Hydrodynamics induce superdiffusive jumps of passive tracers along critical paths of random networks and colloidal gels.

We present a numerical study on the effect of hydrodynamic interactions (HI) on the diffusion of inert point tracer particles in several fixed random structures. As expected, the diffusion is hampered by the extra hydrodynamic friction introduced by the obstacle network. However, a non-trivial effect due to HI appears in the analysis of the van-Hove displacement probability close to the percolation threshold, where tracers diffuse through critical fractal paths. We show that the tracer dynamics can be split up into short and long jumps, the latter being ruled by either exponential or Gaussian van Hove distribution tails. While at short time HI slow down the tracer diffusion, at long times, hydrodynamic interactions with the obstacles increase the probability of longer jumps, which circumvent the traps of the labyrinth more easily. Notably, the relation between the anomalous diffusion exponent and the fractal dimension of the critical (intricate) paths is greater than one, which implies that the long-time (long-jump) diffusion is mildly superdiffuse. A possible reason for such a hastening of the diffusion along the network corridors is the hydrodynamically induced mobility anisotropy, which favours displacements parallel to the walls, an effect which has already been experimentally observed in collagen gels.

Halide Mixing Inhibits Exciton Transport in Two-dimensional Perovskites Despite Phase Purity.

Halide mixing is one of the most powerful techniques to tune the optical bandgap of metal-halide perovskites. However, halide mixing has commonly been observed to result in phase segregation, which reduces excited-state transport and limits device performance. While the current emphasis lies on the development of strategies to prevent phase segregation, it remains unclear how halide mixing may affect excited-state transport even if phase purity is maintained. Here, we study exciton transport in phase pure mixed-halide 2D perovskites of (PEA)2Pb(I1-x Br x )4. Using transient photoluminescence microscopy, we show that, despite phase purity, halide mixing inhibits exciton transport. We find a significant reduction even for relatively low alloying concentrations. By performing Brownian dynamics simulations, we are able to reproduce our experimental results and attribute the decrease in diffusivity to the energetically disordered potential landscape that arises due to the intrinsic random distribution of alloying sites.

Exciton diffusion in two-dimensional metal-halide perovskites.

Two-dimensional layered perovskites are attracting increasing attention as more robust analogues to the conventional three-dimensional metal-halide perovskites for both light harvesting and light emitting applications. However, the impact of the reduced dimensionality on the optoelectronic properties remains unclear, particularly regarding the spatial dynamics of the excitonic excited state within the two-dimensional plane. Here, we present direct measurements of exciton transport in single-crystalline layered perovskites. Using transient photoluminescence microscopy, we show that excitons undergo an initial fast diffusion through the crystalline plane, followed by a slower subdiffusive regime as excitons get trapped. Interestingly, the early intrinsic diffusivity depends sensitively on the choice of organic spacer. A clear correlation between lattice stiffness and diffusivity is found, suggesting exciton-phonon interactions to be dominant in the spatial dynamics of the excitons in perovskites, consistent with the formation of exciton-polarons. Our findings provide a clear design strategy to optimize exciton transport in these systems.

A general phenomenological relation for the subdiffusive exponent of anomalous diffusion in disordered media.

This work numerically investigates the diffusion of finite inert tracer particles in different types of fixed gels. The mean square displacement (MSD) of the tracers reveals a transition to subdiffusive motion MSD ∼ tα as soon as the accessible volume fraction p in the gel decreases from unity. Individual tracer dynamics reveals two types of particles in the gels: mobile tracers cross the system through percolating pores following subdiffusive dynamics MSDmob ∼ tαmob, while a fraction ptrap(p) of the particles remain trapped in finite pores. Below the void percolation threshold p < pc all the particles get trapped and α → 0. By separately studying both populations we find a simple phenomenological law for the mobile tracers αmob(p) ≈ a ln p + c where c ≈ 1 and a ∼ 0.2 depends on the gel type. On the other hand, a cluster-analysis of the gel accessible volume reveals a power law for the trapping probability ptrap ∼ (p/pc)-γ, with γ ≃ 2.9. This yields a prediction for the ensemble averaged subdiffusion exponent α = αmob(1 - ptrap). Our predictions are successfully validated against the different gels studied here and against numerical and experimental results in the literature (silica gels, polyacrylamide gels, flexible F-actin networks and in different random obstacles). Notably, the parameter a ∼ 0.2 presents small differences amongst all these cases, indicating the robustness of the proposed relation.