Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.

Surfaces with artificial roughness were generated by deposition of nanoparticles on single crystalline substrates. Nanoparticles with an average size ≈ 15 nm were produced by inert gas condensation and deposited in situ on the substrate mounted inside a modified ultra high vacuum (UHV) transmission electron microscope (TEM). We have investigated the smoothing behavior on annealing based on the difference in surface energies between cluster and substrate and their heat of mixing. The cluster substrate combination Co/Cu(100) was chosen as a model system in which the cluster has a significantly higher surface energy than the substrate. Upon deposition at 600 K, the clusters do not remain on the surface, but rather burrow into the substrate. This is confirmed by a detailed strain analysis of the particles. Nanoparticles in the system Ge/Si(100) in contrast have a lower surface energy than the substrate and are completely miscible. The particles assume the substrate orientation around 700 K. At 900 K coherent islands form which are arranged in clusters of 4 in the form of a square. The reason for this previously unobserved pattern is not yet understood.

Ion beam mixing of Cu/Mo multilayer samples and demixing of Cu-Mo alloy samples were examined as functions of temperature and ion mass. Even at liquid nitrogen temperature, the mixing of one component in other was very small under 1.0 MeV Kr irradiation. The maximum solubility was about 10%. Irradiation of homogeneous Cu-Mo alloys under the same conditions, moreover, led to phase separation. These conclusions were deduced from bulk X-ray diffraction measurements and corroborated by EXAFS examination. The maximum solubility obtained by irradiating multilayer samples occurred at about 600 K. At lower or higher temperature, the solubility of Cu in Mo-rich phase was lower. A model based on the ballistic difflusion explains these results.

The temperature dependence of disordering of Cu3Au during ion irradiation has been investigated by computer simulations using MONTE CARLO methods. The investigation was motivated by peculiar experimental observations that the initial disordering rate begins to decrease above ~300 K, which can be explained by vacancies just becoming mobile at that temperature, but then at ~ 475 K, it reaches a minimum and then increases rapidly as the temperature is further increased, up to the order-disorder temperature. The present simulation shows that this behavior can be understood in terms of temperatures dependencies in both atomic mixing in the cascade and the efficiency of vacancy annealing of disorder as the vacancies diffuse out of the cascade.

Using a novel ultrahigh vacuum (UHV) transmission electron microscope with in-situ UHV sputtering attachment we have studied the sintering of copper and silver nanoparticles with single crystal copper substrates. Copper and silver particles deposited on (001) copper initially assume random orientations. Upon annealing, however, the particles reorient and assume an epitaxial orientation with the substrate. In the case of copper on copper, homoepitaxy occurs by a process involving sintering and grain growth. In the case of silver on copper, we have observed the particles to wet the substrate surface and sinter to form a thin epitaxial film with the orientation relationship (111)Ag // (001)Cu, [110]Ag // [110]Cu.

Diffuse X-ray scattering is a useful method for studying defects in silicon and metals. Although the traditional approaches of analyzing experimental diffuse X-ray scattering data have given much information about the size of defects and defect clusters, they are not very well suited for determining the atomic configuration. We present a fully atomistic computational method to calculate the diffuse X-ray scattering line profile of an arbitrary atomic configuration, and compare line profiles of point defects and Frenkel pair configurations with experiment.

We study the mechanisms of damage production during ion irradiation using molecular dynamics simulations of 400 eV -10 keV collision cascades in four different materials. The materials Al, Si, Cu and Ge are contrasted to each other with respect to the mass, melting temperature and crystal structure. The results show that the crystal structure clearly has the strongest effect on the nature of the damage produced, and elucidate how the open crystal structure affects the nature of defects produced in silicon.

The sintering of sputtered copper nanoparticles with a thin film copper substrate has been studied in real time using a novel in-situ UHV TEM. Particles were generated by dc sputtering in argon and transferred directly into the microscope along a connecting tube. The particles were deposited onto a clean (001) copper substrate of thickness 40nm. As-deposited particles assume a random orientation on the copper substrate as evidenced by electron diffraction patterns. Upon annealing, however, the particles were observed to reorient and assume the orientation of the substrate. Reorientation of individual, isolated particles occurred at ∼200°C, primarily by grain-boundary motion and not by surface diffusion.

Diffuse x-ray scattering (DXS) and computer simulation techniques were employed to investigate the defect structure produced in Si by low keV ion and MeV electron irradiations. DXS measurements were performed for keV Ga and He implants, demonstrating the ability of the technique to provide both bulk and near-surface measurements at defect concentrations of about 1000 ppm. A rigorous analysis of these results is complicated due to the complex nature of the ion damage in Si. A computer simulation framework is developed to aid in the analysis of this data. In this technique, defects are simulated and their strain fields are calculated by simply relaxing the atoms around the defect to their equilibrium positions. The diffuse scattering is then calculated from the strain field, and the results are compared to the experimental measurements. Computer simulations are presented here only for the case of electron irradiation damage and compared to published measurements. Application of the technique to more complicated structures is planned and should pose no serious problems in the computational framework already developed.

Diffuse x-ray scattering (DXS) and computer simulation techniques were employed to investigate the defect structure produced in Si by low keV ion and MeV electron irradiations. DXS measurements were performed for keV Ga and He implants, demonstrating the ability of the technique to provide both bulk and near-surface measurements at defect concentrations of about 1000 ppm. A rigorous analysis of these results is complicated due to the complex nature of the ion damage in Si. A computer simulation framework is developed to aid in the analysis of this data. In this technique, defects are simulated and their strain fields are calculated by simply relaxing the atoms around the defect to their equilibrium positions. The diffuse scattering is then calculated from the strain field, and the results are compared to the experimental measurements. Computer simulations are presented here only for the case of electron irradiation damage and compared to published measurements.1 Application of the technique to more complicated structures is planned and should pose no serious problems in the computational framework already developed.

The interaction of small energetic clusters of Cu atoms with Cu surfaces has been investigated by molecular dynamics computer simulations. The simulations are fully dynamical and three dimensional; they employ embedded atom method potentials. The simulations described here are an extension of our past work on cluster solid interactions [1]. In this work, the effects of the angle of incidence, energy, size and temperature of the cluster are examined. In addition, soft landings of Cu clusters on Cu are simulated.

Ion beam mixing and damage production at GaAs-AlAs interfaces was studied by Rutherford backscattering and channeling methods. It was observed that the general features of the intermixing of GaAs with AlAs at 100K are typical of that in other semiconductor and metallic systems but that the damage production is not. The GaAs layers amorphize at a very low ion dose whereas the AlAs layers are very resistant to amorphization. Damage in the AlAs begins at one interface of the GaAs and grows through the AlAs layer, but damage at the other interface never nucleates. The ratio of nuclear to electronic stopping influences the growth of the damage zone.

Radiation enhanced diffusion in the intermetallic alloy Cu3Au was measured directly for the first time. Ni and Pd tracer impurities were used to probe the diffusion of atoms occupying Cu and Au sublattice site's, respectively. Measurements were performed temperatures both above and below the ordering temperature, of TC =390°C The ability to grow high quality Cu3Au films by MBE with buried marker layers in the form of either (Cu2Ni)Au or Cu3(AuPd), made these measurements possible. Under irradiation with 0.75MeV Ar+ ions, the diffusion of Ni is approximately equal to that of Pd above Tc, but smaller below Tc. In the absence of irradiation, the thermal diffusion coefficients reveal a similar trend. Activation energies for RED for the two species are similar both above and below Tc whereas, in absence of irradiation, the activation enthalpies below Tc are different. These results are interpreted on the basis of lattice order.

The collision dynamics of Cu, Ni or Al clusters containing 92 atoms with substrates of these same metals were studied using molecular dynamics computer simulations. For energies of 1.0 keV or 326 eV, diverse behavior was observed, depending sensitively on the relative properties of the cluster and substrate. For Cu clusters impacting Cu substrates, the cluster plastically deforms the substrate and creates a deep crater with substrate atoms forming a ridge at the periphery of the crater. In contrast, Al clusters do not much deform Ni substrates, but rather tend to spread epitaxially over the surface. Several Al atoms dissociate from the cluster, and either reflect into the vacuum or scatter over the surface. 326 eV Ni clusters embed themselves almost completely within Al substrates and form localized amorphous zones.

Carbon is a promising p-type dopant in GaAs/AlxGa1−xAs heterojunction bipolar transistors (HBT) because of its low atomic mobility and its potential for achieving very high carrier concentrations. It is generally believed that carbon incorporates substitutionally on the column V sublattice. However, an anomalous behavior at carrier concentrations > 5 × 1019 cm−3 is observed in the electrical properties of carbon doped layers. The strain sustained in these layers may be explained by the presence of interstitial carbon.

We used Rutherford Backscattering Spectrometry in channeling geometry utilizing the nuclear reaction 12C (d,p)13C to determine the lattice locations of carbon in GaAs. The data presented unambiguously show, that up to 25% of the carbon atoms occupy interstitial sites. The presence of interstitial carbon is of importance for applications, since interstitial carbon may exhibit an enhanced diffusivity altering nominally abrupt dopant profiles.

Threshold displacement energies for atomic displacements along 〈110〉, 〈100〉, and 〈111〉 directions, and formation enthalpies of several symmetric interstitial atom configurations were calculated for Ni3Al by computer simulation using “embedded atom method” potentials. The Ni–Ni (100) dumbbell in the plane containing only Ni atoms has the lowest interstitial-atom enthalpy although the enthalpies of other configurations are similar. Interstitial configurations involving Al atoms all have much higher enthalpies. The anisotropy of the threshold energies in Ni3Al is similar to pure metals and no significant difference in threshold energy was observed for 〈110〉 replacement chains in rows containing all Ni atoms or alternating Ni–Al atoms. Various metastable interstitial atom configurations were observed, including crowd-ions. In addition, the spontaneous recombination volume for some configurations can be much smaller than in pure metals. The consequences of these results for radiation induced segregation and amorphization are discussed.

The microstructural development of compacted nanocrystalline TiO2 powder was studied as a function of sintering temperature up to 1000°C. Grain growth was monitored using x-ray diffraction and scanning electron microscopy. The specific surface area and total porosity were determined quantitatively using the nitrogen adsorption BET. The density was measured by gravimetry using Archimedes principle. The green body density of compacted n-TiO2 with average grain size of 14 nm is as high as 75% of theoretical bulk density. Low temperature surface diffusion leads to the disappearance of small pores, while noticeable densification commences at 600°C and reaches near theoretical values at 900°C. Grain growth also begins at 600°C, accelerating rapidly by 1000°C. Hot isostatic pressing is observed to enhance densification while suppressing grain growth.

Nanocrystalline ceramics have been produced by the method of inert gas condensation of ultra-small particles and in situ consolidation. Sintering characteristics and microstructural parameter such as grain size, porosity and pore size distributions have been investigated by a variety of techniques, including: X-ray diffraction, gravimetry, nitrogen adsorption, scanning electron microscopy and small angle neutron scattering. In pure TiO2, the sintering temperatures are drastically lowered compared to conventional ceramics, however, extensive grain growth occurs before full densification is achieved. High density, nanocrystalline ceramics can be prepared by pressure assisted sintering, doping and additions of second phases. High temperature microhardness and creep deformation in compression were measured and it was found that creep processes occur at lower temperatures than in ceramics with larger grain sizes. Nanocrystalline TiO2 with densities > 99 % can be deformed plastically without fracture at temperatures below half the melting point. The total strains exceed 0.6 at strain rates as high as 10−3 s−1. The stress exponent of the strain rate, n, is approximately 3 and the grain size dependence is G-q with q in the range of 1 – 1.5. It is concluded that the creep deformation occurs by an interface reaction controlled mechanism.

The sintering and deformation kinetics of nanocrystalline (n-) TiO2 were studied. It was found that pressureless sintering yields densities above 95 % with modest increase in grain size whereas pressure assisted sintering (1GPa) results in high density samples without grain growth. In addition compression tests were performed. Large true strains up to 0.6 and strain rates as high as 8 × 10−5 s−1 were observed at 810 °C without fracturing. The sintering and creep results are discussed in terms of the microstructure and diffusion coefficients in n-TiO2.

The influence of the specimen temperature during MeV Kr irradiation on the extent of compositional disordering in GaAs-AlAs superlattices (SLs) has been determined. We have investigated whether radiation-enhanced diffusion (RED) could be employed to reduce the dose required to completely disorder a SL by ion implanation. Metalorganic chemical vapor deposition grown GaAs-AlAs SLs were implanted with 0.75 MeV Kr to a dose of 2×1016 cm−2 at various sample temperatures ranging from 133 K to 523 K. The extent of disordering induced by the irradiations was determined by Rutherford backscattering spectrometry and secondary ion mass spectrometry. For low temperature irradiations (133 K to 233 K), complete intermixing of the SL is observed. However, the extent of intermixing of the SL decreases with increasing specimen temperature between room temperature and 523 K. We propose two possible explanations to interpret these results: (i) that the amount of ion beam mixing decreases with increasing temperature; and (ii) that the RED coefficient is negative which suggests the existence of a miscibility gap in the GaAs-AlAs SL system.