Metallocene-mediated cationic polymerization of vinyl ethers: Kinetics of polymerization and synthesis and characterization of statistical copolymers

The cationic polymerization of ethyl, n-butyl and iso-butyl vinyl ether, EVE, BVE and iBVE, respectively, was efficiently conducted using bis(η⁵-cyclopentadienyl)dimethyl hafnium, Cp₂HfMe₂, or bis(η⁵-cyclopentadienyl)dimethyl zirconium, Cp₂ZrMe₂ in combination with either tris(pentafluorophenyl)borate, B(C₆F₅)₃, or tetrakis(pentafluorophenyl)borate dimethylanilinum salt, [B(C₆F₅)₄]^?[Me₂NHPh]⁺, as initiation systems. The evolution of polymer yield, molecular weight and molecular weight distribution with time was examined. In addition, the influence of the initiating system, the monomer and the reaction conditions on the control of the polymerization was studied. Furthermore, statistical copolymers of EVE with BVE were prepared employing Cp₂HfMe₂ and [B(C₆F₅)₄]^?[Me₂NHPh]⁺ as the initiation system. The reactivity ratios were estimated using both linear graphical and non-linear methods. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length, which were derived using the monomer reactivity ratios. The glass transition temperatures, Tg, of the copolymers were measured by Differential Scanning Calorimetry, DSC, and the results were compared with predictions based on several theoretical models. The kinetics of thermal decomposition of the copolymers along with the respective homopolymers was studied by thermogravimetric analysis within the framework of the Ozawa-Flynn-Wall and Kissinger methodologies.     

Mechanism and energetics of dimerization of SiH2 radicals on H-terminated Si(0 0 1)-(2×1) surfaces

The mechanism and energetics are presented of the dimerization of two adsorbed surface SiH₂ groups on the H-terminated Si(0 0 1)-(2 × 1) surface to form Si₂H₄ species during the initial stages of growth in plasma deposition of hydrogenated amorphous silicon (a-Si:H) films. The reactions are observed during classical molecular-dynamics (MD) simulations of a-Si:H film deposition from SiH₂ radical precursors impinging on an initially H-terminated Si(0 0 1)-(2 × 1) surface and substrate temperature, T, over the range 500T700 K. The Si₂H₄ species resulting from the surface SiH₂ dimerization reactions undergo surface conformational changes resulting in either a non-rotated (NRD) or a rotated dimer (RD) configuration. The RD configuration is found to be the energetically favorable one. The MD simulation results for the structure of the NRD and RD surface Si₂H₄ configurations corroborate with ab initio calculations of optimized adsorption configurations of SiH₂ radicals on crystalline Si surfaces, as well as results of STM imaging of the thermal decomposition of disilane on Si(0 0 1).     

First-principles theoretical analysis of silyl radical diffusion on silicon surfaces

We report results from a detailed analysis of the fundamental radical precursor diffusion processes on silicon surfaces and discuss their implications for the surface smoothness of hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of SiH(3) radical migration on the hydrogen-terminated Si(001)-(2 x 1) surface with molecular-dynamics (MD) simulations of SiH(3) radical precursor migration on surfaces of a-Si:H films. Our DFT calculations yield activation energies for SiH(3) migration that range from 0.18 to 0.89 eV depending on the local electronic environment on the Si(001)-(2 x 1):H surface. In particular, when no substantial surface relaxation (Si-Si bond breaking or formation) accompanies the hopping of the SiH(3) radical the activation barriers are highest, whereas hopping between nearest-neighbor overcoordinated surface Si atoms results in the lowest radical diffusion barrier of 0.18 eV; this low barrier is consistent with the activation barrier for SiH(3) migration through overcoordinated sites on the a-Si:H surface. Specifically, the analysis of the MD simulations of SiH(3) radical migration on a-Si:H surfaces yields an effective diffusion barrier of 0.16 eV, allowing for the rapid migration of the SiH(3) radical prior to its incorporation in surface valleys; rapid migration and subsequent incorporation constitute the two-step mechanism responsible for the smoothness of plasma deposited a-Si:H thin films.     

Mechanisms and energetics of hydride dissociation reactions on surfaces of plasma-deposited silicon thin films

We report results from a detailed analysis of the fundamental silicon hydride dissociation processes on silicon surfaces and discuss their implications for the surface chemical composition of plasma-deposited hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of hydride dissociation on the hydrogen-terminated Si(001)-(2x1) surface and molecular-dynamics (MD) simulations of adsorbed SiH(3) radical precursor dissociation on surfaces of MD-grown a-Si:H films. Our DFT calculations reveal that, in the presence of fivefold coordinated surface Si atoms, surface trihydride species dissociate sequentially to form surface dihydrides and surface monohydrides via thermally activated pathways with reaction barriers of 0.40-0.55 eV. The presence of dangling bonds (DBs) results in lowering the activation barrier for hydride dissociation to 0.15-0.20 eV, but such DB-mediated reactions are infrequent. Our MD simulations on a-Si:H film growth surfaces indicate that surface hydride dissociation reactions are predominantly mediated by fivefold coordinated surface Si atoms, with resulting activation barriers of 0.35-0.50 eV. The results are consistent with experimental measurements of a-Si:H film surface composition using in situ attenuated total reflection Fourier transform infrared spectroscopy, which indicate that the a-Si:H surface is predominantly covered with the higher hydrides at low temperatures, while the surface monohydride, SiH((s)), becomes increasingly more dominant as the temperature is increased.     

Combined effects of substrate compliance and film compositional grading on strain relaxation in layer-by-layer semiconductor heteroepitaxy: the case of InAs/In0.50Ga0.50As/GaAs(1 1 1)A

A systematic theoretical analysis is presented of the combined effects of substrate compliance and film compositional grading on the relaxation of strain due to lattice mismatch in layer-by-layer semiconductor heteroepitaxy. The analysis is based on a combination of continuum elasticity theory and a novel atomistic simulation approach for modeling structural and compositional relaxation in layer-by-layer heteroepitaxial systems. Results are presented for InAs epitaxy on GaAs(1 1 1)A compliant substrates with some marginal film compositional grading that consists of one monolayer of In_0.50Ga_0.50As grown on the substrate surface prior to InAs growth. A parametric study is carried out over a wide range of substrate thicknesses. Interfacial stability with respect to misfit dislocation formation, the dependence on substrate thickness of a thermodynamic critical film thickness, and the completion of the coherent-to-semicoherent interfacial transition are examined in detail. In addition, the structural characteristics and compositional distribution of the corresponding semicoherent interfaces, the associated strain fields, as well as the film surface morphological characteristics are analyzed. Most importantly, the role of segregation at defects of a semicoherent interface in the thermodynamics of layer-by-layer heteroepitaxial growth is demonstrated. Our study shows that systematic combination of the mechanical behavior of thin compliant substrates with grading of the epitaxial film composition provides a very promising engineering strategy for strain relaxation in heteroepitaxy.     

Surface morphological response of crystalline solids to mechanical stresses and electric fields

Surface morphological evolution under the action of external fields is a fascinating topic that has attracted considerable attention within the surface science community over the past two decades. In addition to the interest in a fundamental understanding of field-induced nonlinear response and stability of surface morphology, the problem has been technologically significant in various engineering applications such as microelectronics and nanofabrication. In this report, we review theoretical progress in modeling the surface morphological response of stressed elastic solids under conditions that promote surface diffusion and of electrically conducting solids under surface electromigration conditions. A self-consistent model of surface transport and morphological evolution is presented that has provided the basis for the theoretical and computational work that is reviewed. According to this model, the surface morphological response of electrically conducting elastic solids to the simultaneous action of mechanical stresses and electric fields is analyzed. Emphasis is placed on metallic surfaces, including surfaces of voids in metallic thin films.Surfaces of stressed elastic solids are known to undergo morphological instabilities, such as the Asaro–Tiller or Grinfeld (ATG) instability that leads to emanation of crack-like features from the surface and their fast propagation into the bulk of the solid material. This instability is analyzed theoretically, simulated numerically, and compared with experimental measurements. The surface morphological evolution of electrically conducting, single-crystalline, stressed elastic solids under surface electromigration conditions is also examined. We demonstrate that, through surface electromigration, a properly applied and sufficiently strong electric field can stabilize the surface morphology of the stressed solid against both crack-like ATG instabilities and newly discovered secondary rippling instabilities; the effects of important parameters, such as surface crystallographic orientation, on the surface morphological response to the simultaneous action of an electric field and mechanical stress also are reviewed. In addition, electromigration-driven surface morphological response is analyzed systematically, focusing on the current-driven surface morphological evolution of voids in metallic thin films; this analysis has been motivated largely by the crucial role of void dynamics in determining the reliability of metallic interconnects in integrated circuits and has led to the interpretation of a large body of experimental observations and measurements. The electromigration-driven translational motion of morphologically stable voids, effects of current-driven void dynamics on the evolution of the electrical resistance of metallic thin films, and current-driven void–void interactions also are reviewed. Furthermore, theoretical studies are reviewed that demonstrated very interesting current-driven nonlinear void dynamics in stressed metallic thin films, including the inhibition of electromigration-induced instabilities due to the action of biaxial tensile stress, and stress effects on the electromigration-driven translational motion of morphologically stable voids.Complex, oscillatory surface states under surface electromigration conditions have been observed in numerical studies. In this report, emphasis is placed on void surfaces in metallic thin films, for which stable time-periodic states have been demonstrated. It is shown that increasing parameters such as the electric-field strength or the void size past certain critical values leads to morphological transitions from steady to time-periodic states; the latter states are characterized by wave propagation on the surface of a void that migrates along the metallic film at constant speed. The transition onset corresponds to a Hopf bifurcation that may be either supercritical or subcritical, depending on the symmetry of the surface diffusional anisotropy as determined by the crystallographic orientation of the film plane. It is also shown that, in the case where the Hopf bifurcation is subcritical, the simultaneous action of mechanical stress leads the current-driven void morphological response to the stabilization of chaotic attractors; in such cases, as the applied stress level increases, the void dynamics is set on a route to chaos through a sequence of period-doubling bifurcations. The observation of current-driven chaotic dynamics in homoepitaxial islands also is discussed.     

Current-induced stabilization of surface morphology in stressed solids

We examine the surface morphological evolution of a conducting crystalline solid under the simultaneous action of an electric field and mechanical stress based on a fully nonlinear model and combining linear stability theory with self-consistent dynamical simulations. We demonstrate that electric current, through surface electromigration, can stabilize the surface morphology of the stressed solid against cracklike surface instabilities. The results also have more general implications for the morphological response of solid surfaces under the simultaneous action of multiple external forces.     

Surface smoothening mechanism of amorphous silicon thin films

An important concern in the deposition of thin hydrogenated amorphous silicon () films is to obtain smooth surfaces. Herein, we combine molecular-dynamics simulations with first-principles density functional theory calculations to elucidate the smoothening mechanism of plasma deposited thin films. We show that the deposition precursor may diffuse rapidly on the film surface via overcoordinated surface Si atoms and incorporate into the film preferentially in surface valleys, with activation barriers for incorporation dependent on the local surface morphology. Experimental data on smoothening and precursor diffusion are accounted for.