Disordered Energy Landscape Research Articles

Probing the Disorder Inside the Cubic Unit Cell of Halide Perovskites from First-Principles.

Strong deviations in the finite temperature atomic structure of halide perovskites from their average geometry can have profound impacts on optoelectronic and other device-relevant properties. Detailed mechanistic understandings of these structural fluctuations and their consequences remain, however, limited by the experimental and theoretical challenges involved in characterizing strongly anharmonic vibrational characteristics and their impact on other properties. We overcome some of these challenges by a theoretical characterization of the vibrational interactions that occur among the atoms in the prototypical cubic CsPbBr3. Our investigation based on first-principles molecular dynamics calculations finds that the motions of neighboring Cs-Br atoms interlock, which appears as the most likely Cs-Br distance being significantly shorter than what is inferred from an ideal cubic structure. This form of dynamic Cs-Br coupling coincides with very shallow dynamic potential wells for Br motions that occur across a locally and dynamically disordered energy landscape. We reveal an interesting dynamic coupling mechanism among the atoms within the nominal unit cell of cubic CsPbBr3 and quantify the important local structural fluctuations on an atomic scale.

Slow liquid dynamics near solid surfaces: Insights from site-resolved studies of ionic liquids in silica confinement.

We perform molecular dynamics simulations of ionic liquids that are confined between amorphous silica surfaces and composed of 1-butyl-3-methylimidazolium [C4mim] cations and tetrafluoroborate [BF4], hexafluorophosphate [PF6], or bis(trifluoromethylsulfonyl)imide [TFSI] anions. Near the silica surfaces, we observe strong slowdowns of ion dynamics, which involve mainly two layers of ions and amount to about two orders of magnitude, depending on temperature and anion type. For a detailed investigation of the slow interfacial dynamics, we determine the adsorption sites of the various anion species on the amorphous silica surfaces and ascertain the repopulation dynamics of these sites. The analysis reveals that the mean residence times show a broad distribution, where anions stay longer at sites, which provide better opportunities for hydrogen bonding. Furthermore, the mean residence times follow Arrhenius laws, providing access to site-specific activation energies Ei. The distributions G(Ei) have Gaussian shape with mean values from ∼0.40eV for TFSI to ∼0.48eV for PF6 and standard deviations of about 0.31eV. Thus, the amorphous silica surfaces impose static and disordered energy landscapes to the neighboring liquid, which have considerable ruggedness and, in this way, substantially hinder ion rearrangements. We discuss that qualitatively similar situations are expected for all kinds of confined liquids.

Dynamics of Two Distinct Exciton Populations in Methyl-Functionalized Germanane.

Methyl-substituted germanane is an emerging material that has been proposed for novel applications in optoelectronics, photoelectrocatalysis, and biosensors. It is a two-dimensional semiconductor with a strong above-gap fluorescence associated with water intercalation. Here, we use time-resolved photoluminescence spectroscopy to understand the mechanism causing this fluorescence. We show that it originates from two distinct exciton populations. Both populations recombine exponentially, accompanied by the thermally activated transfer of exciton population from the shorter- to the longer-lived type. The two exciton populations involve different electronic levels and couple to different phonons. The longer-lived type of exciton migrates within the disordered energy landscape of localized recombination centers. These outcomes shed light on the fundamental optical and electronic properties of functionalized germanane, enabling the groundwork for future applications in optoelectronics, light harvesting, and sensing.

A numerical study of the statistics of roughness parameters for fluctuating interfaces

Self-affine rough interfaces are ubiquitous in experimental systems, and display characteristic scaling properties as a signature of the nature of disorder in their supporting medium, i.e. of the statistical features of its heterogeneities. Different methods have been used to extract roughness information from such self-affine structures, and in particular their scaling exponents and associated prefactors. Notably, for an experimental characterization of roughness features, it is of paramount importance to properly assess sample-to-sample fluctuations of roughness parameters. Here, by performing scaling analysis based on displacement correlation functions in real and reciprocal space, we compute statistical properties of the roughness parameters. As an ideal, artifact-free reference case study and particularly targeting finite-size systems, we consider three cases of numerically simulated one-dimensional interfaces: (i) elastic lines under thermal fluctuations and free of disorder, (ii) directed polymers in equilibrium with a disordered energy landscape, and (iii) elastic lines in the critical depinning state when the external applied driving force equals the depinning force set by disorder. Our results show that sample-to-sample fluctuations are rather large when measuring the roughness exponent. These fluctuations are also relevant for roughness amplitudes. Therefore a minimum of independent interface realizations (at least a few tens in our numerical simulations) should be used to guarantee sufficient statistical averaging, an issue often overlooked in experimental reports.

Multiscale simulations of the electronic structure of III-nitride quantum wells with varied indium content: Connecting atomistic and continuum-based models

Carrier localization effects in III-N heterostructures are often studied in the frame of modified continuum-based models utilizing a single-band effective mass approximation. However, there exists no comparison between the results of a modified continuum model and atomistic calculations on the same underlying disordered energy landscape. We present a theoretical framework that establishes a connection between atomistic tight-binding theory and continuum-based electronic structure models, here a single-band effective mass approximation, and provide such a comparison for the electronic structure of (In,Ga)N quantum wells. In our approach, in principle, the effective masses are the only adjustable parameters since the confinement energy landscape is directly obtained from tight-binding theory. We find that the electronic structure calculated within effective mass approximation and the tight-binding model differ noticeably. However, at least in terms of energy eigenvalues, an improved agreement between the two methods can be achieved by adjusting the band offsets in the continuum model, enabling, therefore, a recipe for constructing a modified continuum model that gives a reasonable approximation of the tight-binding energies. Carrier localization characteristics for energetically low lying, strongly localized states differ, however, significantly from those obtained using the tight-binding model. For energetically higher lying, more delocalized states, good agreement may be achieved. Therefore, the atomistically motivated continuum-based single-band effective mass model established provides a good, computationally efficient alternative to fully atomistic investigations, at least at when targeting questions related to higher temperatures and carrier densities in (In,Ga)N systems.

Role of an additional interfacial spin-transfer torque for current-driven skyrmion dynamics in chiral magnetic layers

Skyrmions can be driven by spin-orbit torques as a result of the spin Hall effect. Here we model an additional contribution in ultra-thin multilayers, arising from the spin accumulation at heavy metal / ferromagnetic interfaces and observe the effects on a large range of skyrmion diameters. The combination of the interfacial spin-transfer torque and the spin-orbit torque results in skyrmion motion which helps to explain the observation of small skyrmion Hall angles for skyrmion diameters less than 100 nm. We show that this additional term has a significant effect on the skyrmion dynamics and leads to rapidly decreasing skyrmion Hall angles for small skyrmion diameters, as well as a skyrmion Hall angle versus skyrmion velocity dependence nearly independent of the surface roughness characteristics. Also, the effect of various disordered energy landscapes, in the form of surface roughness, on the skyrmion Hall angle and velocity is shown to be largely drive-dependent. Our results show good agreement with those found in experiments thus concluding that the interfacial spin-transfer torque should be included in micromagnetics simulations for the reproduction of experimental results.

Elastic Interfaces on Disordered Substrates: From Mean-Field Depinning to Yielding.

We consider a model of an elastic manifold driven on a disordered energy landscape, with generalized long range elasticity. Varying the form of the elastic kernel by progressively allowing for the existence of zero modes, the model interpolates smoothly between mean-field depinning and finite dimensional yielding. We find that the critical exponents of the model change smoothly in this process. Also, we show that in all cases the Herschel-Buckley exponent of the flow curve depends on the analytical form of the microscopic pinning potential. Within the present elastoplastic description, all this suggests that yielding in finite dimensions is a mean-field transition.

Superfluids, Fluctuations and Disorder

We present a field-theory description of ultracold bosonic atoms in the presence of a disordered external potential. By means of functional integration techniques, we aim to investigate and review the interplay between disordered energy landscapes and fluctuations, both thermal and quantum ones. Within the broken-symmetry phase, up to the Gaussian level of approximation, the disorder contribution crucially modifies both the condensate depletion and the superfluid response. Remarkably, it is found that the ordered (i.e., superfluid) phase can be destroyed also in regimes where the random external potential is suitable for a perturbative analysis. We analyze the simplest case of quenched disorder and then we move to present the implementation of the replica trick for ultracold bosonic systems. In both cases, we discuss strengths and limitations of the reviewed approach, paying specific attention to possible extensions and the most recent experimental outputs.

Response function of a moving contact line

How does a liquid-vapor interface in contact with a plate in motion react to the presence of defects at smaller scales? The hydrodynamics of such a system is investigated theoretically, offering a tractable mathematical framework to explore contact line motion through a disordered energy landscape.

Nanoscopy of Single Charge Carrier Jumps in a Conjugated Polymer Nanoparticle

We present super-resolution (∼2 nm spatial resolution per frame, 1 ms time resolution) tracking of single charge carriers in nanoparticles of the conjugated polymer PFBT. The motion of the charge carrier is determined from fluctuations in the centroid position of the particle fluorescence spot arising from fluorescence quenching by the polaron. A single polaron is observed to hop between a few sites, consistent with dispersive charge transport in a disordered energy landscape. In some shorter segments of the trajectory, there is repeated hopping between two sites, whereas for longer segments and full trajectories, random walk-like behavior consistent with multiple sites is observed. The hopping times range from a few milliseconds to seconds, following a power law distribution, while the hopping distances range from 2 to 5 nm, roughly following an exponential distribution. From the polaron hopping time distribution, we estimate a barrier height of 430–570 meV, with a nearest-neighbor distribution ranging f...

Temperature, electric-field, and carrier-density dependence of hopping magnetoresistivity in disordered organic semiconductors

Based on the extended variable range hopping mechanism in a disordered energy landscape with a Gaussian density of states, we determine the dependence of the magnetoresistivity on temperature, carrier density, magnetic field, and electric field. Experimental electric-field and temperature characteristics in device based on organic semiconductors are excellently reproduced with this unified description of the magnetoresistivity. We further show that the spin transport indeed can be explained by the fact that magnetic field will decrease the density of transport states and similar to the decrease of carrier density without it. We finally demonstrate that magnetoresistivity is strongly dependent on the carrier density; by changing the carrier density in the hopping system, the magnetoresistivity can increase more than 500 times.

Universal depinning transition of domain walls in ultrathin ferromagnets

We present a quantitative and comparative study of magnetic-field-driven domain-wall depinning transition in different ferromagnetic ultrathin films over a wide range of temperature. We reveal a universal scaling function accounting for both drive and thermal effects on the depinning transition, including critical exponents. The consistent description we obtain for both the depinning and subthreshold thermally activated creep motion should shed light on the universal glassy dynamics of thermally fluctuating elastic objects pinned by disordered energy landscapes.

Understanding mobility degeneration mechanism in organic thin-film transistors (OTFT)

Mobility degradation at high gate bias is often observed in organic thin film transistors. We propose a mechanism for this confusing phenomenon, based on the percolation theory with the presence of disordered energy landscape with an exponential density of states. Within a simple model we show how the surface states at insulator/organic interface trap a portion of channel carriers, and result in decrease of mobility as well as source/drain current with gate voltage. Depending on the competition between the carrier accumulation and surface trapping effect, two different carrier density dependences of mobility are obtained, in excellent agreement with experiment data.

Universal Pinning Energy Barrier for Driven Domain Walls in Thin Ferromagnetic Films.

We report a comparative study of magnetic field driven domain wall motion in thin films made of different magnetic materials for a wide range of field and temperature. The full thermally activated creep motion, observed below the depinning threshold, is shown to be described by a unique universal energy barrier function. Our findings should be relevant for other systems whose dynamics can be modeled by elastic interfaces moving on disordered energy landscapes.

Immense Magnetic Response of Exciplex Light Emission due to Correlated Spin-Charge Dynamics

As carriers slowly move through a disordered energy landscape in organic semiconductors, tiny spatial variations in spin dynamics relieve spin blocking at transport bottlenecks or in the electron-hole recombination process that produces light. Large room-temperature magnetic-field effects (MFE) ensue in the conductivity and luminescence. Sources of variable spin dynamics generate much larger MFE if their spatial structure is correlated on the nanoscale with the energetic sites governing conductivity or luminescence such as in co-evaporated organic blends within which the electron resides on one molecule and the hole on the other (an exciplex). Here we show that exciplex recombination in blends exhibiting thermally-activated delayed fluorescence (TADF) produces MFE in excess of 60% at room temperature. In addition, effects greater than 4000% can be achieved by tuning the device's current-voltage response curve by device conditioning. These immense MFEs are both the largest reported values for their device type at room temperature. Our theory traces this MFE and its unusual temperature dependence to changes in spin mixing between triplet exciplexes and light-emitting singlet exciplexes. In contrast, spin mixing of excitons is energetically suppressed, and thus spin mixing produces comparatively weaker MFE in materials emitting light from excitons by affecting the precursor pairs. Demonstration of immense MFE in common organic blends provides a flexible and inexpensive pathway towards magnetic functionality and field sensitivity in current organic devices without patterning the constituent materials on the nanoscale. Magnetic fields increase the power efficiency of unconditioned devices by 30% at room temperature, also showing that magnetic fields may increase the efficiency of the TADF process.

Spin diffusion in disordered organic semiconductors

An analytical theory for spin diffusion in disordered organic semiconductors is derived. It is based on percolation theory and variable range hopping in a disordered energy landscape with a Gaussian density of states. It describes universally the dependence of the spin diffusion on temperature, carrier density, material disorder, magnetic field, and electric field at the arbitrary magnitude of the Hubbard energy of charge pairs. It is found that, compared to the spin transport carried by carriers hopping, the spin exchange will hinder the spin diffusion process at low carrier density, even under the condition of a weak electric field. Importantly, under the influence of a bias voltage, anomalous spreading of the spin packet will lead to an abnormal temperature dependence of the spin diffusion coefficient and diffusion length. This explains the recent experimental data for spin diffusion length observed in Alq3.

Intrinsically disordered energy landscapes.

Analysis of an intrinsically disordered protein (IDP) reveals an underlying multifunnel structure for the energy landscape. We suggest that such ‘intrinsically disordered’ landscapes, with a number of very different competing low-energy structures, are likely to characterise IDPs, and provide a useful way to address their properties. In particular, IDPs are present in many cellular protein interaction networks, and several questions arise regarding how they bind to partners. Are conformations resembling the bound structure selected for binding, or does further folding occur on binding the partner in a induced-fit fashion? We focus on the p53 upregulated modulator of apoptosis (PUMA) protein, which adopts an -helical conformation when bound to its partner, and is involved in the activation of apoptosis. Recent experimental evidence shows that folding is not necessary for binding, and supports an induced-fit mechanism. Using a variety of computational approaches we deduce the molecular mechanism behind the instability of the PUMA peptide as a helix in isolation. We find significant barriers between partially folded states and the helix. Our results show that the favoured conformations are molten-globule like, stabilised by charged and hydrophobic contacts, with structures resembling the bound state relatively unpopulated in equilibrium.

Topologically protected excitons in porphyrin thin films

The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials.

Two-Dimensional Electronic Spectroscopy Reveals Ultrafast Energy Diffusion in Chlorosomes

Chlorosomes are light-harvesting antennae that enable exceptionally efficient light energy capture and excitation transfer. They are found in certain photosynthetic bacteria, some of which live in extremely low-light environments. In this work, chlorosomes from the green sulfur bacterium Chlorobaculum tepidum were studied by coherent electronic two-dimensional (2D) spectroscopy. Previously uncharacterized ultrafast energy transfer dynamics were followed, appearing as evolution of the 2D spectral line-shape during the first 200 fs after excitation. Observed initial energy flow through the chlorosome is well explained by effective exciton diffusion on a sub-100 fs time scale, which assures efficiency and robustness of the process. The ultrafast incoherent diffusion-like behavior of the excitons points to a disordered energy landscape in the chlorosome, which leads to a rapid loss of excitonic coherences between its structural subunits. This disorder prevents observation of excitonic coherences in the experimental data and implies that the chlorosome as a whole does not function as a coherent light-harvester.

Oriented graph structure of local energy minima in the random-field Ising model

In this paper we investigate the structure of the disordered energy landscape of the RFIM with field-driven single-spin-flip dynamics. We show that local energy minima are partitioned into equivalence classes (basins) organized in a binary oriented graph. We discuss two algorithms by which one can explore the oriented graph structure.