The reaction of ultrathin layers of Mo and Ti with Se was investigated, and significantly different reaction pathways were found. However, in both systems postdeposition annealing results in smooth ...dichalcogenide films with specific thicknesses determined by the precursor. X-ray diffraction (XRD) patterns of as-deposited Mo|Se films around a 1:2 ratio of Mo to Se contain weak, broad reflections from small and isolated MoSe2 crystallites that nucleated during deposition and a sharper intensity maximum resulting from the composition modulation created from the alternating deposition of Mo and Se layers. In contrast, as-deposited Ti|Se films around a 1:2 ratio of Ti to Se contain narrow and intense 00l reflections from TiSe2 crystallites and do not contain a Bragg reflection from the sequence of deposited Ti|Se layers. The as-deposited TiSe2 crystallites have a larger c-axis lattice parameter than was previously reported for TiSe2, however, which suggests a poor vertical interlayer registry and/or high defect densities including interstitial atoms. In-plane XRD patterns show the nucleation of both TiSe2 and Ti2Se during deposition, with the Ti2Se at the substrate. For both systems, annealing the precursors decreases the peak width and increases the intensity of reflections from crystalline TiSe2 and MoSe2. Optimized films consist of a single phase after the annealing and show clear Laue oscillations in the specular XRD patterns, which can only occur if a majority of the diffracting crystallites in the film consist of the same number of unit cells. The highest quality films was obtained when an excess of ∼10% Se was deposited in the precursor, which presumably acts as a flux to facilitate diffusion of metal atoms to crystallite growth fronts and compensates for Se loss to the open system during annealing.
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Previous studies have shown increased expression of stromal markers in synovial tissue (ST) of patients with established rheumatoid arthritis (RA). Here, ST expression of stromal markers in early ...arthritis in relationship to diagnosis and prognostic outcome was studied.
ST from 56 patients included in two different early arthritis cohorts and 7 non-inflammatory controls was analysed using immunofluorescence to detect stromal markers CD55, CD248, fibroblast activation protein (FAP) and podoplanin. Diagnostic classification (gout, psoriatic arthritis, unclassified arthritis (UA), parvovirus associated arthritis, reactive arthritis and RA), disease outcome (resolving vs persistent) and clinical variables were determined at baseline and after follow-up, and related to the expression of stromal markers.
We observed expression of all stromal markers in ST of early arthritis patients, independent of diagnosis or prognostic outcome. Synovial expression of FAP was significantly higher in patients developing early RA compared to other diagnostic groups and non-inflammatory controls. In RA FAP protein was expressed in both lining and sublining layers. Podoplanin expression was higher in all early inflammatory arthritis patients than controls, but did not differentiate diagnostic outcomes. Stromal marker expression was not associated with prognostic outcomes of disease persistence or resolution. There was no association with clinical or sonographic variables.
Stromal cell markers CD55, CD248, FAP and podoplanin are expressed in ST in the earliest stage of arthritis. Baseline expression of FAP is higher in early synovitis patients who fulfil classification criteria for RA over time. These results suggest that significant fibroblast activation occurs in RA in the early window of disease.
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We report cross-plane thermoelectric measurements of SnSe and SnSe2 films grown by the modulated element reactant (MER) approach. These materials exhibit ultralow cross-plane thermal conductivities, ...which are advantageous for thermoelectric energy conversion. The initially grown SnSe films have relatively low cross-plane Seebeck coefficients (−38.6 μV/K) due to significant unintentional doping originating from Se vacancies when annealed in nitrogen, as a result of the relatively high vapor pressure of Se. By performing postgrowth annealing at a fixed Se partial pressure (300 °C for 30 min using SnSe2 as the Se source in a sealed tube), a transition from SnSe to SnSe2 is induced, which is evidenced by clear changes in the X-ray diffraction patterns of the films. This results in a 16-fold increase in the cross-plane Seebeck coefficient (from −38.6 to −631 μV/K) after Se annealing due to both the SnSe-to-SnSe2 transition and the mitigation of unintentional doping by Se vacancies. We also observe a corresponding 6-fold drop in the electrical conductivity (from 3 to 0.5 S/m) after Se annealing, which is consistent with both a drop in the carrier concentration and an increase in band gap. The power factor S 2σ increased by 44× (from 4.5 nW/m·K2 to 0.2 μW/m·K2) after Se annealing. We believe that these results demonstrate a robust method for mitigating unintentional doping in a promising class of materials for thermoelectric applications.
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Heterostructures unconstrained by epitaxy have generated considerable excitement due to the discovery of emergent properties-properties not found in either constituent. Heterostructures enable the ...surfaces on either side of two-dimensional (2D) layers to be used to systematically investigate phenomena such as superconductivity and magnetism in the 2D limit. The ability to choose constituents facilitates the prediction of emergent properties created by the unusual coordination environments at incommensurate interfaces. There have already been many reviews on heterostructures, focusing on a variety of topics that reflect the diverse interest in this area as well as the potential for new technologies. Hence this review focuses mainly on the synthesis and structural characterization of heterostructures containing transition metal dichalcogenides (TMD). This review only briefly discusses 2D materials and TMD/TMD heterostructure devices and the performances that have been achieved. This review provides a historical context for the rapid development of this field and discusses proposed mechanisms for emergent properties. Up to now, the materials used in heterostructures have mainly been materials with 2D structures, as these compounds can be easily cleaved into ultrathin layers. This review discusses the expansion of heterostructure constituents to include materials that do not have 2D structures. Structural changes and charge redistribution between adjacent (or even more distant) layers are likely to be larger for 3D constituents than with 2D constituents based on known misfit layer compounds. Systematic changes in properties with layer thickness, layer sequences, and the identity of constituents will increase our understanding of emergent properties and how they can be optimized.
The compound (Pb2MnSe3)0.6VSe2 was predicted to be kinetically stable based on density functional theory (DFT) calculations on an island of Pb2MnSe3 between layers of VSe2. This approach provides a ...high degree of freedom by not forcing interlayer lattice match, making it ideal to investigate the likelihood of formation of new incommensurate layer misfit structures. The free space around the island is critical, as it allows atoms to diffuse and hence exploring the local energy landscape around the initial configuration. (Pb2MnSe3)0.6VSe2 was synthesized via a near diffusionless reaction from precursors where a repeating sequence of elemental layers matches the local composition and layer sequence of the predicted compound. The VSe2 layer consists of a Se–V–Se trilayer with octahedral coordination of the V atoms. The Pb2MnSe3 layer consists of three rock-salt-like planes, with a MnSe layer between the planes of PbSe. The center MnSe plane stabilizes the puckering of the outer PbSe layers. Electrical properties indicate that (Pb2Mn1Se3)0.6VSe2 undergoes a charge density wave transition at ∼100 K and orders ferromagnetically at 35 K. The combination of theory and experiment enables a faster convergence to new heterostructures than either approach in isolation.
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The composition and thickness of thin films determine their physical properties, making the ability to measure the number of atoms of different elements in films both technologically and ...scientifically important. For thin films, below a certain thickness, the X-ray fluorescence intensity of an element is proportional to the number of atoms. Converting this intensity to the number of atoms per unit area is challenging due to experimental geometries and other correction factors. Hence, the ratio of intensities is more commonly used to determine the composition in terms of element ratios using standards or a model. Here, the number of atoms per unit area was determined using X-ray structure information for over 20 different crystallographically aligned samples with integral unit cell thicknesses. The proportionality constant between intensity and the number of atoms per unit area was determined from linear fits of the background subtracted X-ray fluorescence intensity plotted versus the calculated number of atoms per unit area for each element. The results demonstrate that X-ray fluorescence is very sensitive, capable of measuring changes in the number of atoms of less than 1% of a monolayer for some elements in a variety of sample matrices. Using the calibrated values, an 8 unit cell thick MoSe2 was grown and characterized, demonstrating the usefulness of the ablity to quantify the number of atoms per unit area in a film.
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Spurred by recent discoveries of high-temperature superconductivity in Fe–Se-based materials, the magnetic, electronic, and catalytic properties of iron chalcogenides have drawn significant ...attention. However, much remains to be understood about the sequence of phase formation in these systems. Here, we shed light on this issue by preparing a series of binary Fe–Se ultrathin diffusion couples via designed thin-film precursors and investigating their structural evolution as a function of composition and annealing temperature. Two previously unreported Fe–Se phases crystallized during the deposition process on a nominally room-temperature Si substrate in the 27–33 and 37–47% Fe (atomic percent) composition regimes. Both phases completely decompose after annealing to 200 °C in a nitrogen glovebox. At higher temperatures, the sequence of phase formation is governed by Se loss in the annealing process, consistent with what would be expected from the phase diagram. Films rich in Fe (53–59% Fe) crystalized during deposition as β-FeSe (P4/nmm) with preferred c-axis orientation to the amorphous SiO2 substrate surface, providing a means to nonepitaxial self-assembly of crystallographically aligned, iron-rich β-FeSe for future research. Our findings suggest that the crystallization of binary Fe–Se compounds at room temperature via near diffusionless transformations should be a significant consideration in future attempts to prepare metastable ternary and higher-order compounds containing Fe and Se.
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We explore the effect of charge density wave (CDW) on the in-plane thermoelectric transport properties of (PbSe)1+δ(VSe2)1 and (PbSe)1+δ(VSe2)2 heterostructures. In (PbSe)1+δ(VSe2)1 we observe an ...abrupt 86% increase in the Seebeck coefficient, 245% increase in the power factor, and a slight decrease in resistivity over the CDW transition. This behavior is not observed in (PbSe)1+δ(VSe2)2 and is rather unusual compared to the general trend observed in other materials. The abrupt transition causes a deviation from the Mott relationship through correlated electron states. Raman spectra of the (PbSe)1+δ(VSe2)1 material show the emergence of additional peaks below the CDW transition temperature associated with VSe2 material. Temperature-dependent in-plane X-ray diffraction (XRD) spectra show a change in the in-plane thermal expansion of VSe2 in (PbSe)1+δ(VSe2)1 due to lattice distortion. The increase in the power factor and decrease in the resistivity due to CDW suggest a potential mechanism for enhancing the thermoelectric performance at the low temperature region.
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This work presents the preparation of a series of (PbSe)1+δ4TiSe24 isomers via a low temperature synthesis approach that exploits precursor nanoarchitecture to direct formation of specific isomers. ...The targeted isomers formed even when the precursors did not have the correct amount of each element to make a unit cell from each repeating sequence of elemental layers deposited. This suggests that the exact composition of the precursors is less important than the nanoarchitecture in directing the formation of the compounds. The as-deposited diffraction data show that the isomers begin to form during the deposition, and Ti2Se, in addition to PbSe and TiSe2, are present in the specular diffraction patterns. HAADF-STEM images reveal impurity layers above and below an integer number of targeted isomer unit cells. The structural data suggest that Ti2Se forms as Se is deposited on the initial Ti layers and remains throughout isomer self-assembly. During growth, the isomers deplete the local supply of Ti and Pb, creating diffusion gradients that drive additional cations toward the growth front, which leaves surface impurity layers of TiSe2 and TiO2 after the supply of Pb is exhausted. The deposited stacking sequences direct formation of the targeted isomers, but fewer repeating units form than intended due to the lack of material per layer in the precursor and formation of impurity layers. All isomers have negative Hall and Seebeck coefficients, indicating that electrons are the majority carrier. The carrier concentration and conductivity of the isomers increase with the number of interfaces in the unit cell, resulting from charge donation between adjacent layers. The opposite variation of the carrier concentration and mobility with temperature result in minima in the resistivity between 50 and 100 K. The very weak temperature dependence of the carrier concentration likely results from changes in the amount of charge transfer between the layers with temperature.
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