Hybrid Organic-Inorganic Thermoelectric Materials and Devices.

Hybrid organic-inorganic materials have been considered as a new candidate in the field of thermoelectric materials since the last decade owing to their great potential to enhance the thermoelectric performance by utilizing the low thermal conductivity of organic materials and the high Seebeck coefficient, and high electrical conductivity of inorganic materials. Herein, we provide an overview of interfacial engineering in the synthesis of various organic-inorganic thermoelectric hybrid materials, along with the dimensional design for tuning their thermoelectric properties. Interfacial effects are examined in terms of nanostructures, physical properties, and chemical doping between the inorganic and organic components. Several key factors which dictate the thermoelectric efficiency and performance of various electronic devices are also discussed, such as the thermal conductivity, electric transportation, electronic band structures, and band convergence of the hybrid materials.

Thermoelectric Characteristics of A Single-Crystalline Topological Insulator Bi2Se3 Nanowire.

The discovery of topological insulators (TIs) has motivated detailed studies on their physical properties, especially on their novel surface states via strong spin-orbit interactions. However, surface-state-related thermoelectric properties are rarely reported, likely because of the involvement of their bulk-dominating contribution. In this work, we report thermoelectric studies on a TI bismuth selenide (Bi2Se3) nanowire (NW) that exhibit a larger surface/volume ratio. Uniform single-crystalline TI Bi2Se3 NWs were successfully synthesized using a stress-induced growth method. To achieve the study of the thermoelectric properties of a nanowire (NW), including electrical conductivity (σ), Seebeck coefficient (S), and thermal conductivity (κ), a special platform for simultaneously performing all measurements on a single wire was designed. The properties of σ, S, and κ of a 200 nm NW that was well precharacterized using transmission electron microscope (TEM) measurements were determined using the four-probe method, the two-probe EMF across ∇T measurement, and the 3ω technique, respectively. The integrated TE properties represented by the figure of merit ZT (S2σT/κ) were found to be in good agreement with a theoretical study of Bi2Se3 NW.

Compositional Fluctuations Locked by Athermal Transformation Yielding High Thermoelectric Performance in GeTe.

Phase transition in thermoelectric (TE) material is a double-edged sword-it is undesired for device operation in applications, but the fluctuations near an electronic instability are favorable. Here, Sb doping is used to elicit a spontaneous composition fluctuation showing uphill diffusion in GeTe that is otherwise suspended by diffusionless athermal cubic-to-rhombohedral phase transition at around 700 K. The interplay between these two phase transitions yields exquisite composition fluctuations and a coexistence of cubic and rhombohedral phases in favor of exceptional figures-of-merit zT. Specifically, alloying GeTe by Sb2 Te3 significantly suppresses the thermal conductivity while retaining eligible carrier concentration over a wide composition range, resulting in high zT values of >2.6. These results not only attest to the efficacy of using phase transition in manipulating the microstructures of GeTe-based materials but also open up a new thermodynamic route to develop higher performance TE materials in general.

Enhanced lattice perfection by low temperature thermal annealing in photoelectric (CH3NH3)PbBr3.

The coupling between the organic CH3NH3+ cations and inorganic perovskite PbBr3- framework in a large single crystal of (CH3NH3)PbBr3 weighting 13 g was studied using neutron diffraction and inelastic neutron scattering. Two lattice incommensurate (ICM) phases were found, one at higher temperatures, marked ICMHT, which appeared between 147 and 135 K. The second one, marked ICMLT, developed below 143 K and remained at 75 K. The transition from the ICMLT to ICMHT phase upon warming gave rise to extremely large lattice shrinking, followed by extremely large lattice expansion of the tetragonal basal plane of the PbBr3 lattice. There was a progressive decrease in the width of the Bragg peaks from the PbBr3 lattice upon warming, which can be described using a critical exponent for each type of Bragg peak to show complete ordering of the atoms into a (CH3NH3)PbBr3 lattice at 194 K. (CH3NH3)PbBr3 exhibits six definitive acoustic-like phonon branches at 75 K. The six branches renormalizes into two at 200 K, with the frequencies of both the transverse and longitudinal modes greatly enhanced. The asymmetric structure of the CH3NH3 ions helps to understand the observed behaviors.

Thermodynamic Routes to Ultralow Thermal Conductivity and High Thermoelectric Performance.

Thermoelectric (TE) research is not only a course of materials by discovery but also a seedbed of novel concepts and methodologies. Herein, the focus is on recent advances in three emerging paradigms: entropy engineering, phase-boundary mapping, and liquid-like TE materials in the context of thermodynamic routes. Specifically, entropy engineering is underpinned by the core effects of high-entropy alloys; the extended solubility limit, the tendency to form a high-symmetry crystal structure, severe lattice distortions, and sluggish diffusion processes afford large phase space for performance optimization, high electronic-band degeneracy, rich multiscale microstructures, and low lattice thermal conductivity toward higher-performance TE materials. Entropy engineering is successfully implemented in half-Huesler and IV-VI compounds. In Zintl phases and skutterudites, the efficacy of phase-boundary mapping is demonstrated through unraveling the profound relations among chemical compositions, mutual solubilities of constituent elements, phase instability, microstructures, and resulting TE properties at the operation temperatures. Attention is also given to liquid-like TE materials that exhibit lattice thermal conductivity at lower than the amorphous limit due to intensive mobile ion disorder and reduced vibrational entropy. To conclude, an outlook on the development of next-generation TE materials in line with these thermodynamic routes is given.

Origin of the anomalous temperature evolution of photoluminescence peak energy in degenerate InN nanocolumns.

Photoluminescence (PL) behaviour in InN nanocolumns reveal decreasing, increasing and near invariant peak energies (E(PL)) as a function of temperature. Samples, having E(PL)~0.730 eV at 20 K, showed temperature invariance of E(PL). Samples possessing E(PL) on the lower and higher energy side of 0.730 eV demonstrate a normal redshift and anomalous blueshift, respectively, with increasing temperature. This temperature evolution can be effectively explained on the basis of a competition between a conventional red shift from lattice dilation, dominant for low carrier density sample, on one hand, and a blue shift of the electron and hole quasi Fermi-level separation, dominant for high carrier density samples, on the other.

Enhancing thermoelectric performance by Fermi level tuning and thermal conductivity degradation in (Ge1-xBix)Te crystals.

In this work, a high thermoelectric figure of merit, zT of 1.9 at 740 K is achieved in Ge1-xBixTe crystals through the concurrent of Seebeck coefficient enhancement and thermal conductivity reduction with Bi dopants. The substitution of Bi for Ge not only compensates the superfluous hole carriers in pristine GeTe but also shifts the Fermi level (EF) to an eligible region. Experimentally, with moderate 6-10% Bi dopants, the carrier concentration is drastically decreased from 8.7 × 1020 cm-3 to 3-5 × 1020 cm-3 and the Seebeck coefficient is boosted three times to 75 µVK-1. In the meantime, based on the density functional theory (DFT) calculation, the Fermi level EF starts to intersect with the pudding mold band at L point, where the band effective mass is enhanced. The enhanced Seebeck coefficient effectively compensates the decrease of electrical conductivity and thus successfully maintain the power factor as large as or even superior than that of the pristine GeTe. In addition, the Bi doping significantly reduces both thermal conductivities of carriers and lattices to an extremely low limit of 1.57 W m-1K-1 at 740 K with 10% Bi dopants, which is an about 63% reduction as compared with that of pristine GeTe. The elevated figure of merit observed in Ge1-xBixTe specimens is therefore realized by synergistically optimizing the power factor and downgrading the thermal conductivity of alloying effect and lattice anharmonicity caused by Bi doping.

Thermoelectric Figure-of-Merit of Fully Dense Single-Crystalline SnSe.

Single-crystalline SnSe has attracted much attention because of its record high figure-of-merit ZT ≈ 2.6; however, this high ZT has been associated with the low mass density of samples which leaves the intrinsic ZT of fully dense pristine SnSe in question. To this end, we prepared high-quality fully dense SnSe single crystals and performed detailed structural, electrical, and thermal transport measurements over a wide temperature range along the major crystallographic directions. Our single crystals were fully dense and of high purity as confirmed via high statistics 119Sn Mössbauer spectroscopy that revealed <0.35 at. % Sn(IV) in pristine SnSe. The temperature-dependent heat capacity (C p) provided evidence for the displacive second-order phase transition from Pnma to Cmcm phase at T c ≈ 800 K and a small but finite Sommerfeld coefficient γ0 which implied the presence of a finite Fermi surface. Interestingly, despite its strongly temperature-dependent band gap inferred from density functional theory calculations, SnSe behaves like a low-carrier-concentration multiband metal below 600 K, above which it exhibits a semiconducting behavior. Notably, our high-quality single-crystalline SnSe exhibits a thermoelectric figure-of-merit ZT ∼1.0, ∼0.8, and ∼0.25 at 850 K along the b, c, and a directions, respectively.

Layer-edge device of two-dimensional hybrid perovskites.

Two dimensional layered organic-inorganic hybrid perovskites (2D perovskites) are potential candidates for next generation photovoltaic device. Especially, the out-of-plane surface perpendicular to the superlattice plane of 2D perovskites (layer-edge surface) has presented several exotic behaviors, such as layer-edge states which are found to be crucial for improving the efficiency of 2D perovskite solar cells. However, fundamental research on transport properties of layer-edge surface is still absent. In this report, we observe the electronic and opto-electronic behavior in layer-edge device of 2D perovskites. The dark and photo currents are demonstrated to strongly depend on the crystallographic orientation in layer-edge device, and such anisotropic properties, together with photo response, are related to the thickness of inorganic layers. Finally, due to the abundant hydroxyl groups, water molecules are easy to condense on the layer-edge surface, and the conductance is extremely sensitive to the humidity environment, indicating a potential application of humidity sensor.