Matthias Falmbigl

Suppressing a charge density wave by changing dimensionality in the ferecrystalline compounds ([SnSe]1.15)1(VSe2)n with n = 1, 2, 3, 4.

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.

Misfit layer compounds and ferecrystals: Model systems for thermoelectric nanocomposites

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.

Synthesis and characterization of turbostratically disordered (BiSe)1.15TiSe2

The synthesis and characterization of turbostratically disordered (BiSe)1.15TiSe2 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 TiSe2 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) A and b = 4.242(1) A. 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 Ωm with a carrier concentration of n = 5 × 1021 cm−3. Comparing the carrier concentration to (PbSe)1.16TiSe2 suggests that the bismuth is trivalent and donates an electron to the conduction band of the TiSe2 constituent.

Influence of defects on the charge density wave of ([SnSe]1+δ)1(VSe2)1 ferecrystals

A series of ferecrystalline compounds ([SnSe]1+δ)1(VSe2)1 with varying Sn/V ratios were synthesized using the modulated elemental reactant technique. Temperature-dependent specific heat data reveal a phase transition at 102 K, where the heat capacity changes abruptly. An abrupt increase in electrical resistivity occurs at the same temperature, correlated with an abrupt increase in the Hall coefficient. Combined with the magnitude and nature of the specific heat discontinuity, this suggests that the transition is similar to the charge density wave transitions in transition metal dichalcogenides. An ordered intergrowth was formed over a surprisingly wide compositional range of Sn/V ratios of 0.89 ≤ 1 + δ ≤ 1.37. X-ray diffraction and transmission electron microscopy reveal the formation of various volume defects in the compounds in response to the nonstoichiometry. The electrical resistivity and Hall coefficient data of samples with different Sn/V ratios show systematic variation in the carrier concentration with the Sn/V ratio. There is no significant change in the onset temperature of the charge density wave transition, only a variation in the carrier densities before and after the transition. Given the sensitivity of the charge density wave transitions of transition metal dichalcogenides to variations in composition, it is very surprising that the charge density wave transition observed at 102 K for ([SnSe]1.15)1(VSe2)1 is barely influenced by the nonstoichiometry and structural defects. This might be a consequence of the two-dimensional nature of the structurally independent VSe2 layers.

Designed Synthesis of van der Waals Heterostructures: The Power of Kinetic Control.

Selecting specific 2D building blocks and specific layering sequences of van der Waals heterostructures should allow the formation of new materials with designed properties for specific applications. Unfortunately, the synthetic ability to prepare such structures at will, especially in a manner that can be manufactured, does not exist. Herein, we report the targeted synthesis of new metal-semiconductor heterostructures using the modulated elemental-reactant technique to nucleate specific 2D building blocks, control their thickness, and avoid epitaxial structures with long-range order. The building blocks, VSe2 and GeSe2 , have different crystal structures, which inhibits cation intermixing. The precise control of this approach enabled us to synthesize heterostructures containing GeSe2 monolayers alternating with VSe2 structural units with specific sequences. The transport properties systematically change with nanoarchitecture and a charge-density wave-like transition is observed.

Structure, Stability, and Properties of the Intergrowth Compounds ([SnSe]1+δ)m(NbSe2)n, where m = n = 1–20

Intergrowth compounds of ([SnSe]1+δ)m(NbSe2)n, where 1 ≤ m = n ≤ 20, with the same atomic composition but different c-axis lattice parameters and number of interfaces per volume were synthesized using the modulated elemental reactant technique. A c-axis lattice parameter change of 1.217(6) nm as a function of one unit of m = n was observed. In-plane X-ray diffraction shows an increase in distortion of the rock salt layer as a function of m and a broadening of the NbSe2 reflections as n increases, indicating the presence of different coordination environments for Nb (trigonal prismatic and octahedral) and smaller crystallite size, which were confirmed via scanning transmission electron microscopy investigations. The electrical resistivities of all 12 compounds exhibit metallic temperature dependence and are similar in magnitude as would be expected for isocompositional compounds. Carrier concentration and mobility of the compounds vary within a narrow range of 2-6 × 10(21) cm(-3) and 2-6 cm(2) V(-1) s(-1), respectively. Even at a thickness of 12 nm for the SnSe and NbSe2 blocks, the properties of the intergrowth compounds cannot be explained as composite behavior, due to significant charge transfer between them. Upon being annealed at 500 °C, the higher order m = n compounds were found to convert to the thermodynamically stable phase, the (1,1) compound. This suggests that the capacitive energy of the interfaces stabilizes these intergrowth compounds.

Modifying a charge density wave transition by modulation doping: ferecrystalline compounds ([Sn1−xBixSe]1.15)1(VSe2)1 with 0 ≤ x ≤ 0.66

A series of alloyed ferecrystals ([Sn1−xBixSe]1.15)1(VSe2)1 with 0 ≤ x ≤ 0.66 was synthesized via the modulated elemental reactants technique. X-ray diffraction of the compounds reveals systematic changes of the lattice parameter and the intensities of the Bragg peaks confirming the successful alloying of the compounds corroborated by Rietveld refinements. Interestingly, both constituents of the intergrowth compounds exhibit systematic structural changes as a function of the Bi-content indicating interlayer interaction. The a-axis lattice parameter of the VSe2 layer expands with increasing Bi-content, which signifies changes in the electronic structure of this constituent. Electrical resistivities, Hall and Seebeck coefficients of compounds with a varying Bi-content present a complex scenario. At low Bi-contents an enhancement of the charge density wave transition is observed, whereas further substitution results in a suppression of the effect. At Bi-contents exceeding x = 0.55 minority carriers from the Sn1−xBixSe layer contribute to the transport properties.

The Influence of Interfaces on Properties of Thin-Film Inorganic Structural Isomers Containing SnSe–NbSe2 Subunits

Inorganic isomers ([SnSe]1+δ)m(NbSe2)n([SnSe]1+δ)p(NbSe2)q([SnSe]1+δ)r(NbSe2)s where m, n, p, q, r, and s are integers and m + p + r = n + q + s = 4 were prepared using the modulated elemental reactant technique. This series of all six possible isomers provides an opportunity to study the influence of interface density on properties while maintaining the same unit cell size and composition. As expected, all six compounds were observed to have the same atomic compositions and an almost constant c-axis lattice parameter of ≈4.90(5) nm, with a slight trend in the c-axis lattice parameter correlated with the different number of interfaces in the isomers: two, four and six. The structures of the constituents in the ab-plane were independent of one another, confirming the nonepitaxial relationship between them. The temperature dependent electrical resistivities revealed metallic behavior for all the six compounds. Surprisingly, the electrical resistivity at room temperature decreases with increasing number of interfaces. Hall measurements suggest this results from changes in carrier concentration, which increases with increasing thickness of the thickest SnSe block in the isomer. Carrier mobility scales with the thickness of the thickest NbSe2 block due to increased interfacial scattering as the NbSe2 blocks become thinner. The observed behavior suggests that the two constituents serve different purposes with respect to electrical transport. SnSe acts as a charge donor and NbSe2 acts as the charge transport layer. This separation of function suggests that such heterostructures can be designed to optimize performance through choice of constituent, layer thickness, and layer sequence. A simplistic model, which predicts the properties of the complex isomers from a weighted sum of the properties of building blocks, was developed. A theoretical model is needed to predict the optimal compound for specific properties among the many potential compounds that can be prepared.

Synthesis, structure, and thermal conductivity of [(SnSe)1 + y]n[MoSe2]n compounds

A series of semiconducting [(SnSe)1.05]n[MoSe2]n compounds where n = 1–4 were prepared from thin film precursors with designed local compositions and nanoarchitectures to promote formation of the desired products during low temperature annealing. Specular diffraction patterns of annealed precursors contain only 00l reflections that yield c-lattice parameters indicating the formation of layered intergrowths. The in-plane diffraction patterns contain the independent reflections from the two constituents and the in-plane lattice parameters are independent of n. Electron microscopy images suggest significant turbostratic disorder between the constituent layers and between Se–Mo–Se trilayers within the dichalcogenide constituent. The room temperature cross-plane thermal conductivity was found to be low, between 0.08 and 0.22 W m−1 K−1 for the series of isocompositional compounds investigated, and is independent of the density of interfaces.

Superconducting ferecrystals: turbostratically disordered atomic-scale layered (PbSe)1.14(NbSe2)n thin films.

Hybrid electronic heterostructure films of semi- and superconducting layers possess very different properties from their bulk counterparts. Here, we demonstrate superconductivity in ferecrystals: turbostratically disordered atomic-scale layered structures of single-, bi- and trilayers of NbSe2 separated by PbSe layers. The turbostratic (orientation) disorder between individual layers does not destroy superconductivity. Our method of fabricating artificial sequences of atomic-scale 2D layers, structurally independent of their neighbours in the growth direction, opens up new possibilities of stacking arbitrary numbers of hybrid layers which are not available otherwise, because epitaxial strain is avoided. The observation of superconductivity and systematic Tc changes with nanostructure make this synthesis approach of particular interest for realizing hybrid systems in the search of 2D superconductivity and the design of novel electronic heterostructures.