Two-dimensional numerical simulations with the particle tracking method were conducted to analyse the dispersion behind the detonation front and its mean structure. The mixtures were 2H$_2$–O$_2$–7Ar and 2H$_2$–O$_2$ of increased irregularity in ambient conditions. The detonation could be described as a two-scale phenomenon, especially for the unstable case. The first scale is related to the main heat release zone, and the second where some classical laws of turbulence remain relevant. The dispersion of the particles was promoted by the fluctuations of the leading shock and its curvature, the presence of the reaction front, and to a lesser extent transverse waves, jets and vortex motion. Indeed, the dispersion and the relative dispersion could be scaled using the reduced activation energy and the $\chi$ parameter, respectively, suggesting that the main mechanism driving the dispersion came from the one-dimensional leading shock fluctuations and heat release. The dispersion within the induction time scale was closely related to the cellular structure, particles accumulating along the trajectory of the triple points. Then, after a transient where the fading transverse waves and the vortical motions coming from jets and slip lines were present, the relative dispersion relaxed towards a Richardson–Obukhov regime, especially for the unstable case. Two new Lagrangian Favre average procedures for the gaseous detonation in the instantaneous shock frame were proposed and the mean profiles were compared with those from Eulerian procedure. The characteristic lengths for the detonation were similar, meaning that the Eulerian procedure gave the mean structure with a reasonable accuracy.

Two-dimensional (2-D) numerical simulations based on the Eulerian–Lagrangian method that take droplet break-up into account are conducted to clarify the mean structure of gaseous detonation laden with a dilute water spray. The premixed mixture is a slightly diluted stoichiometric hydrogen–oxygen mixture at low pressure. The simulated results are analysed via 2-D flow fields and statistical Favre spatiotemporal averaging techniques. Gaseous detonation with water droplets (WD) propagates stably with a velocity decrease compared with the dry Chapman–Jouguet speed. The mean structure of gaseous detonation with dilute water spray shares a similar structure as the one without water spray. However, the hydrodynamic thickness is changed due to the interaction with water spray. Overall interphase exchanges (mass, momentum and energy) that take place within the hydrodynamic thickness induce a decrease of the detonation velocity and lower the level of fluctuations downstream of the mean leading shock wave. Droplet break-up occurs downstream of the induction zone and in our case, the water vapour from the evaporation of water spray does not affect the reactivity of gaseous detonation. The laminar master equation for gaseous detonation laden with inert WD shows that the hydrodynamic thickness should rely on the gaseous sound speed, and works well as the working mixture is weakly unstable and its cellular structure is regular. The droplet flow regimes and break-up modes have also been determined. The characteristic lengths of detonation and interphase exchanges have been ordered under the present simulation conditions and have been shown to be intimately intertwined.

Ar cluster ions in the size range 1000�16000 atoms/cluster were irradiated onto Si substrates at incident energies of 10 and 20 keV and the sputtering yields were measured. Incident cluster ions were size-selected by using the time-of-flight (TOF) method. The sputtering yield was calculated from the sputtered Si volume and irradiation dose. It was found that the sputtering yields decreased with increasing incident cluster size under the same incident energy conditions. The integrated sputtering yields calculated from the sputtering yields measured for each size of Ar cluster ions, as well as the cluster size distributions, were in good agreement with experimental results obtained with nonselected Ar cluster ion beams.

To investigate the size-effect of reactive clusters on sputtering processes, we performed molecular dynamics (MD) simulations of reactive cluster ions with various sizes impacting on solid targets. Various sizes of fluorine clusters, (F2)30, (F2)300 and (F2)3000, were irradiated on a Si(100) target at the same total incident energy of 6 keV. These clusters were irradiated on the same target one after another in order to reproduce real experimental conditions such as the accumulation of fluorine atoms in the target. The MD simulations of sequential cluster impacts enabled to perform various statistical analyses regarding the sputtered particles. The study of cluster size distributions showed that the sputtering process by reactive cluster ion impact has similarity with the emission from quasi-liquid materials excited to hyper-thermal conditions by ion bombardment. However, the major sputtered particles were different with each other; Si for (F2)30 (100 eV/atom), SiF2 for (F2)300 (10 eV/atom), and SiF3 for (F2)3000 (1 eV/atom). At the impact of a large size cluster with low incident energy, a large number of Si-F bondings were generated at the cluster-target interface surface, which enhances formation of volatile SiFx compounds with many fluorine atoms. In contrast, a small cluster with high kinetic energy-per-atom could cause the formation of numerous energetic surface atoms at the near surface region, which could be sputtered without being well fluoridated.

In order to study the surface reaction process under cluster ion impact, molecular dynamics simulations of sequential cluster impacts of fluorine and neon clusters were performed. (F2)300 and Ne600 clusters were accelerated with totally 6keV and irradiated on bare Si(100) target. By iterating impact simulation sequentially, change of surface morphology and composition of desorbed materials were studied. In the case of fluorine cluster impact, the rough surface structure was made compared with neon cluster impact because fluorine atoms adsorb on the target, which work to keep pillar structure on the surface, whereas Ne atoms evaporate immediately leaving spherical mound structure on the surface. From the study of desorption process, it was observed that large number of Si atoms are desorbed in the form of silicon fluorides. The major sputtered material was SiF2, but various types of silicon-fluorides, including the molecules consists of several tens to hundreds silicon and fluorine atoms, were observed. The distribution of clusters in desorbed materials obeyed the classical model of cluster emission from quasi-liquid phase excited with ion bombardment. From these results, the irradiation effects of reactive cluster ions were discussed.

Cluster ion beam processes can produce high rate sputtering with low damage in comparison with monomer ion beam processes. Especially, it is expected that extreme high rate sputtering can be obtained using reactive cluster ion beams. Reactive cluster ion beams, such as SF6, CF4, CHF3, and CH2F2, were generated and their cluster size distributions were measured using Time-of-Flight (TOF) method. Si substrates were irradiated with the reactive cluster ions at the acceleration energy of 5–65 keV. Each sputtering yield was increased with acceleration energy and was about 1000 times higher than that of Ar monomer ions. The sputtering yield of SF6 cluster ions was about 4600 atoms/ion at 65 keV. With this beam, 12 inches wafers can be etched 0.5 μm per minute at 1 mA of beam current. The TOF measurement showed that the size of SF6 cluster was about 550 molecules and the number of fluorine atoms in a SF6 cluster was about 3300. If the sputtered product was SiF, the yield has to be less than 3300 atoms/ion. These results indicate that the reactive cluster ions etch targets not only chemically, but also physically. This high-speed processing with reactive cluster ion beam can be applied to fabricate nano-devices.

Oblique irradiation using a gas cluster ion beam (GCIB) has been studied in order to achieve low-damage smoothing of magnetic materials. We investigated how the surface morphology and surface roughness depended on the angle of incidence. Quite smooth surfaces could be obtained using both normal and grazing-incidence irradiation. At incident angles larger than 45?, periodic ripples were formed. The orientation of the ripples changed from perpendicular to parallel with respect to the GCIB when the incident angle exceeded a critical value. Surface roughening resulting from the formation of ripples was observed at incident angles between 45° and 65°. Fluctuations in the Ni/Fe component ratio and the intermixing of oxygen from the native oxide were evaluated. As the angle of incidence increased, both the thickness of the layer in which the component ratio was fluctuating and the depth of oxygen intermixing decreased. As a result, it was determined that low-damage smoothing of magnetic materials could be performed by using grazing-incidence irradiation from a GCIB.

Cluster ion beam processes can produce high rate sputtering with low damage in comparison with monomer ion beam processes. Especially, it is expected that extreme high rate sputtering can be obtained using reactive cluster ion beams. High current SF6 cluster ion beams were recently obtained with new modifications in the basic cluster ion beam technique. The cluster size distribution was measured with Time-of-Flight (TOF) method and the mean size of cluster was about 500 molecules. Si substrates were irradiated with SF6 cluster ions at the acceleration energy of 5–45 keV. Sputtering yield with SF6 cluster ions was increased with acceleration energy and was about 2300 atoms/ion at 45 keV. The sputtering yield was about 1000 times higher than that of Ar monomer ions and was also higher than that of Ar cluster ions. It was found that reactive sputtering occurred with SF6 cluster ion irradiation. These results indicate that high-speed fabrication can be realized with reactive cluster ion irradiation at high energy.

In order to understand the characteristics of surface modification process with cluster ion irradiation, molecular dynamics simulations of Ar cluster impacting on Si surface with various surface structures were carried out. It was found that the surface morphology is dynamically deformed with only one cluster impact and the impact process of cluster is different depending on the local surface structure. For example, when an Ar2000 cluster accelerated with 20keV impacted on the convex point of the surface, the hill was compressed and the impact area was smoothed. At the impact on a concave point, a deeper crater was formed compared with the impact on a flat surface. On the other hand, the MD simulations of sequential impacts of large clusters were performed. It was found that the small tip structures on the surface could be removed easily with cluster irradiation. It was shown that surface roughness converges to 15∼20Å and this value agrees with the result obtained by single impact of cluster.

Ar penetration during gas cluster ion beam (GCIB) irradiation has been investigated using secondary ion mass spectroscopy (SIMS). The concentration of Ar rose to a maximum and then decreased gradually with increasing depth. The depth of the Ar penetration peak increased in proportion to the cube root of the acceleration voltage of GCIB and was independent of ion dose. Ar penetration was attributed to fast neutrals in the GCIB and was successfully suppressed by decreasing the pressure of the space downstream of the GCIB or decreasing the monomer ion density in order to suppress charge transfer collisions.

Smoothing effect by large gas cluster ion irradiation was studied. Ar cluster ion beams were irradiated on rough Si surface with various ion dosage. 100×100μm2 AFM image was measured for each surface. These AFM images were treated with fast Fourier transform in order to examine the change of surface morphologies with cluster ion irradiation. Power spectra analysis showed that the intensity at each wave number (the inverse number of wavelength) exponentially decreases with ion dose. The relationship between smoothing rate and wave number was derived. The surface smoothing process was modeled with the use of this wave number dependence on decreasing rate. The calculated and the experimental surface profiles are in good agreements. With this model, roughness of cluster-irradiated surface can be calculated from initial surface images.

In order to understand the damage formation by cluster ion irradiation, Si substrates were irradiated with Ar cluster ions at the acceleration energy of 1–20keV. The mean size of cluster was about 3000 atoms. The amount of damage after Ar cluster ion irradiation was measured with Rutherford backscattering spectrometry (RBS). The amount of damage was decreased with decrease of the energy and no damage formed at less than 2keV. This energy of 2keV represents the threshold energy to generate damage with the cluster size of 3000. According to Molecular dynamics (MD) simulation, the damage formation with cluster ion irradiation also depends on cluster size. The size dependence of amount of damage has been investigated experimentally. The cluster size distribution could be changed with the ionization condition and could be measured using Time-of-Flight (TOF) method. The threshold energy was increased with cluster size. These results indicate that undamaged films can be created by using large size of cluster ion with low acceleration energy.

Defect formation in Si by B10H14 (decaborane) ion implantation has been investigated with photoluminescence measurement. An intense W-line was observed at photon energy of 1.018eV from as-implanted FZ-Si by 30keV B10H14+ implantation. W-line center is considered as an interstitial aggregate and usually observed after ion implantation with subsequent low-temperatureannealing in the case of atomic ion implantation. As W-line is observed from as-implanted Si, the defect formation with B10H14 is expected to be different from that of B+ implantation with the same energy per atom. The energy dependence of W-line intensity is similar to that of diffusivity enhancement after rapid thermal annealing. Molecular dynamics simulation and Rutherford backscattering spectrometry channeling experiment suggest that one B10H14 implantation creates a larger number of dislocated Si atoms than that of B+ implantation with the same energy per atom. This characteristic of B10H14 implantation may cause the different defect reactions in subsequent annealing process.

Molecular dynamics simulations of boron monomer and small clusters (B4 and B10) impacting on Si(001) were performed in order to investigate the damage formation by monomer/cluster impact. These monomer and clusters show similar implant depth and efficiency, but different damage structures. At the impact of B monomer with 230eV of incident energy, some point-defects such as vacancy-interstitial pairs are mainly formed. On the other hand B10 produces several times larger number of vacancies and interstitials compared with B1, This damage structure is different from one by B1 implantation and due to high yield amorphization of implanted region. This characteristic damage formation process is expected to cause different annihilation process.

New surface modification processes have been demonstrated using gas cluster ion irradiations because of their unique interaction between cluster ions and surface atoms. For example, high quality ITO films could be obtained by O2 cluster ion assisted deposition at room temperature. It is necessary to understand the role of cluster ion bombardment during film formation for the further developments of this technology. Variable Temperature Scanning Tunneling Microscope (VT-STM) in Ultra High Vacuum (UHV) allows us to study ion bombardment effects on surfaces and nucleation growth at various temperatures.

The irradiation effects between Ar cluster ion and Xe monomer ion were compared. When a Si(111) surface with Ge deposited to a few Å was annealed to 400°C, it was observed that many islands of Ge were formed. The surface with the Ge islands was irradiated by these ions. In the STM image of cluster-irradiated surface, large craters with diameter of about 100 Å were observed, while only small traces with diameter of about 20 Å were observed in monomer-irradiated surface. The number of Ge atoms displaced by one Ar cluster ion impact was much larger than that by one Xe ion impact. This result indicates that Ar cluster ion impacts can enhance the physical modification of Ge islands. When the sample irradiated with Ar cluster was annealed at 600°C, the hole remained, but the outer rim of the crater disappeared and the surface structure was reconstructed at the site of the rim. The depth of damage region in the target became shallower with decrease of the impact energy. These results indicate that low damage and useful surface modification can be realized using the cluster ion beam.

Molecular dynamics (MD) simulations of various cluster ions impacting on solid targets were performed in order to examine the implant and damage formation processes. Ne and Ar rare gas cluster with various cluster sizes, and fullerene (C60) were impacted on diamond (001) surface. It was shown that the impact process of cluster ion depends on the cluster size. When the cluster size is small and incident energy-per-atom is high, such as Ar15 with 800eV/atom, all incident Ar atoms penetrate the surface and reside in the substrate. As the cluster size increases and the incident energy-per-atom decreases, the implant depth decreases and the profile of the displacement becomes shallower. A large cluster, such as Ar60 with 200eV/atom, shows a shallower implant depth and a higher sputtering yield than Ar15. However, Ar240 with 50eV/atom shows a shallower implant depth, but less sputtering yield than Ar60.These results suggest that there is proper cluster size and incident energy where the maximum sputtering yield is achieved.

Secondary Ion Mass Spectrometry (SIMS) with Gas Cluster Ion Beams (GCIB) was studied with experiments and molecular dynamics (MD) simulations to achieve a high-resolution depth profiling. For this purpose, it is important to prevent both ion-mixing and the surface roughening due to energetic ions. As the Ar cluster ion beam shows surface smoothing effects and high secondary-ion yield in the low-energy regime, the cluster ion beam would be suitable for the primary ion beam of SIMS. From MD simulations of Ar cluster ion impact on a Si substrate, the ion-mixing is heavier than for Ar monomer ions at the same energy per atom, because the energy density at the impact point by clusters is extremely high. However, the sputtering yields with Ar cluster ions are one or two orders of magnitude higher than that with Ar monomer ions at the same energy per atom. Comparing at the ion energy where the ion-mixing depths are the same by both cluster and monomer ion impacts, cluster ions show almost ten times higher sputtering yield than Ar monomer ions. Preliminary experiment was done with a conventional SIMS detector and a mass resolution of several nm was achieved with Ar cluster ions as a primary ion beam.

Implantation of B cluster ions into Si using decaborane (B10H14) has been demonstrated. SIMS measurements show that the depth distribution of boron atoms implanted with a monomer ion is exactly matched by that of boron atoms implanted from decaborane ions, if the cluster ion has an order of magnitude larger acceleration energy. According to the Langmuir-Child equation, two orders of magnitude larger space-charge limited ion beam current is possible when decaborane ions are used. Implanted boron atoms from decaborane ions are electrically activated after annealing. Junction depth of the implanted layer with 3 keV decaborane ions is approximately 20nm after annealing at 900°C. Molecular dynamic caluculations show that implantation efficency of boron monomer ions and decaborane ions are the same. However, the number of displaced silicon atoms per implanted boron atom from a decaborane ion impact is 4 times larger than that by boron monomer impact so that a heavily damaged region is created near the impact zone by decaborane ion penetration.

In order to interpret the projection range and to reveal the mechanism of damage formation by cluster ion impact, molecular dynamics simulations of a fullerene carbon cluster (C60) impacting on diamond (001) surfaces were performed. When the kinetic energy of C60 is as low as 200eV/atom, C60 implants into the substrate deeper than a monomer ion with the same energy per atom because of the clearing-way effect. The kinetic energy of the cluster disperses isotropically because of the multiple-collision effect, and then a large hemispherical damage region is formed. When the energy of the cluster is as high as 2keV/atom, the cluster dissociates in the substrate, and then cascade damage is formed like in a case of a monomer ion impact. The projection range of incident atoms becomes similar to that of the monomer with the same energy per atom. However, the number of displacements of C60 is larger than the summation of 60 monomer carbons. The displacement yield of fullerene is 4 to 7 times higher than that of monomer carbon. This result agrees with the measurement of the displacements made on sapphire substrates with C60 and C2 irradiation.