of the layers along the nuclear track due to the high-density electronic excitation, which is produced by nuclear collision between incident He⁺ ions and frozen molecules.     

The effect of high iron-ion implantation doses on the X-ray emission spectra of silicon

X-ray emission spectroscopy (Si L _{2, 3} spectra, 3d3s → 2p electronic transition) was employed to study p-and n-type silicon samples implanted with Fe⁺ ions in a pulse mode (the implantation energy was 30 keV, the pulse current was varied up to 0.5 A, the pulse duration was 400 μs, and the ion irradiation doses ranged from 10¹⁴ to 10¹⁷ cm⁻²). The x-ray emission spectra were found to be dependent on the ion irradiation dose and the electron-accelerating voltage that was used in the x-ray studies. By comparing the Si L spectra with the spectra of reference materials and by modeling the former spectra, it was revealed that, as the ion-irradiation dose increases, there occur disordering of the structure, partial amorphization of the sample in a surface layer approximately 7200-? thick, and its subsequent recrystallization (under high irradiation doses). It was shown that this effect is most pronounced in a layer at a depth of ∼1000 ? and is not associated with the formation of iron silicide FeSi in the bulk of the sample but rather is due to the breakage of Si-Si bonds caused by ion implantation under the irradiation doses used. Original Russian Text ? D.A. Zatsepin, E.S. Yanenkova, é.Z. Kurmaev, V.M. Cherkashenko, S.N. Shamin, S.O. Cholakh, 2006, published in Fizika Tverdogo Tela, 2006, Vol. 48, No. 2, pp. 204–209.     

Field ion microscopy of cascades of atomic displacements in metals and alloys after various types of irradiation

Experimental results on atomic-spatial investigation of radiative defect formation in surface layers of materials, initiated by neutron bombardment (of Pt, E > 0.1 MeV) and ion implantation (in Cu₃Au: E = 40 keV, F = 10¹⁶ ion/m², j = 10^?3 A/cm²), are considered. Quantitative estimates are obtained for the size, shape, and volume fraction of cascades of atomic displacements formed under various types of irradiation in the surface layers of the materials. It is shown that the average size of radiation clusters after irradiation of platinum to a fast neutron fluence of 6.7 × 10²² m^?2 (E > 0.1 MeV) is about 3.8 nm. The experimentally established average size of a radiation cluster (disordered zone) in the alloy after ion bombardment is 4 × 4 × 1.5 nm.     

Effect of oxide surface metallization under ion-beam irradiation

Changes in the surface chemical composition of WO₃, Ta₂O₅, MoO₃, and Nb₂O₅ oxides after Ar⁺ ion irradiation and those of the WO₃ surface after He⁺ ion irradiation under high vacuum were investigated by X-ray photoelectron spectroscopy. Upon Ar⁺ ion irradiation with an energy of 3 keV, the pronounced effect of ion-beam metallization was observed on the WO₃ oxide surface; a moderate effect was found for the Ta₂O₅ oxide surface; a weak one for the MoO₃ oxide surface; and no effect was discovered for the Nb₂O₅ oxide surface. At the saturation dose, 44 at % W, 12 at % Ta, and 2 at % Mo form on the oxide surfaces. Irradiation by light He⁺ ions with energies of 1 and 3 keV results in WO₃ surface metallization. At the saturation dose, 2 and 10 at % W (at 1 and 3 keV, respectively) forms on the oxide surface. The nature, mechanisms, and features of the oxide surface metallization effect induced by ion-beam irradiation are discussed.     

Cluster SIMS using metal cluster complex ions

Metal cluster complexes are chemically synthesized organometallic compounds, which have a wide range of chemical compositions with high molecular weight. Using a metal cluster complex ion source, sputtering characteristics of silicon bombarded with normally incident Ir₄(CO)₇⁺ ions were investigated. Experimental results showed that the sputtering yield at 10 keV was 36, which is higher than that with Ar⁺ ions by a factor of 24. In addition, secondary ion mass spectrometry (SIMS) of boron-delta-doped silicon samples and organic films of poly(methyl methacrylate) (PMMA) was performed. Compared with conventional O₂⁺ ion beams, Ir₄(CO)₇⁺ ion beams improved depth resolution by a factor of 2.5 at the same irradiation conditions; the highest depth resolution of 0.9 nm was obtained at 5 keV, 45° with oxygen flooding of 1.3 × 10⁻⁴ Pa. Furthermore, it was confirmed that Ir₄(CO)₇⁺ ion beams significantly enhanced secondary ion intensity in high-mass region.     

X-ray emission and photoluminescence spectroscopy of nanostructured silica with implanted copper ions

Quartz glass samples and compacted SiO₂ nanopowders have been studied by x-ray emission (CuL _{2, 3} transition 3d4s → 2p _{1/2, 3/2}) and photoluminescence spectroscopy following pulsed Cu⁺ ion implantation (energy, 30 keV; pulse current up to 0.5 A; pulse duration, 400 μs; irradiation doses, 10¹⁵, 10¹⁶, and 2 × 10¹⁷ cm^?2). It has been established that ion irradiation gives rise to the formation of glassy and compacted SiO₂ samples of nanosized metallic and oxide phases in the structure. An analysis of CuL x-ray emission spectra has shown that copper nanoparticles are thermodynamically metastable and chemically active because ion beam bombardment transfers them readily to the oxide form. This results from the radiation-stimulated fracture of regular Si-O-Si bonds in amorphous SiO₂ and the formation of defective Si-Si bonds, followed by capture of oxygen by copper atoms. The enhanced degree of oxidation of copper ions in SiO₂ nanostructured pellets can be reduced by coimplantation and thermal annealing. Optical spectroscopy studies suggest that, in glasses and SiO₂ nanostructured pellets, there exist metallic Cu _n ⁰ nanoclusters, which at low temperatures exhibit quantum-confined photoluminescence with a characteristic stepped excitation spectrum.     

Cu+ ion conductivity of K2Cu(CNS)3

K₂Cu(CNS)₃ is found to be a Cu⁺ ion conductor with a room temperature (30°C) conductivity of ～5×10^?3ω^?1 cm^?1. The phase structure of the CuCNS + KCNS system and data on temperature variation of the conductivity of K₂Cu(CNS)₃ is reported. The related compound KAg(CNS)₂ is found to be a Ag⁺ ion conductor.     

Ion beam shaping of embedded metal nanoparticles by Si+ ion irradiation

Fine Co and Pt nanoparticles are nucleated when a silica sample is implanted with 400 keV Co⁺ and 1370 keV Pt⁺ ions. At the implanted range, Co and Pt react to form small Co _x Pt_(1?x) nanoparticles during Si⁺ ion irradiation at 300 °C. Thermal annealing of the pre-implanted silica substrate at 1000 °C results in the formation of spherical nanoparticles of various sizes. When irradiated with Si⁺ ions at 300 °C, particles in the size range of 5–17 nm undergo rod-like shape transformation with an elongation in the direction of the incident ion beam, while those particles in the size range of 17–26 nm turn into elliptical shape. Moreover, it is suspected that very big nanoparticles (size >26 nm) decrease in size, while small nanoparticles (size <5 nm) do not undergo any transformation. During Si⁺ ion irradiation, the crystalline nature of the nanoparticles is preserved. The results are discussed in the light of the thermal spike model.     

Structural features of aluminium alloy 1441 irradiated by Ar+ ions

Using electron microscopy it was found that irradiation of clad cold-worked specimens made of commercial aluminium-lithium alloy 1441 by the Ar ⁺ ions of energy 40 keV at low doses of irradiation (10¹⁵ cm⁻², irradiation time 1 s, T < 70 °C) and ion-current density of about 100 μA/cm² results in the transformation of the cellular structure formed in the alloy under deformation. As the dose of irradiation is increased up to 10¹⁶ cm⁻², a transition from a cellular to a subgrain structure close to a polygonal one is observed. The efficiency of the process is increased with ion-current density. Furthermore, under ion irradiation at increased ion-current densities, the β′(Al ₃ Zr) and Al ₈ Fe ₂ Si particles present in the deformed alloy dissolve, and disperse particles of a new Al ₂ LiMg phase of platelet shape are formed. The changes in the dislocation structure and phase composition in alloy 1441 are observed several seconds after irradiation not only in the surface layer adjacent to the ion incorporation band but also through the thickness of the specimen tens of thousands times greater than ion projective ranges. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 73–81, February, 2007.     

Study of the radiation resistance of a carbon fiber based on viscose in carbon-carbon and carbon-ceramic composites

The results of the experimental study of the crystalline structure and morphology of carbon fibers based on viscose in a FEBUS carbon-ceramic composite and its preform as functions of temperature ranging from room values to ～400°C under irradiation with Ar⁺ ions with an energy of 10–30 keV are obtained. The average level of radiation damage corresponding to the initial fiber graphitization (〈ν_gr> ～ 80 dpa) is determined based on an analysis of the energy dependences of the ion-electron emission coefficient at different irradiation temperatures. It is shown that carbon fibers based on viscose are immune (in contrast to polyacrylonitrile fibers) to ion-induced destruction in the form of crimping. This is indicative of their enhanced radiation resistance.     

Excitation of resonance lines of a Zn+ ion by electron impact

Excitation of individual components of the resonance 4p ² P ₁ ^2,3/2/0 doublet of a Zn⁺ ion by electron impact is studied for the first time by the spectroscopic method in crossed beams. A distinct structure (above the ionization potential of an ion as well) found in the energy dependences of the effective excitation cross section is associated mainly with the decay to the resonance levels (direct or cascade) of autoionization states of zinc atoms and ions formed through the excitation of electrons from the subvalence 3d ¹⁰ shell. The results obtained are compared with data of other experiments and theoretical calculations by the method of strong coupling of five and fifteen states, as well as with the semiempirical calculation using the Van Regemorter formula.     

On the nature of ion bombardment-induced phase transformations in films of transition metals

Abstract

Electron diffraction studies have been made of polycrystalline Ni films irradiated with well separated beams of ions of different nature, namely ions of inert (He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺) and reactive (N⁺ and O⁺) gases. The Ni films were prepared under vacuum conditions (P? 3·10^?6Pa during evaporation) preventing an appreciable contamination of the films with impurities. The samples were irradiated at T? 300 K with ion beams of energies from 10 to 100 keV in the dose range between 5·10¹⁶ cm^?2 and the value leading to sample destruction.

Irradiation with noble gas ions revealed no phase transitions in the Ni films. A similar result was obtained in irradiation of Fe and Cr films with He⁺ ions. The bombardment of Ni films with reactive gas ions does cause changes in the lattice structure of the samples under study, depending on the nature of the bombarding ions. The N⁺ ion bombardment gives rise to the hcp phase with the lattice parameters typical of the Ni₃N compound, and the O⁺ ion bombardment results in the fcc phase with the NiO-type parameter.

The conclusion is drawn on the chemical origin of the phase transformations in the Ni films under ion bombardment. The necessity of revising the concept about the polymorphous nature of phase transformations induced in the films of transition metals by ion bombardment is substantiated.     

Positive secondary Ion emission from Si1−xGex bombarded by O2

The positive secondary ion yields of B⁺ (dopant), Si⁺ and Ge⁺ were measured for Si_1−xGe_x (0 ≤ x ≤ 1) sputtered by 5.5 keV ¹⁶O₂⁺ and ¹⁸O₂⁺. It is found that the useful yields of Ge⁺ and B⁺ suddenly drop by one order of magnitude by varying the elemental composition x from 0.9 to 1 (pure Ge). In order to clarify the role of oxygen located near surface regions, we determined the depth profiles of ¹⁸O by nuclear resonant reaction analysis (NRA: ¹⁸O(p,α)¹⁵N) and medium energy ion scattering (MEIS) spectrometry. Based on the useful yields of B⁺, Si⁺ and Ge⁺ dependent on x together with the elemental depth profiles determined by NRA and MEIS, we propose a probable surface structure formed by 5.5 keV O₂⁺ irradiation.     

Optical pumping of ions in buffer gases

Transient signals measured with a pulsed rf-optical pumping method are used to determine longitudinal relaxation rates for Sr⁺ ions (even isotopes) in noble gas buffers. Depolarization cross sections of the electronic spin in the Sr⁺5² S _1/2 ground state for binary collisions with rare gas atoms are deduced. The results for σ(Sr⁺5² S _1/2) in Ų are (at temperatures between 374 and 449 °K): 2·10^?5(He),4·10^?5(Ne), 5.7·10^?3(Ar), 1.8·10^?2(Kr), and 4.0·10^?2(Xe). These cross sections for the Sr⁺ ion are about two to three orders of magnitude larger than the corresponding ones for the isoelectronic neutral Rb atom. The large increase of the Sr⁺ relaxation rates is explained with the relaxation mechanism of spin-orbit coupling, taking into account two “indirect” effects of the ionic charge: the increase in the gas kinetic cross sections and the more intimate collisions of the Sr⁺ ion with the noble gas atoms. The depolarization is shown to be predominantly due to short-range interactions. A contribution to the relaxation of the Sr⁺ ion from Sr⁺-noble gas molecule formation, induced by three-body or resonant two-body collisions, could not be established for applied pressuresp between 1.5 and 15 Torr of Ar, Kr, and Xe.     

Zur Bildungskinetik der F-Folgezentren in KCl

The process of F-center aggregation under light irradiation, which involves ionic movement at low temperatures (observable down to — 60°C), is not at all understood in its mechanism. It is the aim of this work to evaluate quantitatively the kinetics of this process for different F-aggregate centers. In part I the assoziation of F-centers in KCl crystals with isolated Na⁺ or Li⁺ ions was thoroughly investigated as the clearest model case of F-center-aggregation. The reaction product in these crystals after light irradiation, an F-center associated to a Na⁺ or Li⁺ ion as nearest (100) neighbor (F _A -center), is well established in its model and can be detected by its double peak absorption structure. By optical measurements of the rate of F _A -center formation in dependence on light-intensity, time, Na⁺ or Li⁺-concentration, F→F′ conversion rate and temperature, the kinetics of this reaction could be evaluated in a simple equation of bimolecular type. The analysis leads to the conclusion, that either the anion vacancy or the F′-center must be regarded as a unit of high thermal mobility (activation energy 0·6±0·05 eV, jump frequency about 10² sec^?1 at room temperature) which diffuses randomly in the lattice and can be captured by a Na⁺ or Li⁺ ion.     

Effect of high doses on the Si <Emphasis Type="Italic">L</Emphasis><Subscript>2,3</Subscript> x-ray emission spectra of silicon implanted with iron ions under steady-state conditions

The effect of high doses on p-and n-type silicon samples implanted with Fe⁺ ions under steady-state conditions (implantation energy, 100 keV; ion current density, 0.6–0.8 μA/cm²; irradiation dose, 10¹⁴–10¹⁶ ions/cm²) is investigated using Si L _{2, 3} x-ray emission spectroscopy (the 3d3s → 2p electronic transition). An analysis of the Si L x-ray emission spectra of the silicon samples is performed by comparison with the spectra of reference materials and the spectra of silicon samples implanted with Fe⁺ ions in a pulsed mode. The Si L x-ray emission spectra are simulated by the molecular dynamics and full-potential linearized augmented-plane-wave (FLAPW) methods. It is revealed that the effect of high doses under steady-state conditions of Fe⁺ ion implantation into the semiconductor crystal matrix exhibits specific features: the disordering of the structure and partial amorphization of the sample from the surface deep into the bulk are more pronounced than those observed under conditions of pulsed ion implantation, although virtually no recrystallization of the sample at the threshold dose occurs. The most probable origins and mechanisms of the effect of high doses on the samples under investigation are discussed.