The interface chemistry of silicon nanocrystals (NCs) embedded in amorphous oxide matrix is studied through molecular dynamics simulations with the chemical environment described by the reactive force field model. Our results indicate that the Si NC-oxide interface is more involved than the previously proposed schemes which were based on solely simple bridge or double bonds. We identify different types of three-coordinated oxygen complexes, previously not noted. The abundance and the charge distribution of each oxygen complex is determined as a function of the NC size as well as the transitions among them. The oxidation at the surface of NC induces tensile strain to Si-Si bonds which become significant only around the interface, while the inner core remains unstrained. Unlike many earlier reports on the interface structure, we do not observe any double bonds. Furthermore, our simulations and analysis reveal that the interface bond topology evolves among different oxygen bridges through these three-coordinated oxygen complexes.
The GaSb and Ga0.62In0.38Sb nanocrystals were embedded in the SiO2 films by radio-frequency magnetron co-sputtering and were grown on GaSb and Si substrates at different temperatures. We present results on the 10K excitonic photoluminescence (PL) properties of nanocrystalline GaSb and Ga0.62In0.38Sb as a function of their size. The measurements show that the PL of the GaSb and Ga0.62In0.38Sb nanocrystallites follows the quantum confinement model very closely. By using deconvolution of PL spectra, origins of structures in photoluminescence were identified.
Crystalline nanoparticles of cadmium iodide where suspended in the amorphous matrix of antimony trisulphide. Both materials are layered structured and have large band-gaps however cadmium iodide exhibits polytypism, i.e. it exists in various different crystalline states. Different crystalline states are marked by wholely different dielectric constants which give rise to sharp surface plasmon resonance (SPR) peaks in the UV-visible. The manuscript details the variation in SPR's with heat-treatment of the films.
Amorphous complexions in nanocrystalline metals have the potential to improve mechanical properties and radiation tolerance, as well as resistance to grain growth. In this study, the stability of amorphous complexions in binary and ternary Cu-based alloys is investigated by observing the effect of cooling rate from high temperature on the occurrence of amorphous-to-ordered complexion transitions. Bulk Cu-Zr and Cu-Zr-Hf alloy samples were annealed to induce boundary premelting and then quenched through a procedure that induces a gradient of local cooling rate through the sample height. Amorpho…
In a recent letter (Phys. Rev. Lett. 84, 4629 (2000)), Lacks presents evidence of a first order amorphous-amorphous transition in silica at T=0. He calculates the free energy along a path of compression and successive decompression of a sample of 108 SiO2 units. The free energy of the two branches cross each other, and this is interpreted as evidence of a first order transition. We show that this conclusion does not follow from the shown data, since qualitatively the same phenomenology is obtained in a model where a first order transition does not exist.
Engineering the structure of core-shell colloidal semiconductor nanoparticles (CSNPs) is attractive due to the potential to enhance photo-induced charge transfer (PICT) and induce favourable optical and electronic properties. Nonetheless, the sensitivity of telluride CSNPs to high temperatures makes it challenging to precisely modulate their surface crystallinity. Herein, we have developed an efficient strategy for synthesising telluride CSNPs with thin amorphous shells using aqueous cation exchange (ACE). By changing the synthesis temperature in the range 40 to 110C, the crystallinity of the …
We have studied the photoinduced transformation of small rings (3-membered) in amorphous silica by Car-Parrinello simulations. The process of ring opening leading to the formation of a couple of paramagnetic centers, namely an E' and a non-bridging-oxygen hole center (NBOHC), has been proposed experimentally to occur in silica exposed to F2 laser irradiation (at 7.9 eV). By using a new scheme for the simulation of rare events in ab-initio molecular dynamics (Iannuzzi, Laio and Parrinello, Phys. Rev. Lett. 90, 238303 (2003)), we have identified the transformation path for the opening of a 3-mem…
The effect of silica-promotion on the reduction of iron oxides in hydrogen was investigated using in situ X-ray diffraction and aberration-corrected transmission electron microscopy to understand the mechanism of reduction and the identity of the iron(II) silicate phase that has historically been designated as the cause of the iron-silica interaction in such materials. In the absence of a silica promoter the reduction of hematite to α-Fe proceeds via magnetite. Silica promoted amorphous iron oxide is reduced to α-Fe via stable magnetite and wüstite phases. During reduction of silica-promoted i…
Amorphous silica deforms viscoplastically at elevated temperatures, as is common for brittle glasses. The key mechanism of viscoplastic deformation involves interatomic bond switching, which is known to be a thermally activated process. In this study, through systematic in-situ compression tests by scanning electron microscopy, the viscoplastic deformation of amorphous silica is observed without thermal activation. Furthermore, ductility does not increase monotonically with acceleration voltage and current density of the SEM e-beam but is maximized by a factor of three at a specific accelerati…
We report experimental evidence of the existence of two variants of the E' gamma centers induced in silica by gamma rays at room temperature. The two variants are distinguishable by the fine features of their line shapes in paramagnetic resonance spectra. These features suggest that the two E' gamma differ for their topology. We find a thermally induced interconversion between the centers with an activation energy of about 34 meV. Hints are also found for the existence of a structural configuration of minimum energy and of a metastable state.
We investigate the adsorption and diffusion behaviors of CO2, CH4, and N2 in interfacial systems composed of a polymer of intrinsic microporosity (PIM-1) and amorphous silica using grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. We build model systems of mixed matrix membranes (MMMs) with PIM-1 chains sandwiched between silica surfaces. Gas adsorption analysis using GCMC simulations shows that gas molecules are preferentially adsorbed in microcavities distributed near silica surfaces, resulting in an increase in the solubility coefficients of CO2, CH4, and N2 compar…
Grain size engineering, particularly reducing grain size into the nanocrystalline regime, offers a promising pathway to further improve the strength-to-weight ratio of Al alloys. Unfortunately, the fabrication of nanocrystalline metals often requires non-equilibrium processing routes, which typically limit the specimen size and require large energy budgets. In this study, multiple dopant atoms in ternary Al alloys are deliberately selected to enable segregation to the grain boundary region and promote the formation of amorphous complexions. Three different fully dense bulk nanocrystalline Al a…
Glasses have a large excess of low-frequency vibrational modes in comparison with continuous elastic body, the so-called Boson Peak, which appears to correlate with several crucial properties of glasses, such as transport or fragility. I review recent results showing that the Boson Peak is a necessary consequence of the weak connectivity of the solid. I explain why in assemblies repulsive spheres the boson peak shifts up to zero frequency as the pressure is lowered toward the jamming threshold, and derive the corresponding exponent. I show how these ideas capture the main low-frequency feature…
The nucleation and structure of silicon nanocrystals formed by different preparation conditions and silicon concentration (28 - 70 area %) have been studied using Transmission Electron Microscopy (TEM), Energy Filtered TEM (EFTEM) and Secondary Ion Mass Spectroscopy (SIMS). The nanocrystals were formed after heat treatment at high temperature of a sputtered 10 nm thick silicon rich oxide on 3 nm SiO$_2$ layer made by Rapid Thermal Oxidation (RTO) of silicon. Nanocrystals precipitate when the excess silicon concentration exceeds 50 area %. Below this percentage amorphous silicon nanoclusters we…
A combination of classical molecular dynamics (MD) and ab initio Car-Parrinello molecular dynamics (CPMD) simulations is used to investigate the adsorption of water on a free amorphous silica surface. From the classical MD SiO_2 configurations with a free surface are generated which are then used as starting configurations for the CPMD.We study the reaction of a water molecule with a two-membered ring at the temperature T=300K. We show that the result of this reaction is the formation of two silanol groups on the surface. The activation energy of the reaction is estimated and it is shown that …
We discuss a novel approach that allows to obtain effective potentials from ab initio trajectories. Our method consists in fitting the weighted radial distribution functions obtained from the ab initio data with the ones obtained from simulations with the effective potential, and using the parameters of the latter as fitting variables. As a case study, we consider the example of amorphous silica, a material that is highly relevant in the field of glass science as well as in geology. Our approach is able to obtain an effective potential that gives a better description with respect to structural…
We present the results of an experiment where amorphous carbon was irradiated by femtosecond x-ray free electron laser pulses. The 830 eV laser pulses induce a phase transition in the material which is characterized ex-situ. The phase transition energy threshold is determined by measuring the surface of each irradiated area using an optical Nomarski microscope. The threshold fluence is found to be 282 +/- 11 mJ/cm^2, corresponding to an absorbed dose at the surface of 131 +/-5 meV/atom. Atomic force microscopy measurements show volume expansion of the irradiated sample area, suggesting a solid…
Monte Carlo simulations, supplemented by ab initio calculations, shed light into the energetics and thermodynamic stability of nanostructured amorphous carbon. The interaction of the embedded nanocrystals with the host amorphous matrix is shown to determine in a large degree the stability and the relative energy differences among carbon phases. Diamonds are stable structures in matrices with sp^3 fraction over 60%. Schwarzites are stable in low-coordinated networks. Other sp^2-bonded structures are metastable.
Crystalline and amorphous nanoparticles of silicon in thin silica layers were examined by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS) and x-ray photoelectron spectroscopy (XPS). We used XPS data in the form of the Auger parameter to separate initial and final state contributions to the Si$_{2p}$ energy shift. The electrostatic charging and electron screening issues as well as initial state effects were also addressed. We show that the chemical shift in the nanocrystals is determined by initial state rather than final state effects, and that the electron scr…
Silicon nanocrystals (SiNCs) have been under active investigation in the last decades and have been considered as a promising candidate for many optoelectronic applications including highly-efficient solar cells. Some of the fundamental properties of interest in these nanostructures is the temperature dependence of their optical absorption onset, and how this is controlled by different passivation regimes. In the present work we employ first-principles calculations in conjunction with the special displacement method to study the temperature dependence of the band gap renormalization of free-st…
Combining dielectric crystals with mesoporous solids allows a versatile design of functional nanomaterials, where the porous host provides a mechanical rigid scaffold structure and the molecular filling adds the functionalization. Here, we report a study of the complex lattice dynamics of a SiO$_2$:KH$_2$PO$_4$ nanocomposite consisting of a monolithic, mesoporous silica glass host with KH$_2$PO$_4$ nanocrystals embedded in its tubular channels $\sim$12 nm across. A micro-Raman investigation performed in the spectral range of 70-1600 cm$^{-1}$ reveals the complex lattice dynamics of the confine…
We use density functional theory (DFT) to study the thermodynamic stability and migration of copper ions and small clusters embedded in amorphous silicon dioxide. We perform the calculations over an ensemble of statistically independent structures to quantify the role of the intrinsic atomic-level variability in the amorphous matrix affect the properties. The predicted formation energy of a Cu ion in the silica matrix is 2.7+/-2.4 eV, significantly lower the value for crystalline SiO2. Interestingly, we find that Cu clusters of any size are energetically favorable as compared to isolated ions;…
Nucleation and growth of solids from solutions impacts many natural processes and are fundamental to applications in materials engineering and medicine. For a crystalline solid, the nucleus is a nanoscale cluster of ordered atoms, which forms through mechanisms that are still poorly understood. These mechanisms have important consequences on the morphology and nucleation rates of the resultant crystals but it is unclear whether a nucleus forms spontaneously from solution in a single step or through multiple steps. Using in-situ electron microscopy, we observe and quantify how gold and silver n…
The structural and dynamic properties of silica melts under high pressure are studied using molecular dynamics (MD) computer simulation. The interactions between the ions are modeled by a pairwise-additive potential, the so-called CHIK potential, that has been recently proposed by Carre et al. The experimental equation of state is well-reproduced by the CHIK model. With increasing pressure (density), the structure changes from a tetrahedral network to a network containing a high number of five- and six-fold Si-O coordination. In the partial static structure factors, this change of the structur…
Disordered hyperuniformity (DHU) is a recently proposed new state of matter, which has been observed in a variety of classical and quantum many-body systems. DHU systems are characterized by vanishing infinite-wavelength density fluctuations and are endowed with unique novel physical properties. Here we report the first discovery of disordered hyperuniformity in atomic-scale 2D materials, i.e., amorphous silica composed of a single layer of atoms, based on spectral-density analysis of high-resolution transmission electron microscope images. Subsequent simulations suggest that the observed DHU …
We studied the optical absorption induced by 4.7eV pulsed laser radiation on Ge-doped a-SiO2 synthesized by a sol-gel technique. The absorption spectra in the ultraviolet spectral range were measured during and after the end of irradiation with an in situ technique, evidencing the growth of an absorption signal whose profile is characterized by two main peaks near 4.5eV and 5.7eV and whose shape depends on time. Electron spin resonance measurements performed ex situ a few hours after the end of exposure permit to complete the information acquired by optical absorption by detection of the param…
Using a combination of numerical simulations and atom-probe tomography experiments, we determine the interfacial energy of Cu nanocrystals precipitated within the amorphous matrix of FINEMET (molar composition Fe72.89Si16.21B6.90Nb3Cu1). Specifically, we use the Langer-Schwartz model implemented in the software Thermocalc to carry out parametric simulations of growth and coarsening of Cu clusters for different interface energies. We have carried out atom-probe tomography (APT) experiments to determine the interface energy as the value for which the simulated particle size distribution best mat…
The dispersion and coordination of aluminium species on the surface of silica-alumina based materials are essential for controlling their catalytic activity and selectivity. Al(IV) and Al(VI) are two common coordinations of Al species in the silica network and alumina phase, respectively. Al(V) is rare in nature and was found hitherto only in the alumina phase or interfaces containing alumina, a behavior which negatively affects the dispersion, population, and accessibility of Al(V) species on the silica-alumina surface. This constraint has limited the development of silica-alumina based catal…
We study the static and dynamic properties of liquid silica over a wide range of temperature T and density using computer simulations. The results reveal a change in the potential energy landscape as T decreases that underlies a transition from a fragile liquid at high T to a strong liquid at low T. We also show that a specific heat anomaly is associated with this fragile-to-strong transition, and suggest that this anomaly is related to the polyamorphic behaviour of amorphous solid silica.
Proper consideration of anharmonicity is important for the calculation of the thermal conductivity. However, how the anharmonicity influences the thermal conduction in amorphous materials is still an open question. In this work, we uncover the role of anharmonicity on the thermal conductivity of amorphous silica (a-SiO2) by comparing the thermal conductivity predicted from the harmonic theory and the anharmonic theory. Moreover, we explore the effect of anharmonicity-induced frequency shift on the prediction of the thermal conductivity. It is found that the thermal conductivity calculated by t…
The passivation by diffusing H2 of silicon dangling bond defects (E' centers, induced by laser irradiation in amorphous SiO_2 (silica), is investigated in situ at several temperatures. It is found that the reaction between E' center and H_2 requires an activation energy of 0.38eV, and that its kinetics is not diffusion-limited. The results are compared with previous findings on the other fundamental paramagnetic point defect in silica, the non bridging oxygen hole center, which features completely different reaction properties with H_2. Besides, a comparison is proposed with literature data on…
We compare, through first-principles pseudopotential calculations, the structural, electronic and optical properties of different size silicon nanoclusters embedded in a SiO2 crystalline or amorphous matrix, with that of free-standing, hydrogenated and hydroxided silicon nanoclusters of corresponding size and shape. We find that the largest effect on the opto-electronic behavior is due to the amorphization of the embedded nanocluster. In that, the amorphization reduces the fundamental gap while increasing the absorption strength in the visible range. Increasing the nanocluster size does not ch…
This experimental PhD work deals with the generation and transformation processes of point defects induced by UV laser irradiation on amorphous silicon dioxide (silica). The investigation relies on several spectroscopic techniques used to probe the microscopic damage induced by UV laser on the material. The most innovative approach, however, is the measurement in situ of the absorption signals related to laser-induced point defects. This technique yields new information on the kinetics of defect processes, inaccessible to previous works based only on stationary measurements of laser-induced da…
Strain has a crucial effect on the optical and electronic properties of nanostructures. We calculate the atomistic strain distribution in silicon nanocrystals up to a diameter of 3.2 nm embedded in an amorphous silicon dioxide matrix. A seemingly conflicting picture arises when the strain field is expressed in terms of bond lengths versus volumetric strain. The strain profile in either case shows uniform behavior in the core, however it becomes nonuniform within 2-3 Ådistance to the nanocrystal surface: tensile for bond lengths whereas compressive for volumetric strain. We reconsile their coex…
The mobility of O atoms at very low temperatures is not generally taken into account, despite O diffusion would add to a series of processes leading to the observed rich molecular diversity in space. We present a study of the mobility and reactivity of O atoms on an amorphous silicate surface. Our results are in the form of RAIRS and temperature-programmed desorption spectra of O2 and O3 produced via two pathways: O + O and O2 + O, investigated in a submonolayer regime and in the range of temperature between 6.5 and 30 K. All the experiments show that ozone is formed efficiently on silicate at…
The structural, electronic and optical properties of Si nanocrystals of different size and shape, passivated with hydrogens, OH groups, or embedded in a SiO2 matrix are studied. The comparison between the embedded and free, suspended nanocrystals shows that the silica matrix produces a strain on the embedded NCs, that contributes to determine the band gap value. By including the strain on the hydroxided nanocrystals we are able to reproduce the electronic and optical properties of the full Si/SiO2 systems. Moreover we found that, while the quantum confinement dominates in the hydrogenated nano…
Visible luminescence is observed from the composite of SiO2 with embedded silicon nanocrystallites produced by femtosecond laser irradiation of hydrogenated amorphous silicon (a-Si:H) film in air. The photoluminescence originates from the defect states at the interface between silicon crystallites and SiO2 matrix. The method could be used for fabrication of luminescent layers to increase energy conversion of a-Si:H solar cells.
Resistive switching in amorphous silicon carbide (a-SiC) films deposited by a single composite target magnetron sputtering process is reported. Switching performance as a function of thickness of the films (50, 100 and 300 nm) as well as different top metal electrodes (Cu, Pt and Ag) with the bottom electrode fixed as Au, is investigated. The switching parameters (Forming Voltage, Set and Reset voltages and corresponding currents) are found to be dependent on thickness of SiC films and it is observed that 100 nm is the optimal thickness for best endurance. The interface between metal electrode…
The structure and transport properties of SiO2-Al2O3 melts containing 13 mol% and 47 mol% Al2O3 are investigated by means of large scale molecular dynamics computer simulations. The interactions between the atoms are modelled by a pair potential which is a modified version of the one proposed by Kramer et al. [J. Am. Chem. Soc. 64, 6435 (1991)]. Fully equilibrated melts in the temperature range 6000 K >= T > 2000 K are considered as well as glass configurations, that were obtained by a rapid quench from the lowest melt temperatures. Each system is simulated at two different densities in order …
