Metastable solid solutions are phases that are synthesized far from thermodynamic equilibrium and offer a versatile route to design materials with tailor-made functionalities. One of the most investigated classes of metastable solid solutions with widespread technological implications is vapor deposited ternary transition metal ceramic thin films (i.e., nitrides, carbides, and borides). The vapor-based synthesis of these ceramic phases involves complex and difficult to control chemical interactions of the vapor species with the growing film surface, which often makes the fundamental understanding of the composition-properties relations a challenging task. Hence, in the present study, we investigate the phase stability within an immiscible binary thin film system that offers a simpler synthesis chemistry, i.e., the Ag-Mo system. We employ magnetron co-sputtering to grow Ag1−xMox thin films over the entire composition range along with x-ray probes to investigate the films structure and bonding properties. Concurrently, we use density functional theory calculations to predict phase stability and determine the effect of chemical composition on the lattice volume and the electronic properties of Ag-Mo solid solutions. Our combined theoretical and experimental data show that Mo-rich films (x ≥ ∼0.54) form bcc Mo-Ag metastable solid solutions. Furthermore, for Ag-rich compositions (x ≤ ∼0.21), our data can be interpreted as Mo not being dissolved in the Ag fcc lattice. All in all, our data show an asymmetry with regards to the mutual solubility of Ag and Mo in the two crystal structures, i.e., Ag has a larger propensity for dissolving in the bcc-Mo lattice as compared to Mo in the fcc-Ag lattice. We explain these findings in light of isostructural short-range clustering that induces energy difference between the two (fcc and bcc) metastable phases. We also suggest that the phase stability can be explained by the larger atomic mobility of Ag atoms as compared to that of Mo. The mechanisms suggested herein may be of relevance for explaining phase stability data in a number of metastable alloys, such as ternary transition metal-aluminum-nitride systems.
The cover image shows a high angle annular dark field scanning transmission electron microscopy micrograph of elongated Ag-Cu atomic islands supported on a SiO 2 substrate.Intensity variation within each island stems from mass contrast caused by segregation into Ag-and Cu-rich domains.
The elongation transition thickness (θElong) is a central concept in the theoretical description of thin-film growth dynamics on weakly interacting substrates via scaling relations of θElong with respect to rates of key atomistic film-forming processes. To date, these scaling laws have only been confirmed quantitatively by simulations, while experimental proof has been left ambiguous as it has not been possible to measure θElong. Here, we present a method for determining experimentally θElong for Ag films growing on amorphous SiO2: an archetypical weakly interacting film/substrate system. Our results confirm the theoretically predicted θElong scaling behavior, which then allow us to calculate the rates of adatom diffusion and island coalescence completion, in good agreement with the literature. The methodology presented herein casts the foundation for studying growth dynamics and cataloging atomistic-process rates for a wide range of weakly interacting film/substrate systems. This may provide insights into directed growth of metal films with a well-controlled morphology and interfacial structure on 2D crystals—including graphene and MoS2—for catalytic and nanoelectronic applications.
The goal of my doctorate project is to contribute to the understanding of fundamental physical mechanisms that determine growth of thin films synthesized using time-dependent and highly ionized deposition processes.
Pulsed, ionized vapour fluxes, generated from high power impulse magnetron sputtering (HiPIMS) discharges, are employed to study the effects of time-domain and energetic bombardment on the nucleation and coalescence characteristics during Volmer–Weber growth of metal (Ag) films on amorphous (SiO2) substrates. In situ monitoring of the film growth, by means of wafer curvature measurements and spectroscopic ellipsometry, is used to determine the film thickness where a continuous film is formed. This thickness decreases from ∼210 to ∼140 Å when increasing the pulsing frequency for a constant amount of material deposited per pulse or when increasing the amount of material deposited per pulse and the energy of the film forming species for a constant pulsing frequency. Estimations of adatom lifetimes and the coalescence times show that there are conditions at which these times are within the range of the modulation of the vapour flux. Thus, nucleation and coalescence processes can be manipulated by changing the temporal profile of the vapour flux. We suggest that other than for elucidating the atomistic mechanisms that control pulsed growth processes, the interplay between the time scales for diffusion, coalescence and vapour flux pulsing can be used as a tool to determine characteristic surface diffusion and island coalescence parameters.
The initial formation stages (i.e., island nucleation, island growth, and island coalescence) set characteristic length scales during growth of thin films from the vapor phase. They are, thus, decisive for morphological and microstructural features of films and nanostructures. Each of the initial formation stages has previously been well-investigated separately for the case of Volmer-Weber growth, but knowledge on how and to what extent each stage individually and all together affect the microstructural evolution is still lacking. Here, we address this question using growth of Ag on SiO2 from pulsed vapor fluxes as a case study. By combining in situ growth monitoring, ex situ imaging and growth simulations we systematically study the growth evolution all the way from nucleation to formation of a continuous film and establish the effect of the vapor flux time domain on the scaling behaviour of characteristic growth transitions (elongation transition, percolation and continuous film formation). Our data reveal a pulsing frequency dependence for the characteristic film growth transitions, where the nominal transition thickness decreases with increasing pulsing frequency up to a certain value after which a steady-state behaviour is observed. The scaling behaviour is shown to result from differences in island sizes and densities, as dictated by the initial film formation stages. These differences are determined solely by the interplay between the characteristics of the vapor flux and time required for island coalescence to be completed. In particular, our data provide evidence that the steady-state scaling regime of the characteristic growth transitions is caused by island growth that hinders coalescence from being completed.
The morphology of thin metal films and nanostructures synthesized from the vapor phase on insulating substrates is strongly influenced by the coalescence of islands. Here, we derive analytically the quantitative criterion for coalescence suppression by combining atomistic nucleation theory and a classical model of coalescence. Growth simulations show that using this criterion, a coalescence-free growth regime can be reached in which morphological evolution is solely determined by island nucleation, growth, and impingement. Experimental validation for the ability to control the rate of coalescence using this criterion and navigate between different growth regimes is provided by in situ monitoring of Ag deposition on SiO2. Our findings pave the way for creating thin films and nanostructures that exhibit a wide range of morphologies and physical attributes in a knowledge-based manner.
This thesis presents fundamental mechanisms of nucleation and early growth of and stress generation in thin polycrystalline metal films deposited using pulsed energetic deposition fluxes. The effects of a pulsed deposition flux and energetic bombardment on film nucleation was investigated using in situ stress measurements and in situ ellipsometry to determine the film thickness at which the films become continuous. Ag films where deposited using high power impulse magnetron sputtering (HiPIMS) in two series - one with constant low pulse power to minimize energetic bombardment while varying the pulse frequency and one with a constant pulse frequency while varying the pulse power, resulting in different amounts of energetic bombardment and different deposition rates - to separate the effects of a pulsed deposition flux and energetic bombardment. The thickness at which the film becomes continuous was found to decrease both with increasing pulse frequency and increasing pulse power. The effects of the increased energetic bombardment and deposition rate cannot be separated due to their coupling. Adatom lifetimes and the coalescence times for islands where calculated for different coverages and island sizes and compared to the time between pulses. It was found that the time between pulses was lower than the adatom lifetimes for certain conditions; this leads to an increase in the adatom density and therefore an increase of the nucleation density resulting in smaller thicknesses for the formation of continuous film. It was also found that the coalescence time for clusters becomes longer than the time between pulses, retarding the coalescence process; this leads to formation of long lived elongated clusters also resulting in a decrease of the thickness at which the films become continuous.Energetic bombardment during growth of Mo films using HiPIMS is found to result in large compressive stresses without the commonly observed defect induced associated lattice expansion seen when depositing films using energetic bombardment. This and a correlation between the magnitude of the compressive stress and the film density allow us to conclude that the compressive stress is generated by grain boundary densification. Two mechanisms leading to grain boundary densification and thus generation of compressive stresses are proposed.
