Remarkably Weak Anisotropy in Thermal Conductivity of Two-Dimensional Hybrid Perovskite Butylammonium Lead Iodide Crystals.

Two-dimensional (2D) hybrid organic-inorganic perovskites consisting of alternating organic and inorganic layers are a new class of layered structures. They have attracted increasing interest for photovoltaic, optoelectronic, and thermoelectric applications, where knowing their thermal transport properties is critical. We carry out both experimental and computational studies on thermal transport properties of 2D butylammonium lead iodide crystals and find their thermal conductivity is ultralow (below 0.3 W m-1 K-1) with very weak anisotropy (around 1.5) among layered crystals. Further analysis reveals that the unique structure with the preferential alignment of organic chains and complicated energy landscape leads to moderately smaller phonon lifetimes in the out-of-plane direction and comparable phonon group velocities in in-plane and out-of-plane directions. These new findings may guide the future design of novel hybrid materials with desired thermal conductivity for various applications.

Synthesis and Thermal Properties of Solid-State Structural Isomers: Ordered Intergrowths of SnSe and MoSe2.

A family of structural isomers [(SnSe)1.05]m(MoSe2)n were prepared using the modulated elemental reactant method by varying the layer sequence and layer thicknesses in the precursor. By varying the sequence of Sn-Se and Mo-Se layer pairs deposited and annealing the precursors to self-assemble the targeted compound, all six possible isomers [(SnSe)1.05]4(MoSe2)4, [(SnSe)1.05]3(MoSe2)3[(SnSe)1.05]1(MoSe2)1, [(SnSe)1.05]3(MoSe2)2[(SnSe)1.05]1(MoSe2)2, [(SnSe)1.05]2(MoSe2)3[(SnSe)1.05]2(MoSe2)1, [(SnSe)1.05]2(MoSe2)1[(SnSe)1.05]1(MoSe2)2[(SnSe)1.05]1(MoSe2)1, and [(SnSe)1.05]2(MoSe2)2[(SnSe)1.05]1(MoSe2)1[(SnSe)1.05]1(MoSe2)1 were prepared. The structures were characterized by X-ray diffraction and electron microscopy which showed that all of the compounds have very similar c-axis lattice parameters and in-plane constituent lattice parameters yet distinct isomeric structures. These studies confirm that the structure, order, and thickness of the constituent layers match that of the precursors. The cross-plane thermal conductivity is found to be very low (∼0.08 Wm(-1) K(-1)) and independent of the number of SnSe-MoSe2 interfaces within uncertainty. The poor thermal transport in these layered isomers is attributed to a large cross-plane thermal resistance created by SnSe-MoSe2 and MoSe2-MoSe2 turbostratically disordered van der Waals interfaces, the density of which has less variation among the different compounds than the SnSe-MoSe2 interface density alone.

Ultralow thermal conductivity in polycrystalline CdSe thin films with controlled grain size.

Polycrystallinity leads to increased phonon scattering at grain boundaries and is known to be an effective method to reduce thermal conductivity in thermoelectric materials. However, the fundamental limits of this approach are not fully understood, as it is difficult to form uniform sub-20 nm grain structures. We use colloidal nanocrystals treated with functional inorganic ligands to obtain nanograined films of CdSe with controlled characteristic grain size between 3 and 6 nm. Experimental measurements demonstrate that thermal conductivity in these composites can fall beneath the prediction of the so-called minimum thermal conductivity for disordered crystals. The measurements are consistent, however, with diffuse boundary scattering of acoustic phonons. This apparent paradox can be explained by an overattribution of transport to high-energy phonons in the minimum thermal conductivity model where, in compound semiconductors, optical and zone edge phonons have low group velocity and high scattering rates.

Water-processable polymer-nanocrystal hybrids for thermoelectrics.

We report the synthesis and thermoelectric characterization of composite nanocrystals composed of a tellurium core functionalized with the conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Solution processed nanocrystal films electronically out perform both PEDOT:PSS and unfunctionalized Te nanorods while retaining a polymeric thermal conductivity, resulting in a room temperature ZT ∼ 0.1. This combination of electronic and thermal transport indicates the potential for tailored transport in nanoscale organic/inorganic heterostructures.

Chain-Length Dependence of Thermal Conductivity in 2D Alkylammonium Lead Iodide Single Crystals.

In 2D organic-inorganic hybrid perovskite materials, layers of conducting inorganic material are separated by insulating organic spacers whose length and composition can be tuned. We report the heat capacity and cross-plane thermal conductivity of 2D alkylammonium lead iodide single crystals with increasing chain length, (CnH2n+1NH3)2PbI4 (n = 4-7). The measured thermal conductivities are some of the lowest ever recorded for single crystals, with averages in the range k = 0.099-0.125 W/m K. Although a model based on independent interface resistances between adjacent layers predicts an increase in thermal conductivity with a chain length of more than 30%, experimentally we find that the thermal conductivity is nearly independent of chain length and possibly decreases. We hypothesize that phonons carry an appreciable portion of the heat across the interface coherently, rather than being limited by individual weak interfaces.

Structure Evolution and Thermoelectric Properties of Carbonized Polydopamine Thin Films.

Carbonization of nature-inspired polydopamine can yield thin films with high electrical conductivity. Understanding of the structure of carbonized PDA (cPDA) is therefore highly desired. In this study, neutron diffraction, Raman spectroscopy, and other techniques indicate that cPDA samples are mainly amorphous with some short-range ordering and graphite-like structure that emerges with increasing heat treatment temperature. The electrical conductivity and the Seebeck coefficient show different trends with heat treatment temperature, while the thermal conductivity remains insensitive. The largest room-temperature ZT of 2 × 10-4 was obtained on samples heat-treated at 800 °C, which is higher than that of reduced graphene oxide.

Pump-probe measurements of the thermal conductivity tensor for materials lacking in-plane symmetry.

We previously demonstrated an extension of time-domain thermoreflectance (TDTR) which utilizes offset pump and probe laser locations to measure in-plane thermal transport properties of multilayers. However, the technique was limited to systems of transversely isotropic materials studied using axisymmetric laser intensities. Here, we extend the mathematics so that data reduction can be performed on non-transversely isotropic systems. An analytic solution of the diffusion equation for an N-layer system is given, where each layer has a homogenous but otherwise arbitrary thermal conductivity tensor and the illuminating spots have arbitrary intensity profiles. As a demonstration, we use both TDTR and time-resolved magneto-optic Kerr effect measurements to obtain thermal conductivity tensor elements of <110> α-SiO2. We show that the out-of-phase beam offset sweep has full-width half-maxima that contains nearly independent sensitivity to the in-plane thermal conductivity corresponding to the scanning direction. Also, we demonstrate a Nb-V alloy as a low thermal conductivity TDTR transducer layer that helps improve the accuracy of in-plane measurements.

Probing anisotropic heat transport using time-domain thermoreflectance with offset laser spots.

An analytic solution is derived for the time-domain thermoreflectance signal that occurs using non-concentric pump and probe beams on multilayer anisotropic materials. When in-plane heat transport is negligible, the experimental signal is the same as for the concentric case. However, for samples where in-plane heat diffusion distances are comparable to the spot size, the signal is sensitive to in-plane heat transport. This sensitivity to in-plane transport can be exploited to measure the in-plane thermal conductivity. Examples with experimental data are given for thin-film Al and the in-plane thermal conductivity of pyrolytic graphite.

Enhanced thermopower in PbSe nanocrystal quantum dot superlattices.

We examine the effect of strong three-dimensional quantum confinement on the thermopower and electrical conductivity of PbSe nanocrystal superlattices. We show that for comparable carrier concentrations PbSe nanocrystal superlattices exhibit a substantial thermopower enhancement of several hundred microvolts per Kelvin relative to bulk PbSe. We also find that thermopower increases monotonically as the nanocrystal size decreases due to changes in carrier concentration. Lastly, we demonstrate that thermopower of PbSe nanocrystal solids can be tailored by charge-transfer doping.