Ion beam assisted deposition (IBAD) has been used to deposit chromium nitride coatings using 1200 eV nitrogen ions from an RF-type ion source and thermally evaporated chromium. The ion/atom arrival ratio R was varied from 0 to 8 to modify the coating composition, microstructure, growth rate and stress state in order to optimize the properties of the material for use as a possible substitute for electroplated chromium in a number of anti-corrosion and tribological applications. The coatings were examined using Rutherford backscattering spectrometry and x-ray photoelectron spectroscopy, and contained up to 44 at % nitrogen in a mixture of bcc Cr-N, Cr2N, and CrN. The microstructure of the coatings was examined by scanning electron microscopy, and the tribological behavior of the coatings was examined using an automated scratch testing and nanoindentation. XPS examination of the coatings indicates that nitrogen near the surface was bound to the metal as CrN and Cr2N in most of the coatings studied by XPS, which is expected to significantly affect their corrosion behavior. The high R values needed to form large amounts of the CrN phase in the bulk of the coating causes significant sputtering during deposition. This study indicates that it is not possible to form a coating consisting solely of cubic CrN by IBAD under these experimental conditions (room temperature substrate and partial pressure of nitrogen of 1.8 × 10−2 Pa). Nevertheless, the IBAD coatings produced were hard, in a compressive stress state, and highly adherent, all properties that make them candidates for use in selected Army applications.

High austenitic stainless steel of composition Fe62Ni2OCrl8 was implanted with Eu ions and analyzed with Depth Selective Conversion Electron Mössbauer Spectroscopy (DCEMS). DCEMS gives information about the depth profile of phases, in this case about implantation induced changes in phase composition as function of depth. The samples were complementary analyzed with Rutherford Backscattering Spectrometry (RBS) to get the element profile of the implanted ions. The main experimental result is a martensitic transformed depth region that coincides with the Eu depth distribution. The potential of DCEMS for application in the field of materials modification by implantation techniques is demonstrated.

Monocrystals of magnesium oxide and sapphire have been subjected to ion implantation with 86 keV Si− ions to a dose of 5×1016 cm−2 and with 3 MeV H+ ions with a dose of 4.8×1017 cm−2 prior to thermal stress testing in a pulsed plasma. Fracture and deformation characteristics of the surface layer were measured in ion implanted and unimplanted samples using optical and scanning electron microscopy. Ion implantation is shown to modify the near-surface structure of samples by introducing damage, which makes crack nucleation easier under the applied stress. The effect of ion dose on the thermal stress resistance is investigated and the critical doses which produce a noticeable change in the stress resistance is determined for sapphire crystals implanted with 86 keV Si−. In comparison with 86 keV Si− ions the high energy implantation of sapphire and magnesium oxide crystals with 3 MeV H+ ions results in the formation of large-scale defects, which produce a low density crack system and cause a considerable reduction in the resistance to damage. Fracture mechanics principles are applied to evaluate the size of the implantation-induced microcracks which are shown to be comparable with the ion range and the damage range in the crystals tested. Possible mechanisms of crack nucleation for a low and high energy ion implantation are discussed.

The collision cascade, the fundamental event in ion-solid interactions, is responsible for the beneficial effects on thin films deposited by low energy ion beam assisted deposition (IBAD) or by energetic ion assisted deposition processes in general. However, the fundamental implications of the marriage of collision cascades and film growth processes have yet to be fully realized. The first half of this paper reviews the effects of ion bombardment on film growth and reaches some new conclusions. We propose that IBAD represents a different ion-solid interaction in a fundamental sense, and that as such, it should lead to new microstructures unattainable by other materials synthesis methods.

The second part of this paper discusses the deposition of metal nanoclusters in a dielectric matrix by means of beam assisted phase separation (BAPS), a term coined here to describe deposition of phase-separated multicomponent materials. Examples discussed are gold nanoparticles in both niobium oxide and silica matrices.

In-plane aligned MgO thin films (∼100Å) have been obtained on various amorphous substrates by Ar+ ion-assisted electron-beam evaporation. Based on RHEED and cross-section TEM, we have shown that the MgO texture appears at a very early stage of film growth and is optimized at a thickness of around 100Å. Optimal thickness is the stage at which the surface is fully covered by MgO crystallites. The planar-view TEM of grain structure evolution in samples at different stages of growth reveals the dynamics of the texture developing process. Small, (100)-faceted MgO grains were observed both in planar-view and cross-section TEM images.

Amorphous carbon films and CN films were prepared by ion beam deposition using isotopically mass-separated, hyper-thermal (50–400eV) ion species such as 12C2−, 12C14N− or simultaneous 12C2− and 14N+ under high vacuum condition. Film properties such as structures, bonding states, compositions, etc. were investigated. The optical band gaps of amorphous carbon films deposited by using 12C2−ions or CN films deposited by using 12C14N− ions were estimated from optical constants. The gaps were about 2.3eV for the amorphous carbon films and about 0.8 eV for the CN films. Energy dependence of optical constants of CN films formed by simultaneous deposition of C2− and N+ was investigated. The refractive index (n) and extinction coefficient (k) at λ = 675nm increased 1.5 to 2.4 and 0.3 to 1.3, respectively, with increasing N+ kinetic energy. The relations between bonding states and kinetic energy of hyper-thermal ions are discussed.

Tin oxide films were deposited on in-situ heated Si (100)substrates using reactive ionassisted deposition and the effect of average impinging energy of oxygen ions on the crystalline structure and the stoichiometry of deposited films were examined. The transformation from SnO phase to SnO2 phase of the films was dependent on the change of the average impinging energy of oxygen ion (Ea), and the relative arrival ratio of oxygen to tin. Perfect oxidation of SnO2 was performed at Ea = 100, 125 eV/atom at as low as 400 Å substrate temperature. The composition (No/Nsn) of films increased from 1.21 to 1.89, and was closely related to the average impinging energy of oxygen ion. The surface morphology of the films was also investigated by scanning electron microscopy.

Aluminum oxide (A12O3) films were prepared on a nickel based superalloy (Inconel 718) by ion beam assisted plasma CVD at the multiple incident angles of the ion beams to a substrate. Crystal structure of these films was analyzed by X-ray diffraction (XRD). Electrical resistance of the films was measured at temperatures ranging from room temperature to 850°C. The incident angle of the ion beams influenced the orientation of A12O3 crystals. The net integrated intensity was calculated in order to compare the intensity among the different thickness samples whose thickness is thinner than X-ray penetration depth. The electrical resistivity depends on the relative X-ray intensity of (110) and (300) of α-A12O3.

Complex nonlinear optical materials comprising elemental, compound or alloy quantum dots embedded in appropriate dielectric or semiconducting hosts may be suitable for deployment in photonic devices. Ion implantation, ion exchange followed by ion implantation, and pulsed laser deposition have all been used to synthesize these materials. However, the correlation between the parameters of energetic-beam synthesis and the nonlinear optical properties is still very rudimentary when one starts to ask what is happening at nanoscale dimensions. Systems integration of corplex nonlinear optical materials requires that the mesoscale materials science be well understood within the context of device structures. We discuss the effects of beam energy and energy density on quantum-dot size and spatial distribution, thermal conductivity, quantum-dot composition, crystallinity and defects — and, in turn, on the third-order optical susceptibility of the composite material. Examples from recent work in our laboratories are used to illustrate these effects.

Samples of fused silica were implanted at room temperature with 300 keV-Ag+ for doses ranging from 0.8×1016 to 14×1016 ions/cm2. A multi-technique approach including Rutherford backscattering spectrometry (RBS), x-ray diffraction (XRD), optical absorption and Raman scattering spectroscopies has been used to characterize silver precipitate. The Ag-depth profiles of samples implanted with doses higher than 6×1016 Ag+/cm2 show a bi-modal distribution, with the appearance of a secondary maximum near the surface. XRD spectra indicated the formation of silver nanocrystals of ∼10 nm in size within the heavily implanted samples. Optical absorption has been used to monitor the effects of ion doses on the optical properties of the metal clusters in the UV-Vis region. A single broad absorption band, due to surface plasmon resonance, is peaked at about 400 nm for low implantation doses. For doses higher than 4.3×1016 Ag+/cm2, a second broad band originates at higher wavelengths, peaking at 625 nm for the highest dose. The evolution of optical spectra is tentatively discussed in terms of the formation of silver particle aggregates with no longer spherical shape. An estimate of the mean size of silver nanoclusters of about 5.5 nm is obtained from low-frequency Raman scattering due to acoustic vibrations localized at the cluster surface. The discrepancies in the metal particle size obtained from XRD and Raman scattering measurements are discussed with respect to optical absorption data.

Nanoparticles of Cu were fabricated by negative-ion implantation, leading to spontaneous formation at high beam fluxes. Negative ions, alleviating surface charging, exhibit significant merits in carrying out low-energy implantation at high dose rates. The kinetic processes were studied by measuring dose-rate dependence of colloid formation and resultant optical properties. Negative-Cu ions of 60 keV were implanted into silica glasses at high-current densities, up to 260 μA/cm2, fixing the total dose at 3.0 × 1016 ions/cm2. Spherical nanocrystals of Cu atoms formed within a narrow region, near the projectile range of Cu ions. Simultaneously, much smaller particles spread out beyond a depleted zone, deeper than the projectile range. The nanocrystal growth and optical properties were greatly dependent on the dose rate and the specimen boundary condition. The growth process is explained by a droplet-model based on surface tension and radiation-induced diffusion. Beam-surface interactions also play an important role in the mass transport from the beam flux to the interior solid.

We present the results of our investigation of the change in the optical properties of silica, "suprasil", after keV through MeV implantation of copper, tin, silver and gold and after annealing. Suprasil, name brand of silica glass produced by Hereaus Amersil, which is chemically highly pure with well known optical properties. Both linear and nonlinear optical properties of the implanted silica were investigated before and after thermal annealing. All implants showed strong optical absorption bands in agreement with Mie theory. For implants with a measurable optical absorption band we used Doyle's theory and the full width half maximum of the absorption band to calculate the predicted size of the formed nanoclusters at various heat treatment temperatures. These results are compared with those obtained from direct observation using transmission electron microscopic techniques.

We report the results of characterization of linear and nonlinear optical properties of a light guide structure produced by MeV Ag ion implantation of LiNbO3 crystal (z-cut) in relation to the mechanisms of formation.

We present the results of characterization of linear absorption and nonlinear refractive index of Au, Ag, Cu and Sn ion implantation into LiNbO3. Silver was implanted at 1.5 MeV to fluences of 2 to 17 × 1016/cm2 at room temperature. Gold and copper were implanted to fluences of 5 to 20 × 1016/cm2 at an energy of 2.0 MeV. Tin was implanted to a fluence of 1.6 × 1017/cm2 at 160 kV. After heat treatment at 1000°C a strong optical absorption peak for the Au implanted samples appeared at ∼620 nm. The absorption peaks of the Ag implanted samples shifted from ∼450 nm before heat treatment to 550 nm after 500°C for lh. Heat treatment at 800°C returned the Ag implanted crystals to a clear state. Cu nanocluster absorption peaks disappears at 500°C. No Sn clusters were observed by optical absorption or XRD. The size of the Ag and Au clusters as a function of heat treatment were determined from the absorption peaks. The Ag clusters did not appreciably change in size with heat treatment. The Au clusters increased from 3 to 9 nm in diameter upon heat treatment at 1000°C. TEM analysis performed on a Au implanted crystal indicated the formation of Au nanocrystals with facets normal to the c-axis. Measurements of the nonlinear refractive indices made using the Z-scan method showed that Ag implantation changed the sign of the nonlinear index of LiNbO3 from negative to positive.

The effect of the ion implantation (Fe) on LiNbO3, MgO, and A12O3 crystals is studied using electron paramagnetic resonance (EPR). EPR measurements on these crystals were performed as a function of fluence at room temperature. The fluence was 1 × 1014 and 1 × 1016 ions/cm2. The unpaired carrier concentration increases with increasing fluence. The photosensitivity of these crystals was determined by observing in situ the effect of the laser illumination on the EPR signal and measuring the decay and the growth of the EPR signal. The EPR signal of Fe3+ was found to decrease in both MgO, and Al2O3; and was found to increase in LiNbO3. This indicated that in case of MgO, and A12O3 Fe3+ will transfer into Fe2+/Fe4+, but in case of LiNbO3 Fe2+/ Fe4+ will transfer into Fe3+; increasing the EPR signal. This was found primary due to some Fe2+ and Fe4+ ions, which is not intentionally doped on the LiNbO3 crystal but exist as a defect on the crystal.

We have implanted ions of Sn, Au and Cu at energies between 160 keV and 2.0 MeV into single crystals of MgO (100) at room temperature. The formation of nanoclusters was confirmed using photospectrometry, in combination with Mie's theory, which was indirect but nondestructive. Using Doyle's theory, as well as Rutherford Backscattering Spectrometry (RBS), we correlated the full width half maximum of the absorption bands to the estimated size of the metallic nanoclusters between 1–10 nm. These clusters were formed both by over implantation and by a combination of threshold fluence of the implanted species and post thermal annealing. The changes in the estimated size of the nanoclusters, after annealing at temperatures ranging from 500°C to 1000°C, were observed using photospectrometry.

We have studied the formation of nano-crystals, after implantation of 2.0 MeV gold, 1.5 MeV silver, 160 keV copper and 160 keV tin into single crystal of A12O3. We also studied the change in the linear optical properties of the implanted Al2O3 before and after subsequent annealing by measuring the increase in resonance optical absorption. Applying Doyle's theory and the results obtained from Rutherford backscattering spectrometry (RBS) as well as the full width half maximum of the absorption band from Optical Absorption Photospectrometry (OAP), we measured the average size of the metallic clusters for each sample after heat treatment. The formation and crystallinity of the nanoclusters were also confirmed using transmission electron microscopy (TEM) technique.

Hydrogen in deposited optical ceramics can modify the optical properties, and therefore the role of the hydrogen needs to be understood to control its effects. Erbium-doped amorphous alumina films were deposited using simultaneous electron beam evaporation of aluminum and erbium while bombarding the sample with 30 eV 02+ ions from an electron cyclotron resonance (ECR) plasma. The hydrogen content was measured, using elastic recoil detection, as a function of isochronal annealing treatments. The data was fit to a simple trap-release model in order to determine an effective activation energy for the thermal release of H from alumina and Er-doped alumina. The intensity of the ion-beam stimulated luminescence from these samples was monitored in the visible and near infrared regions as a function of the thermal treatments. In order to gain a better understanding of the influence of hydrogen, the ionoluminescence (IL) data from samples containing hydrogen were fit with a simple linear equation.

Some vanadium oxides undergo phase transformations which give rise to attributable for large variations in optical and electronic properties. Since one can expect dynamic rearrangement of implanted species and a distorted lattice due to implantation, we investigated the precipitation process under ion implantation at high temperature. Sapphire samples were implanted with 300-keV V+ ions at temperatures from 470 to 1070 K in a transmission electron microscope interfaced with ion accelerators. Evolution of vanadium oxide precipitates was observed simultaneously. Damage evolution such as dislocation loops and voids were observed at fluences of the order of 1018-1019 and 1020 ions/m2, respectively. At implantation fluence of the order of 1021 ions/m2, dot and plate contrast was observed in addition to radiation damage. Electron diffraction analysis reveals that hexagonal and monoclinic V2O3, tetragonal and monoclinic VO2, and V7O13 precipitates were formed in the substrate depending on the surface normal of the substrate. Some of precipitates were thermally unstable phases. Crystallographic relationship between matrix and the precipitates was investigated as well as the swelling effect both in the substrate and in the precipitates. Temperature dependence reveals precipitation starts at temperature higher than 670 K.

Sequential ion implantation followed by thermal annealing has been used to form encapsulated CdS, ZnS, and PbS nanocrystals in SiO2 and Al2O3 matrices. In SiO2, nanoparticles are nearly spherical and randomly oriented, and ZnS and PbS nanocrystals exhibit bimodal size distributions. In Al2O3, nanoparticles are facetted and oriented with respect to the matrix. Initial photoluminescence (PL) results are presented.