Keywords: Layered compounds / Thin films / Electronic structure / Thermoelectric materials / Charge transfer (SnSe) 1.2 TiSe 2 was found to self-assemble from a precursor containing modulated layers of Sn-Se and Ti-Se over a surprisingly large range of layer thicknesses and compositions. The constituent lattices form an alternating layer superstructure with rotational disorder present between the layers. This compound was found to have the highest Seebeck coefficient measured for analogous TiX 2 containing misfit layered compounds to date, suggesting potential for [a]83 low-temperature thermoelectric applications. Electrical characterization suggests that electrons transferred from SnSe to TiSe 2 are responsible for the higher carrier concentration observed relative to bulk TiSe 2 . The transfer of charge from one constituent to the other may provide a mechanism for doping layered dichalcogenides for various applications without negatively affecting carrier mobility.

The compounds, ([SnSe]1.15)1(VSe2)n with n = 1, 2, 3, and 4, were prepared using designed precursors in order to investigate the influence of the thickness of the VSe2 constituent on the charge density wave transition. The structure of each of the compounds was determined using X-ray diffraction and scanning transmission electron microscopy. The charge density wave transition observed in the resistivity of ([SnSe]1.15)1(VSe2)1 was confirmed. The electrical properties of the n = 2 and 3 compounds are distinctly different. The magnitude of the resistivity change at the transition temperature is dramatically lowered and the temperature of the resistivity minimum systematically increases from 118 K (n = 1) to 172 K (n = 3). For n = 1, this temperature correlates with the onset of the charge density wave transition. The Hall-coefficient changes sign when n is greater than 1, and the temperature dependence of the Hall coefficient of the n = 2 and 3 compounds is very similar to the bulk, slowly decreasing as the temperature is decreased, while for the n = 1 compound the Hall coefficient increases dramatically starting at the onset of the charge density wave. The transport properties suggest an abrupt change in electronic properties on increasing the thickness of the VSe2 layer beyond a single layer.

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The synthesis and characterization of turbostratically disordered (BiSe) 1.15 TiSe 2 is reported. Specular and in-plane x-ray diffraction studies indicate an alternating structure containing two planes of a distorted rock salt structured BiSe and a Se-Ti-Se trilayer of TiSe 2 with independent lattices. The title compound was found to be turbostratically (rotationally) disordered about the c-axis, and the BiSe layer displays an orthorhombic in-plane structure with a = 4.562(2) Å and b = 4.242(1) Å. Temperature dependent electrical resistivity reveals that the disordered compound is metallic, but with less temperature dependence than may be expected for a 3D crystal, which is attributed to the lack of coherent vibrations due to the turbostratic disorder. The room temperature resistivity was found to be ρ = 5.0 × 10 −6 m with a carrier concentration of n = 5 × 10 21 cm −3 . Comparing the carrier concentration to (PbSe) 1.16 TiSe 2 suggests that the bismuth is trivalent and donates an electron to the conduction band of the TiSe 2 constituent.

The compounds ([SnSe]1+δ) m (NbSe2)1, where 1 ≤ m ≤ 10, were prepared from a series of designed precursors. The c-axis lattice parameter systematically increases by 0.577(5) nm as the value of m is increased, which indicates that an additional bilayer of rock salt structured SnSe is inserted for each unit of m. The in-plane structure of both constituents systematically changes as the thickness of SnSe increases. Both X-ray diffraction and electron microscopy studies show the presence of turbostratic disorder between the different constituent layers. The electrical resistivity and Hall coefficient increase systematically as a function of m stronger than would be expected for noninteracting metallic NbSe2 and semiconducting SnSe layers, suggesting the presence of charge transfer between the layers. The temperature dependence of the resistivity changes from metallic behavior for m < 4 to weakly increasing, for higher m, as temperature decreases. Compounds with m > 3 show an upturn in the resistivity below 50 K and a corresponding increase in the Hall coefficient, which both become more pronounced as m increases. This suggests localization of carriers, which is expected in two-dimensional crystals. The extent of charge transfer in ([SnSe]1+δ) m (NbSe2)1 can be tuned as a function of SnSe thickness and spans over the same range as reported in the literature for various NbX2 based intercalated and misfit layer compounds.

A new polytype of the misfit layer compound ([SnSe] 1.16) 1 (NbSe 2) 1 with extensive rotational disorder was prepared from designed modulated elemental reactants. This polytype, previously referred to as a ferecrystal due to the extensive rotational disorder, formed over a range of compositions and precursor thicknesses and the resulting c-axis lattice parameters ranged from 1.2210(4) to 1.2360(4) nm. These values bracket the value published for the crystalline misfit compound prepared at high temperature. The a-and b-axis in-plane lattice parameters of both the SnSe and NbSe 2 constituents were incommensurate, which differs from the misfit layered compound formed via high temperature reaction that has a common b-axis lattice parameter for the two constituents. The in-plane area per unit cell of the ferecrystal is 1-2% larger than the compound formed at high temperature. The ferecrystalline ([SnSe] 1.16) 1 (NbSe 2) 1 compound is 1.6 times more conductive than the misfit layer compound. Hall effect measurements indicate that the ferecrystal is a p-type metal and that the higher conductivity is a consequence of higher mobility of carriers in the ferecrystalline compound.

A basic summary of thermoelectric principles is presented in a historical context, following the evolution of the field from initial discovery to modern day high-zT materials. A specific focus is placed on nanocomposite materials as a means to solve the challenges presented by the contradictory material requirements necessary for efficient thermal energy harvest. Misfit layer compounds are highlighted as an example of a highly ordered anisotropic nanocomposite system. Their layered structure provides the opportunity to use multiple constituents for improved thermoelectric performance, through both enhanced phonon scattering at interfaces and through electronic interactions between the constituents. Recently, a class of metastable, turbostratically-disordered misfit layer compounds has been synthesized using a kinetically controlled approach with low reaction temperatures. The kinetically stabilized structures can be prepared with a variety of constituent ratios and layering schemes, providing an avenue to systematically understand structure-function relationships not possible in the thermodynamic compounds. We summarize the work that has been done to date on these materials. The observed turbostratic disorder has been shown to result in extremely low cross plane thermal conductivity and in plane thermal conductivities that are also very small, suggesting the structural motif could be attractive as thermoelectric materials if the power factor could be improved. The first 10 compounds in the [(PbSe)1+δ]m(TiSe2)n family (m, n ≤ 3) are reported as a case study. As n increases, the magnitude of the Seebeck coefficient is significantly increased without a simultaneous decrease in the in-plane electrical conductivity, resulting in an improved thermoelectric power factor.

We show how finite-size scaling of bulk photovoltaic effect-generated electric field in epitaxial ferroelectric insulating BaTiO3(001) films and photo-Hall response involving the bulk photovoltaic current reveal large room-temperature mean free path of photogenerated non-thermalized electrons. Experimental determination of mesoscopic ballistic optically generated carrier transport opens a new paradigm for hot electron-based solar energy conversion, and for facile control of ballistic transport distinct from existing low-dimensional semiconductor interfaces, surfaces, layers or other structures.