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Solid-state reaction kinetics on atomic length scales have not been heavily investigated due to the long times, high reaction temperatures, and small reaction volumes at interfaces in solid-state reactions. All of these conditions present significant analytical challenges in following reaction pathways. Herein we use in situ and ex situ X-ray diffraction, in situ X-ray reflectivity, high-angle annular dark field scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy to investigate the mechanistic pathways for the formation of a layered (Pb0.5Sn0.5Se)1+δ(TiSe2)m heterostructure, where m is the varying number of TiSe2 layers in the repeating structure. Thin film precursors were vapor deposited as elemental-modulated layers into an artificial superlattice with Pb and Sn in independent layers, creating a repeating unit with twice the size of the final structure. At low temperatures, the precursor undergoes only a crystallization event to form an intermediate (SnSe2)1+γ(TiSe2)m(PbS...

Preparing homologous series of compounds allows chemists to rapidly discover new compounds with predictable structure and properties. Synthesizing compounds within such a series involves navigating a free energy landscape defined by the interactions within and between constituent atoms. Historically, synthesis approaches are typically limited to forming only the most thermodynamically stable compound under the reaction conditions. Presented here is the synthesis, via self-assembly of designed precursors, of isocompositional incommensurate layered compounds [(BiSe)1+δ] m[TiSe2] m with m = 1, 2, and 3. The structure of the BiSe bilayer in the m = 1 compound is not that of the binary compound, and this is the first example of compounds where a BiSe layer thicker than a bilayer in heterostructures has been prepared. Specular and in-plane X-ray diffraction combined with high-resolution electron microscopy data was used to follow the formation of the compounds during low-temperature annealing and the subsequent decomposition of the m = 2 and 3 compounds into [(BiSe)1+δ]1[TiSe2]1 at elevated temperatures. These results show that the structure of the precursor can be used to control reaction kinetics, enabling the synthesis of kinetically stable compounds that are not accessible via traditional techniques. The data collected as a function of temperature and time enabled us to schematically construct the topology of the free energy landscape about the local free energy minima for each of the products.

Single- and few-layer metal chalcogenide compounds are of significant interest due to structural changes and emergent electronic properties on reducing dimensionality from three to two dimensions. To explore dimensionality effects in SnSe, a series of [(SnSe)1+δ]mTiSe2 intergrowth structures with increasing SnSe layer thickness (m = 1-4) were prepared from designed thin-film precursors. In-plane diffraction patterns indicated that significant structural changes occurred in the basal plane of the SnSe constituent as m is increased. Scanning transmission electron microscopy cross sectional images of the m = 1 compound indicate long-range coherence between layers whereas the m ≧ 2 compounds show extensive rotational disorder between the constituent layers. For m ≧ 2, the images of the SnSe constituent contain a variety of stacking sequences of SnSe bilayers. Density functional theory calculations suggest that the formation energy is similar for several different SnSe stacking sequences. The compounds show un...

The discovery of emergent phenomena in two-dimensional (2D) materials has sparked substantial research efforts in the materials community. A significant experimental challenge for this field is exerting atomistic control over the structure and composition of the constituent 2D layers and understanding how the interactions between layers drives both structure and properties. Segregation of Pb to the surface of three bilayer thick PbSe-SnSe alloy layers was discovered within [(PbxSn1-xSe)1+δ]n(TiSe2)1 heterostructures using electron microscopy. We demonstrate that this segregation is thermodynamically favored to occur when PbxSn1-xSe layers are interdigitated with TiSe2 monolayers. Density-functional theory (DFT) calculations indicate that the observed segregation depends on what is adjacent to the PbxSn1-xSe layers. The interplay between interface and volume free energies controls both the structure and composition of the constituent layers, which can be tuned using layer thickness.

Self-assembly of designed precursors has enabled the synthesis of novel heterostructures that exhibit extensive rotational disorder between constituents. In (SnSe)1.2TiSe2 nanoscale regions of long-range order were observed in scanning transmission electron microscopy (STEM) cross sectional images. Here a combination of techniques are used to determine the structure of this compound, and the information is used to infer the origin of the order. In-plane X-ray diffraction indicates that the SnSe basal plane distorts to match TiSe2. This results in a rectangular unit cell that deviates from both the bulk structure and the square in-plane unit cell previously observed in heterostructures containing SnSe bilayers separated by layers of dichalcogenides. The distortion results from lattice matching of the two constituents, which occurs along the SnSe and the TiSe2 directions as √3 × aTiSe2 equals aSnSe. Fast Fourier transform analysis of the STEM images exhibits sharp maxima in hkl families where h,...

Controlling carrier concentration is critical in many device applications, and both chemical substitution and modulation doping have been used in industry. For most inorganic materials, very low doping efficiencies are observed as site occupancies depend on both thermodynamic and kinetic factors. We demonstrate that we can make kinetically controlled site-specific substitutions in a series of (BixSn1–xSe)1+δTiSe2 compounds using the modulated elemental reactants method. These compounds were characterized using a combination of X-ray diffraction, resistivity and Hall coefficient measurements, and high angle annular dark field scanning transmission electron microscopy (HAADF STEM). For small x, the doping efficiency is 0.7, close to that observed for B in silicon. For higher x values, a structural distortion is observed in X-ray diffraction data in which the symmetry of the in-plane unit cell decreases. HAADF STEM data reveals the presence of antiphase boundaries (Bi–Bi pairs) in the BixSn1–xSe layers, whic...

Solid-state reaction kinetics on atomic length scales have not been heavily investigated due to the long times, high reaction temperatures, and small reaction volumes at interfaces in solid-state reactions. All of these conditions present significant analytical challenges in following reaction pathways. Herein we use in situ and ex situ X-ray diffraction, in situ X-ray reflectivity, high-angle annular dark field scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy to investigate the mechanistic pathways for the formation of a layered (Pb

The role of interfacial nonidealities and disorder on thermal transport across interfaces is traditionally assumed to add resistance to heat transfer, decreasing the thermal boundary conductance (TBC). However, recent computational studies have suggested that interfacial defects can enhance this thermal boundary conductance through the emergence of unique vibrational modes intrinsic to the material interface and defect atoms, a finding that contradicts traditional theory and conventional understanding. By manipulating the local heat flux of atomic vibrations that comprise these interfacial modes, in principle, the TBC can be increased. In this work, experimental evidence is provided that interfacial defects can enhance the TBC across interfaces through the emergence of unique high-frequency vibrational modes that arise from atomic mass defects at the interface with relatively small masses. Ultrahigh TBC is demonstrated at amorphous SiOC:H/SiC:H interfaces, approaching 1 GW m-2 K-1 and are further increased through the introduction of nitrogen defects. The fact that disordered interfaces can exhibit such high conductances, which can be further increased with additional defects, offers a unique direction to manipulate heat transfer across materials with high densities of interfaces by controlling and enhancing interfacial thermal transport.

A series of (BiSe)1+δ(TiSe2)n compounds where n was varied from two to four were synthesized and electrically characterized to explore the extent of charge transfer from the BiSe layer to the TiSe2 layers. These kinetically stable heterostructures were prepared using the modulated elemental reactants (MER) method, in which thin amorphous elemental layers are deposited in an order that mimics the nanostructure of the desired product. X-ray diffraction (XRD), X-ray area diffraction, and scanning transmission electron microscopy (STEM) data show that the precursors formed the desired products. Specular diffraction scans contain only 00l reflections, indicating that the compounds are crystallographically aligned with the c-axis perpendicular to the substrate. The c-axis lattice parameter increases by 0.604(3) nm with each additional TiSe2 layer. In-plane diffraction scans contain reflections that can be indexed as the (hk0) of the BiSe and TiSe2 constituents. Area diffraction scans are also consistent with th...

Targeted substitutions in extended solids have been historically challenging, limited by high temperature and the synthetic routes traditionally used. Here, we report the synthesis of new compounds in the (PbxSn1–xSe)1+δTiSe2 intergrowth family from designed amorphous precursors. By controlling local composition and using low reaction temperatures, the metastable quaternary compounds can be synthesized over the entire range of 0 ≤ x ≤ 1 as crystallographically aligned thin films. X-ray diffraction and electron microscopy confirm the formation of a solid solution in the PbxSn1–xSe layer, with the overall and constituent structure both changing as a function of composition as predicted by Vegard’s law. Charge transfer between constituents and subsequent conduction in the TiSe2 describes the observed transport properties. The mobility of the charge carriers is increased in compounds with the alloyed PbxSn1–xSe layer, providing direct evidence that charge transport occurs predominantly in the dichalcogenide l...

This work provides a review on the in-plane structure of a recently established subgroup of misfit layer compounds, namely ferecrystals. While misfit layer compounds can be described as layered intergrowths of two distinct substructures in which only one axis of the subunits remains incommensurate, for ferecrystals both constituents retain independent in-plane crystalline structures. This is accompanied by extensive rotational disorder, a key feature of ferecrystals. Our comparison of the in-plane structures of misfit layer compounds and ferecrystals suggests that the weaker registration between the subunits in ferecrystals allows the synthesis of a wider variety of compounds, varying both the range of constituents, their mismatch and their thicknesses. The in-plane structures of the individual constituents in ferecrystalline compounds exhibit interesting features such as 2D-symmetry, size induced structural transformation, misfit parameters that depend on the component thicknesses, and pairing distortions of constituent layers.

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.

Preparing homologous series of compounds allows chemists to rapidly discover new compounds with predictable structure and properties. Synthesizing compounds within such a series involves navigating a free energy landscape defined by the interactions within and between constituent atoms. Historically, synthesis approaches are typically limited to forming only the most thermodynamically stable compound under the reaction conditions. Presented here is the synthesis, via self-assembly of designed precursors, of isocompositional incommensurate layered compounds [(BiSe)

Single- and few-layer metal chalcogenide compounds are of significant interest due to structural changes and emergent electronic properties on reducing dimensionality from three to two dimensions. To explore dimensionality effects in SnSe, a series of [(SnSe)

Synthesis and electrical properties of kinetically stabilized (PbSe)1+δ(TiSe2)n thin-film intergrowths are reported for 1 ≤ n ≤ 18. A linear increase in the c-lattice parameter of the intergrowth is observed as n is increased and the slope is consistent with the inclusion of an additional TiSe2 structural unit as n is incremented by 1 and the observed intercept is consistent with the expected thickness of a PbSe bilayer. The charge donated to the TiSe2 constituent from the PbSe is diluted across more layers as n is increased, leading to a systematic increase in the Seebeck coefficient. The room temperature resistivity values of the reported compounds are all on the order of 10−5 Ω m and depend on defect densities that affect the mobility, making the magnitude of the resistivity less sensitive to n. The temperature dependence is metallic for large n, with a slight upturn at low temperatures due to localization of carriers for small n values. The power factor increases with n, including the highest reported for chalcogenide misfit layered and related compounds, showing that nanostructuring and modulation doping are an effective means of tuning the power factor of thermoelectric intergrowth materials. Since these compounds have very low thermal conductivity due to structural anisotropy and misregistration between intergrowth constituents, this suggests that varying their nanoarchitecture is a promising approach to obtain high values of zT.

Self-assembly of designed precursors has enabled the synthesis of novel heterostructures that exhibit extensive rotational disorder between constituents. In (SnSe)

(SnSe)1.2TiSe2 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 TiX2 containing misfit layered compounds to date, suggesting potential for low-temperature thermoelectric applications. Electrical characterization suggests that electrons transferred from SnSe to TiSe2 are responsible for the higher carrier concentration observed relative to bulk TiSe2. 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.

Targeted heterostructures containing intergrown two dimensional (2D) layers of 3 different constituent layers, SnSe2, PbSe and TiSe2, were prepared by controlling the composition and sequence of elemental bilayers within a designed precursor. Varying the structure of the precursor enabled the number of structural units of each constituent and the sequence of crystalline 2D layers to be precisely controlled. The stacking of the 2D layers, their structures, and the segregation of the elements between them were determined using X-ray diffraction and electron microscopy techniques, with the observed sequence of the 2D layers consistent with the targeted intergrowth. This ability to prepare targeted heterostructures is critical, since the number of possible configurations in the final compound increases rapidly as the number of constituents increases, from almost 60 000 with two constituents to over 130 million with three constituents and to over 35 billion with four constituents for 20 or fewer distinct layers in the unit cell. This general route for synthesizing specific multiple component heterostructures will accelerate the feedback loop in this growing research area, permitting theorists to assume specific structures in the search for enhanced properties and providing experimentalists with crystallographically aligned samples to test these predictions.

A variety of metal oxide films (InGaOx, AlOx, “HafSOx”) prepared from aqueous solutions were found to have non-uniform electron density profiles using X-ray reflectivity. The inhomogeneity in HafSOx films (Hf(OH)4–2x−2y(O2)x(SO4)y·zH2O), which are currently under investigation as inorganic resists, were studied in more detail by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and medium-energy ion scattering (MEIS). The HAADF-STEM images show a greater concentration of heavy atoms near the surface of a single-layer film. MEIS data confirm the aggregation of Hf at the film surface. The denser “crust” layer in HafSOx films may directly impact patterning resolution. More generally, the phenomenon of surface-layer inhomogeneity in solution-deposited films likely influences film properties and may have consequences in other thin-film systems under investigation as resists, dielectrics, and thin-film transistor components.

Thin films of the new title intergrowth compound consisting of a bilayer of SnSe and TiSe2 trilayer are prepared by self-assembly from a precursor containing modulated layers of Sn-Se and Ti-Se, which is synthesized by deposition of elemental layers (annealing at 350 °C).

To enable the continued scaling of integrated circuits, the semiconductor industry faces ongoing struggles to implement better low-dielectric-constant (low-k) materials within the interconnect system. One of the biggest challenges to integrating new dielectrics is overcoming the low-k death curve—that is, the fatal falloff in mechanical properties associated with the low material densities required to achieve low k values. It is shown that amorphous hydrogenated boron carbide (a-BC:H) films exhibit Young's modulus (E) values between two and ten times greater than those of state-of-the-art Si-based dielectric materials across a wide range of k values. In particular, optimized a-BC:H films with moderate k values in the range of 3–4, in addition to possessing outstanding stiffness (E ≈ 100–150 GPa), simultaneously exhibit excellent electrical properties (leakage current of 5 MV cm–1). Films in this range also demonstrate resistance to Cu diffusion to at least 600 °C, as well as chemical stability and etch properties suitable for low-k diffusion barrier/etch stop applications.

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.