Thin films of amorphous (a)-TiO2 are ubiquitous as photocatalysts, protective coatings, photoanodes and in memory application, where they are exposed to excess electrons and holes. We investigate trapping of excess electrons and holes in the bulk of pure amorphous titanium dioxide, a-TiO2, using hybrid density functional theory (h-DFT) calculations. Fifty 270-atom a-TiO2 structures were produced using classical molecular dynamics and their geometries fully optimised using h-DFT simulations. They have the density, distribution of atomic coordination numbers and radial pair-distribution functions in agreement with experiment. The calculated average a-TiO2 band gap is 3.25 eV with no states splitting into the band gap. Trapping of excess electrons and holes in a-TiO2 is predicted at precursor sites, such as elongated Ti-O bonds. Single electron and hole polarons have average trapping energies (ET) of -0.4 eV and -0.8 eV, respectively. We also identify several types of electron and hole bipolaron states and discuss their stability. These results can be used for understanding the mechanisms of photo-catalysis and improving the performance of electronic devices employing a-TiO2 films.
Force-constant and positional disorder have been introduced into diamond lattice models in an attempt to mimic the vibrational properties of a realistic amorphous silicon model. Neither type of disorder is sufficient on its own to mimic the realistic model. By comparing the spectral densities of these models, it is shown that a combination of both disorders is a better representation, but still not completely satisfactory. Topological disorder in these models was investigated by renumbering the atoms and examining the dynamical matrix graphically. The dynamical matrix of the realistic model is…
We consider the bimolecular charge carrier recombination in amorphous organic semiconductors having a special kind of energetic disorder where energy levels for electrons and holes at a given transport site move in the same direction with the variation of some disorder governing parameter (the parallel disorder). This particular kind of disorder could be found in materials where the dominant part of the energetic disorder is provided by the conformational disorder. Contrary to the recently studied case of electrostatic disorder, the conformational disorder, if spatially correlated, leads to th…
The effects of hole injection in amorphous-IGZO is analyzed by means of first-principles calculations. The injection of holes in the valence band tail states leads to their capture as a polaron, with high self-trapping energies (from 0.44 to 1.15 eV). Once formed, they mediate the formation of peroxides and remain localized close to the hole injection source due to the presence of a large diffusion energy barrier (of at least 0.6eV). Their diffusion mechanism can be mediated by the presence of hydrogen. The capture of these holes is correlated with the low off-current observed for a-IGZO trans…
A disorder-order transition from amorphous carbon (aC) to layered amorphous graphene (LAG) has been predicted using ab-initio methods. Amorphous carbon at densities close to the graphitic density show a strong proclivity to layer in NVT simulations near 3000K . Our calculations have shown that graphitization is strongly dependent on the simulation temperature and is not observed under 2500K. The origin of such a disorder-order transition has been studied using various structural analyses. Each layer of LAG is a layer of amorphous graphene (aG) including pentagons and heptagons in addition to h…
The excited holes occupying the valence band tail states in amorphous oxide semiconductors are found to induce formation of meta-stable O$_2^{2-}$ peroxide defects. The valence band tail states are at least partly characterized by the O-O ppσ* molecular orbital, and the localized-hole-mediated lattice instability results in the formation of the peroxide defects. Along with the O-O bond formation, the ppσ* state is heightened up into the conduction bands, and two electrons are accordingly doped in the electronic ground state. The energy barrier from the O$_2^{2-}$ peroxide state to the normal d…
Molecular dynamics simulations of shear band development over 1000% strain in simple shear are used to test whether the local plastic strain rate is proportional to exp(-1/chi), where chi is a dimensionless quantity related to the "disorder temperature" or "free volume" that characterizes the structural state of the glass. Scaling is observed under the assumption that chi is linearly related to the local potential energy per atom. This analysis permits the extraction of the potential energy per atom at which chi=0 and the approximate energy needed to create a shear transformation zone.
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 …
It is argued that topological disorder in amorphous solids can be described by local strains related to local reference crystals and local rotations. An intuitive localization criterion is formulated from this point of view. The Inverse Participation Ratio and the location of mobility edges in band tails is directly related to the character of the disorder potential in amorphous solid, the coordination number, the transition integral and the nodes of wave functions of the corresponding reference crystal. The dependence of the decay rate of band tails on temperature and static disorder are deri…
We use atomistic computer simulations to provide a microscopic description of the brittle failure of amorphous materials, and we assess the role of rare events and quenched disorder. We argue that brittle yielding originates at rare soft regions, similarly to Griffiths effects in disordered systems. We numerically demonstrate how localized plastic events in such soft regions trigger macroscopic failure via the propagation of a shear band. This physical picture, which no longer holds in poorly annealed ductile materials, allows us to discuss the role of finite size effects in brittle yielding a…
(abridged) We present results of the disorder-induced metal-insulator-transition (MIT) in three-dimensional amorphous indium-oxide films. The amorphous version studied here differs from the one reported earlier [PRB 46, 10917 (1992)] in that it has a much lower carrier concentration. As a measure of the static disorder we use the dimensionless parameter kFl. Thermal annealing is employed as the experimental handle to tune the disorder. On the metallic side of the transition, the low temperature transport exhibits weak-localization and electron-electron correlation effects characteristic of dis…
The structure of very high-density amorphous (VHDA) ice has been modelled by positionally disordering three crystalline phases, namely ice IV, VI and XII. These phases were chosen because only they are stable or metastable in the region of the ice phase diagram where VHDA ice is formed, and their densities are comparable to that of VHDA ice. An excellent fit to the medium range of the experimentally observed pair-correlation function g(r) of VHDA ice was obtained by introducing disorder into the positions of the H2O molecules, as well as small amounts of molecular rotational disorder, disorder…
We present a simple model of the bimolecular charge carrier recombination in polar amorphous organic semiconductors where the dominant part of the energetic disorder is provided by permanent dipoles and show that the recombination rate constant could be much smaller than the corresponding Langevin rate constant. The reason for the strong decrease of the rate constant is the long range spatial correlation of the random energy landscape in amorphous dipolar materials, without spatial correlation even strong disorder does not modify the Langevin rate constant. Our study shows that the significant…
We predict a transition to metallicity when a sufficient amount of disorder is induced in graphene. Calculations were performed by means of a first principles stochastic quench method. The resulting amorphous graphene can be seen as nanopatches of graphene that are connected by a network of disordered small and large carbon rings. The buckling is minimal and we believe that it is a result of averaging of counteracting random in-plane stress forces. The linear response conductance is obtained by a model theory as function of lattice distortions. Such metallic behaviour is a much desired propert…
Two-dimensional (2D) materials like graphene and h-BN usually show high thermal conductivity, which enables rich applications in thermal dissipation and nanodevices. Disorder, on the other hand, is often present in 2D materials. Structural disorder induces localization of electrons and phonons and alters the electronic, mechanical, thermal, and magnetic properties. Here we calculate the in-plane thermal conductivity of both monolayer carbon and monolayer boron nitride in the amorphous form, by reverse nonequilibrium molecular dynamics simulations. We find that the thermal conductivity of both …
This investigation extends earlier studies of a shear-transformation-zone (STZ) theory of plastic deformation in amorphous solids. My main purpose here is to explore the possibility that the configurational degrees of freedom of such systems fall out of thermodynamic equilibrium with the heat bath during persistent mechanical deformation, and that the resulting state of configurational disorder may be characterized by an effective temperature. The further assumption that the population of STZ's equilibrates with the effective temperature allows the theory to be compared directly with experimen…
This paper addresses a difficult inverse problem that involves the reconstruction of a three-dimensional model of tetrahedral amorphous semiconductors via inversion of diffraction data. By posing the material-structure determination as a multi-objective optimization program, it has been shown that the problem can be solved accurately using a few structural constraints, but no total-energy functionals/forces, which describe the local chemistry of amorphous networks. The approach yields highly realistic models of amorphous silicon, with no or only a few coordination defects ($\le$ 1%), a narrow …
We study the ferromagnetism of La0.67Ca0.33MnO3 in bulk polycrystalline, nanocrystalline and amorphous phase. The structural change from crystalline phase to amorphous phase exhibited a systematic decrease of TC(paramagnetic to ferromagnetic transition temperature) and spontaneous magnetization (MS). The experimental results suggested few more features, e.g., appearance of large magnetic irreversibility in the temperature dependence of magnetization, lack of magnetic saturation at high magnetic field, blocking of magnetization below TB, and enhancement of coercivity. In addition, the magnetic …
I discuss the properties of electron states in amorphous Si based on large scale calculations with realistic several thousand atom models. A relatively simple model for the localized to extended (Anderson) transition is reviewed. Then, the effect of thermal disorder on localized electron states is considered. It is found that under readily accessible conditions, localized (midgap or band tail) states and their conjugate energies may fluctuate dramatically. The possible importance of non-adiabatic atomic dynamics to doped or photo-excited systems is briefly discussed.
A theory of vibrational excitations based on power-law spatial correlations in the elastic constants (or equivalently in the internal stress) is derived, in order to determine the vibrational density of states $D(ω)$ of disordered solids. The results provide the first prediction of a boson peak in amorphous materials where spatial correlations in the internal stresses (or elastic constants) are of power-law form, as is often the case in experimental systems, leading to logarithmic enhancement of (Rayleigh) phonon attenuation. A logarithmic correction of the form $\sim -ω^{2}\lnω$ is predicted …
The nature of bosonic excitations in disordered materials has remained elusive due to the difficulties in defining key concepts such as quasi-particles in the presence of disorder. We report on the experimental observation of phonon-polaritons in glasses, including a boson peak (BP), i.e. excess of THz modes over the Debye law. A theoretical framework based on the concept of diffusons is developed to model the broadening linewidth of the polariton due to disorder-induced scattering. It is shown that the scaling of the BP frequency with the diffusion constant of the linewidth strongly correlate…
A theory of phonon-mediated superconductivity in strong-coupling amorphous materials is developed based on an effective description of structural disorder and its effect on the vibrational spectrum. The theory accounts for the diffusive-like transport of vibrational excitations due to disorder-induced scattering within the Eliashberg theory of strong-coupling superconductivity. The theory provides a good analytical description of the Eliashberg function $α^{2}F(ω)$ in comparison with experiments, and allows one to disentangle the effects of transverse and longitudinal excitations on the Eliash…
The dynamics of charge carriers in amorphous semiconductors fundamentally differ from those in crystalline semiconductors due to the lack of long-range order and the high defect density. Despite intensive technology-driven research interests and the existence of well-established experimental techniques, such as photoconductivity time-of-flight and ultrafast optical measurements, many aspects of the dynamics of photo-excited charge carriers in amorphous semiconductors remain poorly understood. Here we demonstrate direct imaging of carrier dynamics in space and time after photo-excitation in hyd…
Much of the discussion in the literature of the low frequency part of the density of states of amorphous solids was dominated for years by comparing measured or simulated density of states to the classical Debye model. Since this model is hardly appropriate for the materials at hand, this created some amount of confusion regarding the existence and universality of the so- called ``Boson Peak'' which results from such comparisons. We propose that one should pay attention to the different roles played by different aspects of disorder, the first being disorder in the interaction strengths, the se…
Using a novel thermodynamic integration scheme, we compute the excess free energy, $γ$, of a glass-forming, binary Lennard-Jones liquid in contact with a frozen amorphous wall, formed by particles frozen into a similar structure as the liquid. We find that $γ$ is non-zero, becoming negative at low temperature. This indicates that the thermodynamics of the system is perturbed by the effect of the amorphous wall.
Doped organic semiconductors are critical to emerging device applications, including thermoelectrics, bioelectronics, and neuromorphic computing devices. It is commonly assumed that low conductivities in these materials result primarily from charge trapping by the Coulomb potentials of the dopant counter-ions. Here, we present a combined experimental and theoretical study rebutting this belief. Using a newly developed doping technique, we find the conductivity of several classes of high-mobility conjugated polymers to be strongly correlated with paracrystalline disorder but poorly correlated w…
Shear transformations (i.e., localised rearrangements of particles resulting in the shear deformation of a small region of the sample) are the building blocks of mesoscale models for the flow of disordered solids. In order to compute the time-dependent response of the solid material to such a shear transformation, with a proper account of elastic heterogeneity and shear wave propagation, we propose and implement a very simple Finite-Element (FE) -based method. Molecular Dynamics (MD) simulations of a binary Lennard-Jones glass are used as a benchmark for comparison, and information about the m…
We analyze, through molecular dynamics simulations, the temperature dependence of the thermal conductivity (k) of chain-oriented amorphous polyethylene (PE). We find that at increasing levels of orientation, the temperature corresponding to a peak k progressively decreases. Un-oriented PE exhibits the peak k at 350 K, while aligned PE under an applied strain of 400% shows a maximum at 100 K. This transition of peak k to lower temperatures with increasing alignment is explained in terms of a crossover from disorder to anharmonicity dominated phonon transport in aligned polymers. Evidence for th…
Understanding the transport mechanism of electronic excitations in conjugated polymers is key to advancing organic optoelectronic applications, such as solar cells, OLEDs and flexible electronics. While crystalline polymers can be studied using solid-state techniques based on lattice periodicity, the characterisation of amorphous polymers is hindered by an intermediate regime of disorder and the associated lack of symmetries. To overcome these hurdles we use a reduced state quantum master equation approach based on the Merrifield exciton formalism. Using this model we study exciton transport i…
We discuss how structural disorder and amorphization affects solid-state diffusion, and consider zirconolite as a currently important case study. By performing extensive molecular dynamics simulations, we disentangle the effects of amorphization and density, and show that a profound increase of solid-state diffusion takes place as a result of amorphization. Importantly, this can take place at the same density as in the crystal, representing an interesting general insight regarding solid-state diffusion. We find that decreasing the density in the amorphous system increases pre-factors of diffus…
Amorphous silicon films prepared by electron beam evaporation have systematically and substantially greater atomic density for higher thickness, higher growth temperature, and slower deposition rate, reaching the density of crystalline Si when films of thickness greater than ~300 nm are grown at 425 $^{\circ}$C and at <1 $Å$/sec. A combination of spectroscopic techniques provide insight into atomic disorder, local strains, dangling bonds, and nanovoids. Electron diffraction shows that the short-range order of the amorphous silicon is similar at all growth temperatures, but fluctuation electron…
When far from equilibrium, many-body systems display behavior that strongly depends on the initial conditions. A characteristic such example is the phenomenon of plasticity of crystalline and amorphous materials that strongly depends on the material history. In plasticity modeling, the history is captured by a quenched, local and disordered flow stress distribution. While it is this disorder that causes avalanches that are commonly observed during nanoscale plastic deformation, the functional form and scaling properties have remained elusive. In this paper, a generic formalism is developed for…
Thin film transistors, with channels composed of In-X-Zn oxides, IXZO, with X dopants: Ga, Sb, Be, Mg, Ag, Ca, Al, Ni, and Cu, were fabricated and their I-V characteristics were taken at selected temperatures in the 77K<T<300K range. The low field mobility, mu, and the interface defect density, Nst were extracted from the characteristics for each of the studied IXZOs. At higher T the mobility follows the Arrhenius law with an upward distortion, increasing as T was lowered, gradually transforming into the exp [-(T0/T)1/4] variation. We showed that mu(T, Nst) follows mu0exp[-Eaeff(T,Nst)/kT], wi…
We report on a non-equilibrium phase of matter, the minimally disordered crystal phase, which we find exists between the maximally amorphous glasses and the ideal crystal. Even though these near crystals appear highly ordered, they display glassy and jamming features akin to those observed in amorphous solids. Structurally, they exhibit a power-law scaling in their probability distribution of weak forces and small interparticle gaps as well as a flat density of vibrational states. Dynamically, they display anomalous aging above a characteristic pressure. Quantitatively this disordered crystal …
Self-assembled monolayers (SAMs) have been used to improve both the positive and negative bias-stress stability of amorphous indium gallium zinc oxide (IGZO) bottom gate thin film transistors (TFTs). N-hexylphosphonic acid (HPA) and fluorinated hexylphosphonic acid (FPA) SAMs adsorbed on IGZO back channel surfaces were shown to significantly reduce bias stress turn-on voltage shifts compared to IGZO back channel surfaces with no SAMs. FPA was found to have a lower surface energy and lower packing density than HPA, as well as lower bias stress turn-on voltage shifts. The improved stability of I…
Atomistic simulations are used to explore the effect of interfacial structure on residual radiation damage. Specifically, an ordered grain boundary is compared to a disordered amorphous intergranular film, to investigate how interface thickness and free volume impacts point defect recombination. The collision cascades induced by neutron bombardment are simulated and residual point defect populations are analyzed as a function of boundary type and primary knock on atom energy. While ordered grain boundaries easily absorb interstitials, these interfaces are inefficient vacancy sinks. Alternative…
