Ion beam modification of dielectric materials in the electronic excitation regime: Cumulative and exciton models

Main experimental evidences and theoretical models, currently used to describe the modification of dielectric materials by swift-heavy ion (SHI) beams, operating in the electronic stopping regime, are reviewed. The emphasis is on the interplay and synergy between point defects and amorphous tracks. This implies a change of focus from purely thermal approaches to those based on the generation and accumulation of irradiation-induced defects followed by some type of lattice collapse and structural change. To that end special attention has been paid to experiments performed at electronic stopping powers around the threshold value for track formation. In particular, approaches based on the non-radiative decay of self-trapped excitons (STEs) have been more extensively discussed. The discussion is illustrated by dealing in some detail a few specific materials such as alkali halides (NaCl), SiO₂ and LiNbO₃ where STEs are, or very likely, ascertained. The review stresses the connection between the SHI-induced effects and those caused by femtosecond laser pulse irradiations. Moreover, electronic effects on SiO₂ materials are discussed due to their technological relevance and because they offer an example of the interplay between thermal and excitonic effects. Finally, the potential of SHI irradiation for various technologies, with particular emphasis on photonics, is discussed.     

Role of electronic energy loss on defect production and interface stability: Comparison between ceramic materials and high-entropy alloys

High-entropy alloys (HEAs) and some complex alloys exhibit desirable properties and significant structural stability in harsh environments, including possible applications in advanced reactors. Energetic ion irradiation is often used as a surrogate for neutron irradiation; however, the impact of ion electronic energy deposition and dissipation is often neglected. Moreover, differences in recoil energy spectrum and density of cascade events on damage evolution must also be considered. In many chemically complex alloys, the mean free path of electrons is reduced significantly, thus their decreased thermal conductivity and slow dissipation of localized radiation energy can have noticeable effects on displacement cascade evolution that is greatly different from metals with high thermal conductivity. In this work, nanocrystalline HEAs of Ni₂₀Fe₂₀Co₂₀Cr₂₀Cu₂₀ and nonequiatomic (NiFeCoCr)₉₇Cu₃, both having much lower room-temperature thermal conductivity than pure Ni or Fe, are chosen as model HEAs to reveal the role that electronic energy loss during ion irradiation has in complex alloys. The response of nanocrystalline HEAs is investigated under irradiation at room temperature using MeV Ni and Au ions that have different ratios of electronic energy to damage energy, which is the energy dissipated in displacing atoms. Different from previously reported amorphization of nanocrystalline SiC, experimental results on these HEAs show that, similar to the process in nanocrystalline oxide materials, both inelastic thermal spikes via electron–phonon coupling and elastic thermal spikes via collisions among atomic nuclei contribute to the overall grain growth. The growth follows a power law dependence with the total deposited ion energy, and the derived value of the power-exponent suggests that the irradiation-induced instability at and near grain boundaries leads to local rapid atomic rearrangements and consequently grain growth. The high power-exponent value can be attributed to the sluggish diffusion and delayed defect evolution arising from the chemical complexity intrinsic to HEAs. This work calls attention to quantified fundamental understanding of radiation damage processes beyond that of simplified displacement events, especially in simulating neutron environments.     

Optimization of ion energy spread in inductively coupled plasma source designed for focused ion beam applications

The ion energy distribution of inductively coupled plasma ion source for focused ion beam application is measured using a four grid retarding field energy analyzer. Without using any Faraday shield, ion energy spread is found to be 50 eV or more. Moreover, the ion energy distribution is found to have double peaks showing that the power coupling to the plasma is not purely inductive, but a strong parasitic capacitive coupling is also present. By optimizing the various source parameters and Faraday shield, ion energy distribution having a single peak, well separated from zero energy and with ion energy spread of 4 eV is achieved. A novel plasma chamber, with proper Faraday shield is designed to ignite the plasma at low RF powers which otherwise would require 300-400 W of RF power. Optimization of various parameters of the ion source to achieve ions with very low energy spread and the experimental results are presented in this article.     

Advances in ion beam modification of semiconductors

This review provides an overview of the current status of ion-implantation research in silicon, germanium and the compound semiconductors SiC, GaN and ZnO. The discussion of silicon includes recent developments in metrology and device simulation, as well as a brief discussion of emerging applications in photovoltaics and quantum electronics. That of Ge includes a more detailed overview of doping, radiation damage and annealing processes due to the renewed research interest in this material. Finally, the discussion of compound semiconductors focuses on the newer wide bandgap materials where there are remaining implantation issues to be solved and potentially new implantation applications emerging.     

The effect of the ion beam energy on the properties of indium tin oxide thin films prepared by ion beam assisted deposition

Indium tin oxide (ITO) thin films have been deposited onto polycarbonate substrates by ion beam assisted deposition technique at room temperature. The structural, optical and electrical properties of the films have been characterized by X-ray diffraction, atomic force microscopy, optical transmittance, ellipsometric and Hall effect measurements. The effect of the ion beam energy on the properties of the films has been studied. The optical parameters have been obtained by fitting the ellipsometric spectra. It has been found that high quality ITO film (low electrical resistivity and high optical transmittance) can be obtained at low ion beam energy. In addition, the ITO film prepared at low ion beam energy gives a high reflectance in IR region that is useful for some electromagnetic wave shielding applications.     

Ion beam surface nanostructuring of noble metal films with localized surface plasmon excitation

Noble metal nanoparticles strongly adhered to dielectric matrices have been extensively studied because of their potential applications in plasmonic devices based on tunable localized surface plasmon (LSP) excitation. Compared with conventional synthesis methods, the noble metal nanoparticles formed by ion-beam irradiation draw significant interest in recent years because a single layer dispersion of nanoparticles strongly bonded on the dielectric substrate can be obtained. In this paper, important phenomena related to ion-beam surface nanostructuring including ion-induced reshaping of metal nanoparticles, ion-induced core-satellite structure formation, and ion-induced burrowing of these nanoparticles are discussed, with their individual effects on LSP excitation. Consequently, ion-induced surface nanostructuring of Ag-Au bimetallic films on amorphous silica glass and sapphire with tunable LSP excitation are presented. In addition, theoretical studies of far-field and near-field optical properties of these nanoparticles under ion irradiation are introduced, and the enhanced localized electric field (hot spot) is interpreted. Finally, the futures and challenges of the emerging plasmonic applications based on tunable LSP excitations in bio-sensing and surface enhanced Raman spectroscopy (SERS) are presented.     

Effect of electronic energy dissipation on strain relaxation in irradiated concentrated solid solution alloys

The effect of energy deposition by energetic particles on Ni and two single-phase concentrated solid solution alloys (NiFe and NiCoCrFe) is investigated through combined experimental and modelling efforts. Damage evolution as a function of increasing ion fluence is monitored via elastic strain developed in the irradiated crystals. We show that damage produced from displacement collision cascades is sensitive to subsequent highly ionizing irradiation that the strain generated by elastic nuclear collisions undergoes partial relaxation upon high-energy irradiation. This finding indicates a change in the damage structure upon electronic energy deposition due to both predominant defect annealing and growth of small defect clusters. Strain relaxation, more pronounced in the alloys than in Ni, is ascribed to both higher thermal conductivity and weaker electron-phonon coupling in Ni.     

Thermal activation energy of silver in ion-exchanged soda–lime glass investigated by X-ray photoelectron spectroscopy

The thermal effect on silver in ion-exchanged glasses was investigated in situ by X-ray photoelectron spectroscopy (XPS) in an ultra-high vacuum environment. Each XPS signal of Ag 3d_3/2 and 3d_5/2 consists of two components, the metallic state (Ag⁰) and the oxidized state (Ag⁺), resolved after curve fitting. The toward-surface diffusion of silver was observed by monitoring the changes in concentration on the surface during sample annealing between 20 and 450°C. Judging from the variations in line shape and binding energy and from the enhancement of surface silver under annealing, both metallic and oxidized silver are accumulated on the surface. By applying the diffusion theory in a semi-infinite system to the experimental data, the thermal activation energy of the oxidized silver in ion-exchanged glass, 0.16 eV, was estimated. The activation energy of metallic Ag precipitated during heating, 0.23 eV, was estimated as well.     

The role of hydrogen in a-C:H films deposited from hexane or acetylene using direct ion beam deposition method

The present work provides results of amorphous hydrogenated carbon (a-C:H) films deposited by direct ion beam deposition method. Hexane (C₆H₁₄+H_delivery) or acetylene (C₂H₂) precursors and their mixture with hydrogen (H₂) were used. The films were characterized by Raman spectroscopy (RS), ellipsometry, and electrical resistance measurements. RS indicates increase in sp³/sp² bonding ratio and disorder in graphite clusters, upon increasing of hydrogen content (from 0% to 50% for acetylene precursor) in the deposition gas mixture. The opposite trend is observed when the hydrogen concentration exceeded 50% (for acetylene) or additional hydrogen was added (for hexane). The data of electrical resistance measurements support the correlations defined by RS.     

Low energy O2 and N2O ion beam modification of polyimide for improving adhesive strength of Cu/PI in roll-to-roll process

To enhance the weak mechanical durability of directly deposited copper layers on polyimide (PI) film due to their poor adhesive strength, a continuous roll-to-roll process involving surface modification using a reactive ion beam irradiation and in-situ deposition process is studied. The polyimide film is modified by an ion source with a linear stationary plasma thruster (LSPT) in the vacuum roll-to-roll process. An O₂ ion beam, with beam energy of 214 eV and beam current density of 0.78 mA/cm², and N₂O ion beam, with 220 eV and 0.69 mA/cm², irradiate PI film in winding speed of 0.5 m/min. The surface energy increases from 38 mN/m for the pristine PI film to 80 mN/m after beam irradiation at an ion fluence of 3.5 × 10¹⁶ ions/s. After beam irradiation, a 10 nm thick tie layer and 200 nm thick copper layer are successively deposited by in-situ DC magnetron web coating. The peel strength of the copper layer on the PI film is enhanced from 0.4 kgf/cm without ion beam treatment to 0.71 kgf/cm after O₂ beam treatment and to 0.75 kgf/cm after N₂O beam treatment. This enhancement is closely related to the increase in the polar force originating from the formation of hydrophilic CO (carbonyl) groups on the modified PI surface.     

Redistribution of indium implanted in silicon due to thermal treatment and swift heavy ion irradiation

Silicon layers of 150 nm thickness supersaturated with indium up to ≈5 at% were prepared by multiple energy ion implantation. A redistribution of the implanted impurities caused by post-implantation annealing and following irradiation with swift Bi ions has been observed by means of Rutherford backscattering spectrometry in channelling configuration (RBS/C). It is demonstrated by TEM that the thermal decomposition of the supersaturated Si〈In〉 solution is accompanied by polycrystalline recrystallisation of amorphous silicon, precipitation of the second phase (In) both within the implanted layer and on the surface, as well as by impurity redistribution. The main features of the structure transformation under the influence of the Bi ion irradiation are discussed.     

具有三维连通网络结构的多孔SiC/C材料的电磁损耗特征

通过有机泡沫浸渍/高温炭化和热压固化/高温炭化两种工艺分别制备了具有宏观三维连通网络结构的SiC/C泡沫和显微三维连通多孔结构的SiC/C泡沫同质压制块。使用谐振腔微扰法对比测试了2450MHz频率下两种材料的电磁参数随电导率的变化。结果表明:随着电导率的增加,SiC/C泡沫及其同质压制块的介电常数实部εr′均逐渐增加;电损耗tgδe均先增加,达到最大值后逐渐减小;SiC/C泡沫的磁损耗tgδm不断增加,而其同质压制块的tgδm值则先快速增加,达到最大值后缓慢下降。当二者具有相同有效电导率时,SiC/C泡沫的εr′值比其同质压制块约小1/2,tgδe值至少大2倍,而压制块的tgδm值超过SiC/C泡沫4倍多。SiC/C泡沫及其同质压制块是非磁性的,它们的磁损耗均由其特殊结构与电磁场相互作用产生的,是一种非本征磁损耗。     

基于有限元能量流模型的复杂耦合结构中低频段耦合损耗因子的计算

有限元能量流模型在随机宽带激励下,得到各子系统的空间及频域平均的能量,将其代入能量平衡方程,得到了柔性体之间的间接耦合损耗因子。与传统有限元模型计算耦合损耗因子的方法相比,该方法计算效率更高;与传统统计能量分析模型计算耦合损耗因子的方法相比,该方法计算精度更加可信。最后,该方法通过试验得到了验证。     

The role of LNG in energy supply

This paper reviews the current status of base-load LNG plants involved in international trade. In the historical review of the development of of the LNG industry brief references are made to peak-shaving LNG plants. The paper also describes the complex co-operative effort required to organize international LNG projects, and presents technical information concerning the refrigeration aspects of base-load LNG projects. The information includes brief reviews of liquefaction cycles, storage tanks, types of ships, receiving terminals, and the potential for utilizing the refrigeration available in revaporized LNG.     

Control of the energy of ion flow affecting electrically insulated surface in plasma processing reactor based on a beam plasma discharge

We compare two ways to control the distribution function of ions on the isolated structure which is treated in a plasma reactor based on beam plasma discharge. In the first case, the periodic pulse voltage is applied to the substrate holder. The calculation of currents and voltages on the surface in contact with the plasma in a simple empirical model has been performed; the comparison of results of calculation and experiment is presented. In the latter case, the pulsed voltage is applied to the discharge collector, thus modulating the plasma potential. The comparison shows that the second method provides more efficient control of the distribution function of ions, acting on the treated substrate.     

Time and energy resolved ion mass spectroscopy studies of the ion flux during high power pulsed magnetron sputtering of Cr in Ar and Ar/N2 atmospheres

Mass spectroscopy was used to analyze the energy and composition of the ion flux during high power pulsed magnetron sputtering (HIPIMS/HPPMS) of a Cr target in an industrial deposition system. The ion energy distribution functions were recorded in the time-averaged and time-resolved mode for Ar⁺, Ar²⁺, Cr⁺, Cr²⁺, N₂⁺ and N⁺ ions. In the metallic mode the dependence on pulse energy (equivalent of peak target current) was studied. In the case of reactive sputtering in an Ar/N₂ atmosphere, variations in ion flux composition were investigated for varying N₂-to-Ar flow ratio at constant pressure and HIPIMS power settings. The number of doubly charged Cr ions is found to increase linearly with increasing pulse energy. An intense flux of energetic N⁺ ions was observed during deposition in the reactive mode. The time evolution of ion flux composition is analyzed in detail and related to the film growth process. The ionization of working gas mixture is hampered during the most energetic phase of discharge by a high flux of sputter-ejected species entering the plasma, causing both gas rarefaction and quenching of the electron energy distribution function. It is suggested that the properties (composition and energy) of the ion flux incident on the substrate can be intentionally adjusted not only by varying the pulse energy (discharge peak current), but also by taking advantage of the observed time variations in the composition of ion flux.     

Thermal behavior and energy storage of a suspension of nano-encapsulated phase change materials in an enclosure

The energy storage capability of a suspension of Nano-Encapsulated Phase Change Material (NEPCM) nanoparticles was addressed in an enclosure during the charging and discharging process. The nanoparticles contain a Phase Change Material (PCM) core, which are capable to absorb a notable quantity of thermal energy on melting. There is a heat pipe in the cavity at the bottom corner, which is enhanced by a layer of metallic matrix. The natural convection flow occurs due to a temperature gradient during the charging or discharging process. The particles of NEPCM move with the natural convection flow and contribute to heat transfer & storage of thermal energy. The regulating equations for the heat transfer & flow of the NEPCM suspension were established & converted in the non-dimensional type. The finite element method (FEM) was utilized in resolving the equations. The results show that there was a rise in the rate of heat transfer & storage of total energy with a rise in nanoparticles volume fraction. The decrease of the Stefan number from 0.2 to 0.6 increases the total stored energy by 25%. The fusion temperature is another important parameter in which its behavior depends on the charging or discharging process.     

Transmission electron microscopy/electron energy loss spectroscopy measurements and ab initio calculation of local magnetic moments at nickel grain boundaries

We have determined local magnetic moments at nickel grain boundaries using a transmission electron microscopy/electron energy loss spectroscopy method assuming that the magnetic moment of Ni atoms is a linear function of the L₃/L₂ (white-line ratio) in the energy loss spectrum. The average magnetic moment measured in the grain interior was 0.55 μ_B, which agrees well with the calculated magnetic moment of pure nickel (0.62 μ_B). The local magnetic moments at the grain boundaries increased up to approximately 1.0 μ_B as the mis-orientation angle increased, and showed a maximum around 50°. The respective enhancement of local magnetic moments at the Σ5 (0.63 μ_B) and random (0.90 μ_B) grain boundaries in pure nickel was approximately 14 and 64% of the grain interior. In contrast, the average local magnetic moment at the (111) Σ3 grain boundary was found to be 0.55 μ_B and almost the same as that of the grain interior. These results are in good agreement with available ab initio calculations.     

Electron energy loss spectroscopy of nano-scale CrAlYN/CrN-CrAlY(O)N/Cr(O)N multilayer coatings deposited by unbalanced magnetron sputtering

The nano-scale chemical distribution and microstructure of a nitride based wear and oxidation resistant coating prepared by unbalanced magnetron sputtering was investigated. The coating consisted of multilayers of CrAlYN/CrN with a partially oxidised CrAlY(O)N/Cr(O)N oxy-nitride surface layer. The multilayer period of both the nitride and oxy-nitride layers was 3.8 ± 0.2 nm. Nano-scale chemical analysis and imaging was performed using sub-nanometer resolution electron energy loss spectroscopic profiling in a spherical aberration corrected scanning transmission electron microscope. Experimentally determined fine edge structure in electron energy loss spectra were in good agreement with theoretically determined spectra, calculated using electron density functional theory. This analysis indicated the CrN layers to be near stoichiometric with a relative Cr/N ratio of 1.05 ± 0.1 while for the CrAlYN layers the best match between the direct chemical analysis and the simulated edges was (Cr_0.5Al_0.5)N. A diffuse interface, ∼ 1 nm wide was observed between the CrAlYN and CrN layers. For the outermost oxy-nitride layer, the chromium to nitrogen ratio remains approximately constant though out the layer, while the aluminium decreases as a function of increasing oxygen content.     

The importance of energy in environmental life cycle assessments of packaging materials

By comparing existing studies and additional scenario calculations it was shown that energy data plays a central role in environmental life cycle assessments (LCA) of packaging materials. More attention should be paid to correctly linking environmental data from energy studies to packaging LCA, if possible adapting the data base to the local conditions. In general terms, it was shown that it is possible to calculate energy and packaging systems separately, because of the predominantly static links between the two. Scenario calculations show that the potential for reducing the environmental impact of packaging production by the use of cleaner energies is still considerable.