This paper reviews gas cluster ion beam (GCIB) technology, including the generation of cluster beams, fundamental characteristics of cluster ion to solid surface interactions, emerging industrial applications, and identification of some of the significant events which occurred as the technology has evolved into what it is today. More than 20 years have passed since the author (I.Y) first began to explore feasibility of processing by gas cluster ion beams at the Ion Beam Engineering Experimental Laboratory of Kyoto University. Processes employing ions of gaseous material clusters comprised of a few hundred to many thousand atoms are now being developed into a new field of ion beam technology. Cluster-surface collisions produce important non-linear effects which are being applied to shallow junction formation, to etching and smoothing of semiconductors, metals, and dielectrics, to assisted formation of thin films with nano-scale accuracy, and to other surface modification applications.

We present an ion-beam based fabrication method for growth of single-crystal-like films that does not utilize epitaxy on single crystal substrates. We use ion-beam assisted texturing to obtain biaxial crystalline alignment in a film. This ion-beam assisted deposition (IBAD) texturing can be done on arbitrary, but smooth substrates, including flexible polycrystalline metal tapes. With IBAD texturing of MgO and subsequent homoepitaxial growth we have demonstrated an in-plane mosaic spread FWHM as low as 2° and out-of-plane alignment of 1°. The deposition system we use includes reel-to-reel tape transport for a linear transport of substrate materials through the deposition zones. This allows for high-throughput experimentation via a linear combinatorial experimental design.

Nanosized materials have been widely applied in biomedical engineering due to their unique nano-effects. In this work, nano-TiO2 coatings and ZrO2 films were prepared using plasma technologies including plasma spraying and cathodic arc plasma deposition. The microstructure the coatings and films were assessed using TEM, SEM, and AFM. Their bioactivity and biocompatibility were evaluated using simulated body fluid soaking tests and cell culturing. Films and coatings with nanostructured surfaces can be obtained using plasma spraying and cathodic arc plasma deposition. The nanostructured surfaces can endow the films and coatings excellent bioactivity and biocompatibility. The UV-illuminated and hydrogen implanted nano-TiO2 coatings and ZrO2 films can induce bone-like apatite formation on their surfaces after immersion in a simulated body fluid for a certain period of time. The nano-TiO2 coating has better cytocompatibility than the micro-TiO2 coating, and the cytocompatibility can be improved by UV-illumination and hydrogen implantation. The bioactivity of the ZrO2 thin film deteriorates after thermal treated. The size of the particles on the surface of the film is thought to be one of the key factors responsible for the bioactivity.

Combined focused ion beam (FIB) and scanning electron microscopy (SEM) methods are becoming increasingly important for nano-materials applications as we continue to develop ways to exploit the complex interplay between primary ion and electron beams and the substrate, in addition to the various subtle relationships with gaseous intermediaries.

We demonstrate some of the recent progress that has been made concerning FIB SEM processing of both conductive and insulating materials for state-of-the-art nanofabrication and prototyping and superior-quality specimen preparation for ultra-high resolution scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) imaging and related in situ nanoanalysis techniques.

This work is focused on nanoscale gold particle formation by low-energy ion irradiation in glow-discharge plasma and studying particle growth by increasing time of exposure.

SiO2+Au films on SiO2 substrates produced by ion beam assisted deposition (IBAD) were exposed to ion irradiation at 1.2 keV energy for 1-2 hours. Plasmon resonance appearance caused by nanoparticle formation was observed by Optical Absorption Spectrometry (OAS).

Fabrication of Nanodots on semiconductor surfaces has immense importance due to their application in memory and optoelectronic devices. Ion irradiation methods display an easy and cost effective route for developing self assembled structures. We have studied the formation of Nano-dots on InP(111) surfaces by 3keV Ar ion irradiation. The distribution of nano Dots on InP surfaces has been investigated by Scanning Probe Microscopy (SPM). A 5 min irradiation of InP surface with Ar ions leads to the appearance of dots on the surface. The density of dots is, however very small. These dots have been obtained at room temperature, in the absence of sample rotation, with an angle of 15 degree between the ion axis and the sample normal. After an irradiation of 10 min a large density of dots appear on InP surface and display a narrow distribution of size and height. The dots at this stage have an average diameter of 25nm and a height of 4nm. With increased irradiation time the average size and the height of the dots increase and their distribution also become broader. This scenario, however, changes after a 40 min irradiation where large rectangular shaped dots of about 100 nm diameters and 40 nm height are observed. Surprisingly, for larger irradiation times a reduction in the size and heights is observed. The studies suggest “Critical Time” tc at t= 40 min such that the dot structures grow with time below tc but diminish in size beyond it.

Ion beam-based techniques offer various possibilities for robust spatial control of nanoparticles. Since ion implantation is inherently good at depth control of solutes or nanoparticles, additional lateral control may lead to 3D control of nanoparticles. We pursue a lateral-control method of nanoparticle assembly by controlling photon-energy field under ion implantation. Laser is irradiated into a-SiO2, either sequentially or simultaneously with ion implantation. Ions of 60 keV Cu- or 3 MeV Cu2+ and photons of 532 nm are used to study effects on nanoparticle evolution. Simultaneous laser irradiation under ion implantation enhances surface plasmon resonance (SPR), i.e., nanoparticle precipitation, while sequential laser irradiation of 532 nm tends to cause a decay of SPR, i.e., dissolution of Cu nanoparticles. The energy-field perturbation of laser, interactive with nanoparticle evolution, can be used for controlling nanoparticle assembly.

We prepared 50 periodic nano-layers of SiO2/AgxSiO2(1-x). The deposited multi-layer films have a periodic structure consisting of alternating layers where each layer is between 1-10 nm thick. The purpose of this research is to generate nanolayers of nanocrystals of Ag with SiO2 as host and as buffer layer using a combination of co-deposition and MeV ion bombardment taking advantage of the electronics energy deposited in the MeV ion track due to ionization in order to nucleate nanoclusters. Our previous work showed that these nanoclusters have crystallinity similar to the bulk material. Nanocrystals of Ag in silica produce an optical absorption band at about 420 nm. Due to the interaction of nanocrystals between sequential nanolayers there is widening of the absorption band. The electrical and thermal properties of the layered structures were studied before and after 5 MeV Si ions bombardment at various fluences to form nanocrystals in layers of SiO2 containing few percent of Ag. Rutherford Backscattering Spectrometry (RBS) was used to monitor the stoichiometry before and after MeV bombardments.

In this work, Ultra High Molecular Weight Poly Ethylene (UHMWPE) samples were implanted with W + C ion by using Metal-Vapour Vacuum Arc (MEVVA) ion implantation technique. Samples were implanted with W and C atoms with a fluence of 1017ion/cm2 and extraction voltage of 30 kV. Mechanism underlies this modification characterized with ATR-FTIR, UV-VIS-NIR Spectrum and Rutherford Backscattering Spectrometry (RBS). Surface morphology of implanted and unimplanted samples were examined in nanoscale with AFM.

Pulsed low-energy (200 eV) ion-beam-induced nucleation during Ge deposition on thin SiO2 film was used to form dense homogeneous arrays of Ge nanocrystals. The ion-beam action is shown to stimulate the nucleation of Ge nanocrystals when being applied after thin Ge layer deposition. Temperature and flux variation was used to optimize the nanocrystal size and array density required for memory device. Kinetic Monte Carlo simulation shows that ion impacts open an additional channel of atom displacement from a nanocrystal onto SiO2 surface. This results both in decrease of the average nanocrystal size and in increase of nanocrystal density.

Thermoelectric power generation is a promising technology for increasing the efficiency of electrical and optical electrical devices. We prepared samples by Electron Beam evaporating Zn4Sb3 and CeFe2Co2Sb12 thin films on silicon dioxide (silica) substrates. The materials were co-evaporated and then were prepared for gold over-coating. Following electron deposition we performed post ion bombardment at a constant energy of 5 MeV while varying fluence from 1×1012, 1×1013, 1×1014, 1×1015 ions/cm2, respectfully. The production of nano-clusters generated from the MeV Si ions bombardment modifies the electrical and phonon interactions in the materials. Also, we will report on the fluence dependence of the figure of merit, Seebeck Coefficient, thermal conductivity and electrical conductivity. In addition, Rutherford backscattering spectrometry (RBS) was used to analyze the elemental composition and the thickness of the deposited material.

Focused ion beam (FIB) techniques have found many applications in nanoscience and nanotechnology applications in recent years. However, not much work has been done using FIB to fabricate carbon nanotube devices. This is mainly due to the fact that carbon nanotubes are very fragile and energetic ion beam from FIB can easily damage the carbon nanotubes. Here we report the fabrication of carbon nanotube (CNT) devices, including electron field emitters, atomic force microscope tips, and nano-pores for biomedical applications. This is made possible by a unique, coaxial configuration consisting of a CNT embedded in a graphitic carbon coating, which was developed by us for FIB processing of carbon nanotubes. The CNT-based atomic force microscope tip has been demonstrated. The electron field emission from the tip and the side wall of CNT will be discussed. We will also report the fabrication of a multiwall carbon nanotube nanopore for future applications.

Irradiation-induced processes are often considered only in their nonequilibrium aspects. The purpose of this brief review is to show that chemistry, and particularly redox properties, play a major role in the thermal evolution of such systems and generally cannot, therefore, be neglected. This is exemplified by the synthesis of Ag nanoclusters in glasses and silica, under both low (gamma-ray) and high (MeV ion) deposited energy density irradiation conditions. The nanocluster formation mechanism is shown to be similar to the latent image formation process in photography. The corresponding information was used to control nucleation and growth of PbS clusters in glasses, leading to promising optical properties. In the course of these studies, we also showed that lognormal size distributions characterize the absence of information on the nanocluster formation process.

Multi quantum wells of InGaAs/InP grown by metal organic chemical vapor deposition have been irradiated using swift heavy ions. Irradiation has been performed using 150MeV Ag and 200MeV Au ions. Both as-grown and irradiated samples were subjected to rapid thermal annealing at 500 and 7000C for 60s. As-grown, irradiated and annealed samples were subjected to high resolution x-ray diffraction studies. Both symmetric and asymmetric scans were analyzed. The as-grown and Ag ion irradiated samples show sharp and highly ordered satellite peaks whereas, the Au ion irradiated samples show broad and low intense peaks. The higher order satellite peaks of the annealed samples vanished with increase of annealing temperature from 500 to 7000C, indicating mixing induced interfacial disorder. Annealing of irradiated samples show higher mixing and disorder and no higher order satellite peaks were observed. Negligible strain was observed after high temperature annealing of as grown samples. Strain values calculated from the X-ray studies indicate that the irradiated samples have higher strain which has been reduced upon annealing. This indicates that the annealing induced mixing occurs maintaining the lattice parameter close to that of the substrate. The effect of electronic energy loss for interface mixing has been discussed in detail. The role of incident ion fluence in combination with the electronic energy loss will also be discussed in detail. The results have been compared with the literature and discussed in detail.

Swift heavy ion beam-based lithography using masks of self-assembled materials has been applied for transferring well-ordered micro- and nanopatterns to rutile TiO2 single crystals. As the induced damage has a high etching selectivity the patterns can be developed in HF with very high contrast. Here we present resulting patterns when using a mask of self-ordered silica spheres. Since the obtained structures are replicas of the mass distribution of the applied mask, the shape and size of resulting structures depend on the geometric configuration of the silica sphere layers. In addition, the resulting pattern can be tuned by varying the applied ion energy and fluence. Direct modifications of the optical properties of TiO2 in a well-defined pattern are also presented.

Semiconducting â-Zn4Sb3 and ZrNiSn-based half-heusler compound thin films were prepared by co-evaporation for the application of thermoelectric (TE) materials. High-purity solid zinc and antimony were evaporated by electron beam to grow the â-Zn4Sb3 thin film while high-purity zirconium powder and nickel tin powders were evaporated by electron beam to grow the ZrNiSn-based half-heusler compound thin film. Rutherford backscattering spectrometry (RBS) was used to analyze the composition of the thin films. The grown thin films were subjected to 5 MeV Si ions bombardments for generation of nanostructures in the films. We measured the thermal conductivity, Seebeck coefficient, and electrical conductivity of these two systems before and after 5 MeV Si ions beam bombardments. The two material systems have been identified as promising TE materials for the application of thermal-to-electrical energy conversion, but the efficiency still limits their applications. The electronic energy deposited due to ionization in the track of MeV ion beam can cause localized crystallization. The nanostructures produced by MeV ion beam can cause significant change in both the electrical and the thermal conductivity of thin films, thereby improving the efficiency. We used the 3ù-method measurement system to measure the cross-plane thermal conductivity ,the Van der Pauw measurement system to measure the cross-plane electrical conductivity, and the Seebeck-coefficient measurement system to measure the cross-plane Seebeck coefficient. The thermoelectric figures of merit of the two material systems were then derived by calculations using the measurement results. The MeV ion-beam bombardment was found to decrease the thermal conductivity of thin films and increase the efficiency of thermal-to-electrical energy conversion.

Ion irradiation has been used to transform spherical bimetallic AuAg nanocluster embedded in silica in a more complex structure made of a central cluster surrounded by a halo of smaller satellite nanoclusters, whose composition, size and distance from the central cluster can be tailored by controlling the irradiation parameters. This peculiar topology produces a red-shift of the surface plasma resonance of the composite through the electromagnetic coupling between the central cluster and the satellites. A calculation of the local field properties of the investigated systems within the fully-interacting generalized Mie theory showed that the satellite topology produces large local field enhancements around the central cluster.

In this study the results of polychromatic X-ray microbeam analysis (PXM) of the structural changes caused by FIB in nitride heterostructures are presented and discussed in connection with micro-photoluminescence (μ-PL), fluorescent analysis, scanning electron (SEM) and transmission electron microscopy (TEM) data. It is shown that FIB processing distorts the lattice in the InGaN/GaN layer not only in the immediate vicinity of the processed area but also in the surroundings. A narrow amorphidized top layer is formed in the direct ion beam impact area.

In order to keep the stoichemistry of Bi2Te3 and Sb2Te3 so as to keep the electrical and thermal conductivity advantage of the layered structure of bulk Bi2Te3 and Sb2Te3 in each period of the superlattice, magnetron sputtering, which is operated at relatively low temperature, was used to deposit multiplayer Bi2Te3/Sb2Te3 thermoelectric superlattice device. The two guns in our magnetron sputtering device is oriented at a certain angle to get off-axis plasma plume, which will form lattice with preferential orientation for electrical conductivity in each layer. The super lattice was then bombarded by MeV Si ions with different fluence in order to form nanoscale cluster quantum dot-like structures. In addition to the effect of quantum well confinement of the phonon transmission, the nanoscale clusters produced by the bombardment of ion beam further adversely affect the thermal conductivity. The defect and disorder in the lattice caused by bombardment and the grain boundary of these nanoscale clusters increase the scattering of phonon and increase the chance of the inelastic interaction of phonon and the annihilation of phonon, this limits phonon mean free path. Phonons are chiefly absorbed and dissipated along the lattice, therefore reduces the cross plane thermal conductivity, The increases of the electron density of state in the miniband of nanoscale cluster quantum dot-like structure formed by bombardment also increases Seebeck coefficient, and the electrical conductivity. Eventually, the thermo-electric figure of merit of superlattice films increases.

We prepared 8 periodic nano-layers of SiO2/SiO2+Zn4Sb3. The deposited multi-layer films have a periodic structure consisting of alternating layers where each layer is between 1-10 nm thick. The purpose of this research is to generate nanolayers of nanostructures of Zn4Sb3 with SiO2 as host and as buffer layer using a combination of co-deposition and MeV ion bombardment taking advantage of the electronics energy deposited in the MeV ion track due to ionization in order to nucleate nanostructures. The electrical and thermal properties of the layered structures were studied before and after bombardment by 5 MeV Si ions at various fluences to form nanostructures in layers of SiO2 containing Zn4Sb3. Rutherford Backscattering Spectrometry (RBS) was used to monitor the stoichiometry before and after MeV bombardments.