Amorphous Configuration Research Articles

Narrow band gap high conducting nc-Si1-xGex:H absorber layers for tandem structure nc-Si solar cells

Advantages of spectral sensitivity in the infrared range and good stability against light exposure together have made nanocrystalline silicon–germanium alloy (nc-Si1-xGex) as an ideal absorber material at the bottom-cell in multi-junction Si thin film solar cells. Evolution of good quality SiGe thin films with sustained nanocrystallinity, particularly at low growth temperature (TS), is a challenging task in view of very different chemical reaction behaviors controlled via different energy requirements of two frequently used source gases, e.g., SiH4 and GeH4. Growth of nc-SiGe:H thin films have been pursued at TS ∼220 °C, using H2-diluted (by ∼96%) (SiH4 + GeH4) plasma in 13.56 MHz RF-PECVD, by varying the RF power applied to the parallel plate capacitively coupled electrodes of the reactor. At lower RF power Ge-dominated low band gap SiGe network has been produced with Si component in mostly amorphous configuration that leads to a low electrical conductivity. At high RF power Si–Si network becomes highly crystalline; however, Ge content reduces drastically. Breaking of weaker Ge–Ge bonds creates defects via dangling bonds and increased grain boundary defects around Si nanocrystals together produce relatively wider band gap SiGe network with degraded electrical conductivity. The novelty and significance of the present investigation remains in realizing the narrowing of the optical band gap (Eg ∼1.499 eV) even at lower Ge content, through moderate crystallization in the SiGe network and a simultaneous high electrical conductivity of the nc-SiGe:H films (σD ∼2.38 × 10−3 S cm−1) obtained at a high growth rate (∼9.5 nm/min), via optimization of the applied RF power at a moderate level (∼100 W). In such circumstances nanocrystallization of the network plays leading role in narrowing the optical band gap, overriding the effect arising out of the restricted presence of Ge.

Atomistic modeling of flexoelectricity in amorphous polymers

In this paper, the amorphous PVDF (Polyvinylidene Fluoride) and PE (Polyethylene) models are established. The relationship between configuration density and temperature is calculated by molecular dynamics simulation. The rationality of model is determined by comparing with the experimentally determined glass transition temperature Tg. Secondly, the strain gradient is applied to the main chain carbon atoms of the amorphous PVDF and PE equilibrium configuration. Electric polarization occurs when the microstructure of the configuration changes. The transverse flexoelectric coefficients μ12 of amorphous PVDF and PE configurations are 1.24×10-9 C/m and −2.63×10-9 C/m, respectively, obtained by fitting the relationship between polarization and strain gradient. Finally, through the micromechanical analysis, the CF2 and CH2 dipoles rotate around the main chain along the inner side of the curved surface under the strain gradient, accompanied by some small structural adjustments. This leads to the electric polarization of the amorphous PVDF and PE configuration. Due to the difference in charge number and electronegativity between the amorphous PVDF and PE groups, the calculated transverse flexoelectric coefficients of the amorphous PVDF and PE are opposite, and the absolute value of the transverse flexoelectric coefficient of PE is greater than that of PVDF.

Incorporating a soft ordered phase into an amorphous configuration enhances its uniform plastic deformation under shear

Amorphous materials of homogeneous structures usually suffer from nonuniform deformation under shear, which can develop into shear localization and eventually destructive shear band. One approach to tackle this issue is to introduce an inhomogeneous structure containing more than one phase, which can reduce the local nonuniform shear deformation and hinder its percolation throughout the system. Using thermostated molecular dynamics (MD) simulations, we compare the deformation behavior between a homogeneous amorphous mixture of bidisperse disc particles, interacting via an n-6 Lennard-Jones potential of tunable softness, with an inhomogeneous one containing an evenly-distributed ordered phase. We change the population ratio of large to small particles to create a homogeneous or an inhomogeneous mixture, where the softness of a chosen phase can be manually adjusted by specifying n of the interparticle potential. Results of applying extensive quasistatic shear on the prepared mixtures reveal that the inhomogeneous amorphous mixture containing a soft ordered phase overall deforms more uniformly than the homogeneous one, which indicates that both the structure inhomogeneity and the inter-phase softness variance play important roles in enhancing the uniformity of the plastic deformation under shear.

Configurational-Bias Monte Carlo Back-Mapping Algorithm for Efficient and Rapid Conversion of Coarse-Grained Water Structures into Atomistic Models

Coarse-grained molecular dynamics (MD) simulations represent a powerful approach to simulate longer time scale and larger length scale phenomena than those accessible to all-atom models. The gain in efficiency, however, comes at the cost of atomistic details. The reverse transformation, also known as back mapping, of coarse-grained beads into their atomistic constituents represents a major challenge. Most existing approaches are limited to specific molecules or specific force fields and often rely on running a long-time atomistic MD of the back-mapped configuration to arrive at an optimal solution. Such approaches are problematic when dealing with systems with high diffusion barriers. Here, we introduce a new extension of the configurational-bias Monte Carlo (CBMC) algorithm, which we term the crystalline-configurational-bias Monte Carlo (C-CBMC) algorithm, which allows rapid and efficient conversion of a coarse-grained model back into its atomistic representation. Although the method is generic, we use a coarse-grained water model as a representative example and demonstrate the back mapping or reverse transformation for model systems ranging from the ice-liquid water interface to amorphous and crystalline ice configurations. A series of simulations using the TIP4P/Ice model are performed to compare the new CBMC method to several other standard Monte Carlo and molecular dynamics-based back-mapping techniques. In all of the cases, the C-CBMC algorithm is able to find optimal hydrogen-bonded configuration many thousand evaluations/steps sooner than the other methods compared within this paper. For crystalline ice structures, such as a hexagonal, cubic, and cubic-hexagonal stacking disorder structures, the C-CBMC was able to find structures that were between 0.05 and 0.1 eV/water molecule lower in energy than the ground-state energies predicted by the other methods. Detailed analysis of the atomistic structures shows a significantly better global hydrogen positioning when contrasted with the existing simpler back-mapping methods. The errors in the radial distribution functions (RDFs) of back-mapped configuration relative to reference configuration for the C-CBMC, MD, and MC were found to be 6.9, 8.7, and 12.9, respectively, for the hexagonal system. For the cubic system, the relative errors of the RDFs for the C-CBMC, MD, and MC were found to be 18.2, 34.6, and 39.0, respectively. Our results demonstrate the efficiency and efficacy of our new back-mapping approach, especially for crystalline systems where simple force-field-based relaxations have a tendency to get trapped in local minima.

ReaxFF Molecular Dynamics Simulation for the Graphitization of Amorphous Carbon: A Parametric Study.

A parametric study of ReaxFF for molecular dynamics simulation of graphitization of amorphous carbon was conducted. The responses to different initial amorphous carbon configurations, simulation time steps, simulated temperatures, and ReaxFF parameter sets were investigated. The results showed that a time step shorter than 0.2 fs is sufficient for the ReaxFF simulation of carbon using both Chenoweth 2008 and Srinivasan 2015 parameter sets. The amorphous carbon networks produced using both parameter sets at 300 K are similar to each other, with the first peak positions of pair distribution function curves located between the graphite sp2 bond peak position and the diamond sp3 bond peak position. In the graphitization process, the graphene fragment size increases and the orientation of graphene layers transforms to be parallel with each other with the increase of temperature and annealing time. This parallel graphene structure is close to the crystalline graphite. Associated with this graphitization is the presence of small voids and pores which arise because of the more efficient atomic packing relative to a disordered structure. For all initial densities, both potential parameter sets exhibit the expected behavior in which the sp2 fraction increases significantly over time. The sp2 fraction increases with increasing temperature. The differences of sp2 fraction at different temperatures are more obvious in lower density at 1.4 g/cm3. When density is increased, the gap caused by different temperatures becomes small. This study indicates that both Chenoweth 2008 and Srinivasan 2015 potential sets are appropriate for molecular dynamics simulations in which the growth of graphitic structures is investigated.

Rational design of stealthy hyperuniform two-phase media with tunable order.

Disordered stealthy hyperuniform materials are exotic amorphous states of matter that have attracted recent attention because of their novel structural characteristics (hidden order at large length scales) and physical properties, including desirable photonic and transport properties. It is therefore useful to devise algorithms that enable one to design a wide class of such amorphous configurations at will. In this paper, we present several algorithms enabling the systematic identification and generation of discrete (digitized) stealthy hyperuniform patterns with a tunable degree of order, paving the way towards the rational design of disordered materials endowed with novel thermodynamic and physical properties. To quantify the degree of order or disorder of the stealthy systems, we utilize the discrete version of the τ order metric, which accounts for the underlying spatial correlations that exist across all relevant length scales in a given digitized two-phase (or, equivalently, a two-spin state) system of interest. Our results impinge on a myriad of fields, ranging from physics, materials science and engineering, visual perception, and information theory to modern data science.

Permanent densification of amorphous zinc oxide under pressure: A first principles study

Ab initio simulations within a generalized gradient approximation are carried out to investigate the densification mechanism of amorphous zinc oxide (a-ZnO) under hydrostatic pressure. In contrast to the crystalline ZnO, the densification of a-ZnO is found to proceed gradually and is associated with a structural modification from a low density amorphous state to a high density amorphous state. Accompanied by the phase transformation, the mean coordination number increases from ~4.0 to ~5.5. The high-density amorphous form of ZnO has a local structure, partially comparable with that of the rocksalt type ZnO crystal and presents a semiconducting behavior. The phase change is irreversible because upon pressure release, an amorphous model largely consisting of fivefold coordination is recovered. The decompressed model can be, therefore, classified as an intermediate phase between the wurtzite-like and the rocksalt-like amorphous configurations.

Molecular dynamics simulations on tensile behaviors of single-crystal bcc Fe nanowire: effects of strain rates and thermal environment

Molecular dynamics simulations were applied to investigate tensile behaviors of single-crystal Fe nanowire in 〈001〉 direction under different strain rates. Results show that the nanowire deforms by twinning with elements of K 1 = {112}, η2 = 〈111〉 and reorients from 〈001〉 to 〈110〉 in the tensile direction. Under low strain rate, tensile stress abruptly drops to zero after strain exceeds a critical value, and the nanowire fractures in a bcc structure. In contrast, tensile stress shows a nonlinear tail and the nanowire fractures in an amorphous configuration at high strain rate, and the higher the strain rate, the longer the tail will be. Furthermore, it demonstrates that Young’s modulus and yield stress are independent from strain rates at low temperature, and that both two properties and yield strain decrease as temperature increases.

In vitro digestibility, protein composition and techno-functional properties of Saskatchewan grown yellow field peas (Pisum sativum L.) as affected by processing

Saskatchewan grown yellow field pea was subjected to different processing conditions including dehulling, micronization, roasting, conventional/microwave cooking, germination, and combined germination and conventional cooking/roasting. Their nutritional and antinutritional compositions, functional properties, microstructure, thermal properties, in vitro protein and starch digestibility, and protein composition were studied. Processed field peas including conventional cooked yellow peas (CCYP), microwave cooked yellow peas (MCYP), germinated-conventional cooked yellow peas (GCCYP), and germinated-roasted yellow peas (GRYP) exhibited the significantly higher in vitro protein digestibility (IVPD), which was in accordance with their significantly lower trypsin inhibitor activity and tannin content. The SDS-PAGE and size exclusion HPLC profiles of untreated pea proteins and their hydrolysates also confirmed the IVPD result that these four treatments facilitated the hydrolysis of pea proteins to a greater extent. The CCYP, MCYP, GCCYP, and GRYP also exhibited significantly higher starch digestibility which was supported by their lower onset (To), peak (Tp), and conclusion (Tc) temperatures obtained from DSC thermogram, their lower pasting properties and starch damage results, as well as their distinguished amorphous flakes' configuration observed on the scanning electron microscopic image. LC/ESI-MS/MS analysis following in-gel digests of SDS-PAGE separated proteins allowed detailed compositional characterization of pea proteins. The present study would provide fundamental information to help to better understand the functionality of field peas as ingredients, and particularly in regards to agri-food industry to improve the process efficiency of field peas with enhanced nutritional and techno-functional qualities.

Theoretical study on the electronic structure properties of a PbS quantum dot adsorbed on TiO2 substrates and their role on solid-state devices

A theoretical study was carried out for the first time in a series of two nanocomposite semiconducting systems (PbS)4@(TiO2)38. We stabilized two structures of TiO2 using a simulated annealing procedure with Molecular Dynamics as a first approach and the second model was optimized at the PBE level of theory, as benchmarking. An amorphous and anatase structures were found for both methodologies, respectively. We adopted the cubic structure of the (PbS)4 quantum dot as suggested by experimental data. The DOS of the isolated systems were assessed and also those of the composites (PbS)4@(TiO2)38. Adsorption energies on both systems were estimated and an attraction with a certain degree of covalency was found for the (PbS)4 at the TiO2 anatase model system. A weaker interaction of the electrostatic-type was found with the TiO2 amorphous configuration. In both systems, the attraction is favored in STi bond pairs. The DOS for the composite systems presents a different nature for the amorphous and anatase cases that is evidenced in the size of the band gaps. The (PbS)4@(TiO2)38 anatase composite systems results in a more favorable electronic structure that may readily provide fundamental data to develop and design photocatalytic devices for hydrogen production, energy storage and photovoltaic applications.

Influence of an amorphous wall on the distribution of localized excitations in a colloidal glass-forming liquid

Elucidating the nature of the glass transition has been the holy grail of condensed matter physics and statistical mechanics for several decades. A phenomenological aspect that makes glass formation a conceptually formidable problem is that structural and dynamic correlations in glass-forming liquids are too subtle to be captured at the level of conventional two-point functions. As a consequence, a host of theoretical techniques, such as quenched amorphous configurations of particles, have been devised and employed in simulations and colloid experiments to gain insights into the mechanisms responsible for these elusive correlations. Very often, though, the analysis of spatio-temporal correlations is performed in the context of a single theoretical framework, and critical comparisons of microscopic predictions of competing theories are thereby lacking. Here, we address this issue by analysing the distribution of localized excitations, which are building blocks of relaxation as per the dynamical facilitation (DF) theory, in the presence of an amorphous wall, a construct motivated by the random first-order transition theory (RFOT). We observe that spatial profiles of the concentration of excitations exhibit complex features such as non-monotonicity and oscillations. Moreover, the smoothly varying part of the concentration profile yields a length scale , which we compare with a previously computed length scale . Our results suggest a method to assess the role of dynamical facilitation in governing structural relaxation in glass-forming liquids.

Calculations of the magnetic entropy change in amorphous through a microscopic anisotropic model: Applications to Dy70Zr30 and DyCo3.4 alloys

We report theoretical investigations on the magnetocaloric effect, described by the magnetic entropy change in rare earth—transition metal amorphous systems. The model includes the local anisotropy on the rare earth ions in Harris-Plischke-Zuckermann assumptions. The transition metals ions are treated in terms of itinerant electron ferromagnetism and the magnetic moment of rare earth ions is coupled to the polarized d-band by a local exchange interaction. The magnetocaloric effect was calculated in DyCo3.4 system, which presents amorphous sperimagnetic configuration. The calculations predict higher refrigerant capacity in the amorphous DyCo3.4 than in DyCo2 crystal, highlighting the importance of amorphous magnetocaloric materials. Our calculation of the magnetocaloric effect in Dy70Zr30, which presents amorphous asperomagnetic configuration, is in good agreement with the experimental result. Furthermore, magnetic entropy changes associated with crystal-amorphous configurations change are estimated.

Influence of vacancy defects on the thermal stability of silicene: a reactive molecular dynamics study

The effect of vacancy defects on the structural properties and the thermal stability of free standing silicene – a buckled structure of hexagonally arranged silicon atoms – is studied using reactive molecular dynamics simulations. Pristine silicene is found to be stable up to 1500 K, above which the system transits to a three-dimensional amorphous configuration. Vacancy defects result in local structural changes in the system and considerably reduce the thermal stability of silicene: depending on the size of the vacancy defect, the critical temperature decreases by more than 30%. However, the system is still found to be stable well above room temperature within our simulation time of 500 ps. We found that the, stability of silicene can be increased by saturating the dangling bonds at the defect edges by foreign atoms (e.g., hydrogen).

Electrical properties of colloidal polyaniline‐2‐naphthalene sulfonic acid/graphene nanoparticle composite films

Polyaniline (PANI) nanocomposites containing different weight percentages of graphene (GR) are chemically prepared in the presence of β‐naphthalene sulfonic acid (NSA) and characterized using attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The characterization results suggest that the composites are formed via the interconnected fibrillar structure forming the semi‐crystalline/amorphous configuration by the β‐napthalene sulfonic acid (β‐NSA). The conductivities of the composites suggest that the composites undergo by two different regions of I and II before and after 378 K. The electrical conductivity of the composites is increased by increasing temperature. The dependence of conductivity on temperature implies that the PANI‐NSA/GR composites are organic semiconductors. POLYM. COMPOS., 35:60–67, 2014. © 2013 Society of Plastics Engineers

Crystallization time scales for polydisperse hard-sphere fluids

We study the evolution of crystallization in dense mono- and polydisperse hard sphere fluids, initially quenched to an amorphous configuration. We use as signatures of crystallization both the decay of the reduced pressure Z and the increase in the local and global orientational order parameters Q[over ¯](6). For a given realization of the crystallization process these parameters show sudden changes, both large and small, separated by long periods of quiescence. However, averaging over a large number of realizations, a well-defined scenario for their evolution appears. We find an initial fast relaxation to a disordered state, followed by a period of slow variation, associated to the presence of nucleation events, followed by a fast change, composed of the growth of a few crystals with different orientations, and a final and slow coarsening in a domain-growth process. No clear scaling for this whole process was found. We also find that the transition to an stable glassy fluid is quite sharp as the polydispersity is increased, showing a probable first-order phase transition behavior. A well-defined boundary between crystallizing and permanently amorphous fluids should exist, at least for a region in packing fractions. We looked for segregation at large values of polydispersity, but no effects of this type were found.

Structural distribution in mixed ternary noble gas and Lennard-Jones clusters

The geometrical structures and energies of mixed 38- and 55-atom Ar–Kr–Xe clusters are investigated. The interaction is described by ternary Lennard-Jones (TLJ) potential. The stable structures are optimized by adaptive immune optimization algorithm. Results show that in Ar12KrmXen (m+n=26) clusters, there exist amorphous and polytetrahedral configurations, and in Ar13KrmXen (m+n=42) clusters, structures are categorized into four classes, i.e., 8 Mackay icosahedra, 19 amorphous structures, 4 sixfold pancake structures, and 10 ring-like structures. Furthermore, strain energies in Ar–Kr–Xe clusters are studied to propose the possible ways of reducing strain. To investigate the potential energy surface of Ar–Kr–Xe clusters in TLJ model potential, the bond numbers of the Ar12Kr13Xe13 cluster and A12B13C13 TLJ model potential are compared, and the case of the former one is studied in the bond number phase diagram of the latter one.

Nonequilibrium static growing length scales in supercooled liquids on approaching the glass transition

The small wavenumber k behavior of the structure factor S(k) of overcompressed amorphous hard-sphere configurations was previously studied for a wide range of densities up to the maximally random jammed state, which can be viewed as a prototypical glassy state [A. Hopkins, F. H. Stillinger, and S. Torquato, Phys. Rev. E 86, 021505 (2012)]. It was found that a precursor to the glassy jammed state was evident long before the jamming density was reached as measured by a growing nonequilibrium length scale extracted from the volume integral of the direct correlation function c(r), which becomes long-ranged as the critical jammed state is reached. The present study extends that work by investigating via computer simulations two different atomic models: the single-component Z2 Dzugutov potential in three dimensions and the binary-mixture Kob-Andersen potential in two dimensions. Consistent with the aforementioned hard-sphere study, we demonstrate that for both models a signature of the glass transition is apparent well before the transition temperature is reached as measured by the length scale determined from the volume integral of the direct correlation function in the single-component case and a generalized direct correlation function in the binary-mixture case. The latter quantity is obtained from a generalized Ornstein-Zernike integral equation for a certain decoration of the atomic point configuration. We also show that these growing length scales, which are a consequence of the long-range nature of the direct correlation functions, are intrinsically nonequilibrium in nature as determined by an index X that is a measure of the deviation from thermal equilibrium. It is also demonstrated that this nonequilibrium index, which increases upon supercooling, is correlated with a characteristic relaxation time scale.

Molecular dynamics simulation of polyethylene/silver-nanoparticle composites

Molecular dynamics simulations of polyethylene/silver-nanoparticle composites are implemented to calculate the structures, electrical, thermal and mechanical properties, thereby investigating their relationships with the nanoparticle dimension and simulation temperature. The results show that polyethylene/silver-nanoparticle composites are of isotropic amorphous structure, and the dispersion of nanoparticles in composite can be enhanced at a relatively higher temperature. Multi-layers of atoms on nanoparticle surface change into amorphous configurations, and electrical polarization interface layers are formed between silver nanoparticles and polyethylene matrix. The interface region shrinks and expends respectively with nanoparticle dimension and temperature increasing. Compared with polyethylene system, the polyethylene/silver-nanoparticle composite presents explicitly high polarizability which increases with temperature and nanoparticle size rising simultaneously. The silver nanopaticle dimension directly influences the intensity and frequency of interfacial dipole moment, resulting in corresponding variations of peak position and intensity in infrared spectrum. The polyethylene/silver-nanoparticle composite also shows higher isometric heat capacity and negative thermal pressure coefficient with better temperature stability, which decreases explicitly with temperature and nanoparticle size increasing respectively, than polyethylene system. The mechanical property of polyethylene/silver-nanoparticle composite shows isotropic elastic constant tensor with considerably higher Young modulus and Poisson ratio than the polyethylene system, both of which decrease with temperature and nanoparticle dimension increasing, which indicates the improvement on mechanical property with Ag nanoparticle filler.

Molecular dynamics simulation study of polyimide/copper-nanoparticle composites

Molecular dynamics simulations of polyimide/copper-nanoparticle composites are implemented to calculate the morphological structures, thermodynamic and mechanical properties, and to investigate their relationships with the nanoparticle dimension and simulation temperature. The results demonstrate that polyimide/copper-nanoparticle composites are of isotropic amorphous structures, in which the copper nanoparticles combine with polyimide matrix due to van der Waals effect and multi-layers of atoms on nanoparticle surface change into amorphous configurations, forming interface layers between them. The interface regions shrink and expand respectively with increased nanoparticle dimension and temperature. The polyimide/copper-nanoparticle composites exhibit the explicit increase of isometric heat capacity with larger nanoparticle dimension in moderated temperature dependence, resulting in lower heat capacities at relatively low temperature for nanocomposites with relatively small nanoparticle size, compared with polyimide system. The thermal pressure coefficients of polyimide/copper-nanoparticle composites are distinctly higher than those of polyimide system, and increase substantially with enlarged nanoparticle dimension and reduce slightly with elevated temperature. The thermodynamic properties of polyimide/copper-nanoparticle composites manifest obvious scale-effect and distinctly higher temperature stability than polyimide system. The mechanical properties of polyimide/copper-nanoparticle composites represent isotropic elastic constant tensors with distinctly lower Young modulus and Poisson ratio than those of polyimide system, which decrease and increase respectively with increasing simulation temperature, exactly contrary to polyimide system and with substantially higher temperature stability of Young modulus. The composites with larger nanoparticle dimension exhibit considerably higher Poisson ratio with slight change of Young modulus, indicating the remarkably different mechanical properties of new nanocomposites with Cu nanoparticle filler.

Microstructure and mechanical properties of dissimilar Al alloy/steel joints prepared by a flat spot friction stir welding technique

The 6061-T6 Al alloy and mild steel plate with a thickness of 1mm were successfully welded by the flat spot friction stir welding technique, which contains two steps during the entire welding process. The rotating tools with different probe lengths of 1.0, 1.3 and 1.5mm were used in the first step, during which a conventional spot FSW was conducted above a round dent previously made on the back plate. However, sound Al/Fe welds with similar microstructure and mechanical properties can still be obtained after the second step, during which a probe-less rotating tool was used to flatten the weld surface. The sound welds have smooth surface without keyholes and other internal welding defects. No intermetallic compound layer but some areas with amorphous atomic configuration was formed along the Al/Fe joint interface due to the lower heat input. The shear tensile failure load can reach a maximum value of 3607N and fracture through plug mode. The probe length has little effect on the weld properties, which indicates that the tool life can be significantly extended by this new spot welding technique.