Materials Science (cond-mat.mtrl-sci)

Abstract: Twisted heterostructures of two-dimensional crystals can create a moir\'{e} landscape, which can change the properties of it's parent crystals. However, the reproducibility of manual stacking is far from perfect. Here, the alternated stacking of post-transition metal monochalcogenides and transition metal dichalcogenides in misfit layer compound crystals is used as a moir\'{e} generator. Using X-ray diffraction, the presence of twins with a well-defined small twist angle between them is shown. Due to the twist, the surface electrical potential from the induced ferroelectricity is observed using scanning probe microscopy and electron microscopy.

Abstract: Graphene, with its unique band structure, mechanical stability, and high charge mobility, holds great promise for next-generation electronics. Nevertheless, its zero band gap challenges the control of current flow through electrical gating, consequently limiting its practical applications. Recent research indicates that atomic oxygen can oxidize epitaxial graphene in a vacuum without causing unwanted damage. In this study, we have investigated the effects of chemisorbed atomic oxygen on the electronic properties of epitaxial graphene, using scanning tunneling microscopy (STM). Our findings reveal that oxygen atoms effectively modify the electronic states of graphene, resulting in a band gap at its Dirac point. Furthermore, we demonstrate that it is possible to selectively induce desorption or hopping of oxygen atoms with atomic precision by applying appropriate bias sweeps with an STM tip. These results suggest the potential for atomic-scale tailoring of graphene oxide, enabling the development of graphene-based atomic-scale electronic devices.

Abstract: The self-assembly of anisotropic nanocrystals (stabilized by organic capping molecules) with pre-selected composition, size, and shape allows for the creation of nanostructured materials with unique structures and features. For such a material, the shape and packing of the individual nanoparticles play an important role. This work presents a synthesis procedure for {\omega}-thiol-terminated polystyrene (PS-SH) functionalized gold nanooctahedra of variable size (edge length 37, 46, 58, and 72 nm). The impact of polymer chain length (Mw: 11k, 22k, 43k, and 66k g/mol) on the growth of colloidal crystals (e.g. mesocrystals) and their resulting crystal structure is investigated. Small-angle X-ray scattering (SAXS) and scanning transmission electron microscopy (STEM) methods provide a detailed structural examination of the self-assembled faceted mesocrystals based on octahedral gold nanoparticles of different size and surface functionalization. Three-dimensional angular X-ray cross-correlation analysis (AXCCA) enables high-precision determination of the superlattice structure and relative orientation of nanoparticles in mesocrystals. This approach allows us to perform non-destructive characterization of mesocrystalline materials and reveals their structure with resolution down to the nanometer scale.

Abstract: Hydrogen fuel cells offer a clean and sustainable energy conversion solution. The bipolar separator plate, a critical component in fuel cells, plays a vital role in preventing reactant gas cross-contamination and facilitating efficient ion transport in a fuel cell. High chromium ferritic stainless steel with an artificially formed thin chromium oxide passive film has recently gained attention due to its superior electrical conductivity and corrosion resistance, making it a suitable material for separators. In this study, we investigate the microscopic electrical conductivity of the intrinsic passive oxide film on such ferritic stainless steel. Through advanced surface characterization techniques such as current sensing atomic force microscopy and scanning tunneling microscopy/spectroscopy, we discover highly conductive regions within the film that vary depending on location. These findings provide valuable insights into the behavior of the passive oxide film in fuel cells. By understanding the microscopic electrical properties, we can enhance the design and performance of separator materials in hydrogen fuel cells. Ultimately, this research contributes to a broader understanding of separator materials and supports the wider application of hydrogen fuel cells.

Abstract: The sustainable development of next-generation device technology is paramount in the face of climate change and the looming energy crisis. Tremendous efforts have been made in the discovery and design of nanomaterials that achieve device-level sustainability, where high performance and low operational energy cost are prioritized. However, many of such materials are composed of elements that are under threat of depletion and pose elevated risks to the environment. The role of material-level sustainability in computational screening efforts remains an open question thus far. Here we develop a general van der Waals materials screening framework imbued with sustainability-motivated search criteria. Using ultrawide bandgap (UWBG) materials as a backdrop -- an emerging materials class with great prospects in dielectric, power electronics, and ultraviolet device applications, we demonstrate how this screening framework results in 25 sustainable UWBG layered materials comprising only of low-risks elements. Our findings constitute a critical first-step towards reinventing a more sustainable electronics landscape beyond silicon, with the framework established in this work serving as a harbinger of sustainable 2D materials discovery.

Abstract: The Cd1-xZnxTe semiconductor alloy is a regular system regarding its macroscopic mechanic properties in that its experimental bulk modulus exhibits a linear x-dependence, in line with ab initio predictions. Complexity arises at the bond scale, referring to the intricate Cd1-xZnxTe percolation-type Raman pattern [T. Alhaddad et al., Journal of Applied Physics 133, 065701 (2023)]. This offers an appealing benchmark to test various phonon coupling processes at diverse length scales in a compact multi-oscillator assembly, presently tuned by pressure. At x around 0, an inter-bond long-range/macro electric coupling between the matrix and impurity polar phonons is detuned under pressure. Inversely, at x around 1, an intra-bond short-range/nano mechanic coupling is enforced between the two Zn Te apolar sub-phonons stemming from same and alien percolation-type environments. The pressure-induced macro/nano polar/apolar coupling/decoupling processes are compared within a model of two coupled electric/mechanic harmonic oscillators in terms of a compromise between proximity to resonance and strength of coupling, impacting the degree of mode mixing, with ab initio (apolar case) and analytical (polar case) Raman calculations in support. Notably, the free mechanic coupling at x around 1 opposes the achievement of a phonon exceptional point, manifesting the inhibition of mechanic coupling, earlier evidenced with similar bonds for x smaller than 0.5. Hence, the pressure dependence of a given bond vibration in a disordered alloy basically differs depending on whether the bond is matrix-like, i.e., self-connected in bulk (free coupling), or dispersed, i.e., self-connected in a chain (inhibited coupling). This features pressure-tunable percolation-based on-off phonon switches in complex media.

Abstract: The structure-properties relationship of rhamnolipids, RLs, well known microbial bioamphiphiles (biosurfactants), is exlored in detail by coupling cryogenic transmission electron microscopy (cryo-TEM) and both ex situ and in situ small angle X-ray scattering (SAXS). The self-assembly of three RLs with reasoned variation of their molecular structure (RhaC10, RhaC10C10 and RhaRhaC10C10) and a rhamnose-free C10C10 fatty acid is studied in water as a function of pH. It is found that RhaC10 and RhaRhaC10C10 form micelles in a broad pH range and RhaC10C10 undergoes a micelle-to-vesicle transition from basic to acid pH occurring at pH 6.5. Modelling coupled to fitting SAXS data allows a good estimation of the hydrophobic core radius (or length), the hydrophilic shell thickness, the aggregation number and the surface area per RL. The essentially micellar morphology found for RhaC10 and

Abstract: The Cu2ZnSn(S, Se)4 (CZTSSe) emerging inorganic solar cell is highly promising for accelerating the large-scale and low-cost applications of thin-film photovoltaics. It possesses distinct advantages such as abundant and non-toxic constituent elements, high material stability, and excellent compatibility with industrial processes. However, CZTSSe solar cells still face challenges related to complex defects and charge losses. To overcome these limitations and improve the efficiency of CZTSSe solar cells, it is crucial to experimentally identify and mitigate deep defects. In this study, we reveal that the dominant deep defect in CZTSSe materials exhibits donor characteristics. We propose that incomplete cation exchange during the multi-step crystallization reactions of CZTSSe is the kinetics mechanism responsible for the defect formation. To address this issue, we introduce an elemental synergistic alloying approach aimed at weakening the metal-chalcogen bond strength and the stability of intermediate phases. This alloying strategy has facilitated the kinetics of cation exchange, leading to a significant reduction in charge losses within the CZTSSe absorber. As a result, we have achieved a cell efficiency of over 14.5%. These results represent a significant advancement for emerging inorganic solar cells and additionally bring more opportunities for the precise identification and regulation of defects in a wider range of multinary inorganic compounds.

Abstract: Hard X-ray angle-resolved photoemission spectroscopy reveals the momentum-resolved band structure in an epitaxial Mn2Au(001) film capped by a 2 nm thick ferromagnetic Permalloy layer. By magnetizing the Permalloy capping layer, the exceptionally strong exchange bias aligns the Neel vector in the Mn2Au(001) film accordingly. Uncompensated interface Mn magnetic moments in Mn2Au were identified as the origin of the exchange bias using X-ray magnetic circular dichroism in combination with photoelectron emission microscopy. Using time-of-flight momentum microscopy, we measure the asymmetry of the band structure in Mn2Au resulting from the homogeneous orientation of the Neel vector. Comparison with theory shows that the Neel vector, determined by the magnetic moment of the top Mn layer, is antiparallel to the Permalloy magnetization. The experimental results demonstrate that hard X-ray photoemission spectroscopy can measure the band structure of epitaxial layers beneath a metallic capping layer and corroborate the asymmetric band structure in Mn2Au that was previously inferred only indirectly.

Abstract: In this study, we systematically investigated the mechanical response of monolayer molybdenum ditelluride (MoTe2) using molecular dynamics simulations. The tensile behavior of the trigonal prismatic phase (2H phase) MoTe2 under uniaxial strain was simulated in both the armchair and zigzag directions. We also investigated the crack formation and propagation in both armchair and zigzag directions at 10K and 300K to understand the fracture behavior of monolayer MoTe2. The crack simulations show clean cleavage for the armchair direction and the cracks were numerous and scattered in the case of the zigzag direction. Finally, we investigated the effect of temperature on Young's modulus and fracture stress of monolayer MoTe2. The results show that at a strain rate of 10^-4 ps^-1, the fracture strength of 2H-MoTe2 in the armchair and zigzag direction at 10K is 16.33 GPa (11.43 N/m) and 13.71429 GPa (9.46 N/m) under a 24% and 18% fracture strain, respectively. The fracture strength of 2H-MoTe2 in the armchair and zigzag direction at 600K is 10.81 GPa (7.56 N/m) and 10.13 GPa (7.09 N/m) under a 12.5% and 12.47% fracture strain, respectively. Although experimental results on MoTe2 are limited for a wide range of temperatures, we have found that Young's modulus agrees with existing literature for pristine MoTe2. For 2H-MoTe2 in both armchair and zigzag directions, the fracture stresses, fracture strengths, and Young's modulus decrease as the temperature rises, resulting from the increased atomic thermal vibrations.

Abstract: Symmetry plays a key role in determining the physical properties of materials. By Neumann's principle, the properties of a material are invariant under the symmetry operations of the space group to which the material belongs. Continuous phase transitions are associated with a spontaneous reduction in symmetry. (For example, the onset of ferromagnetism spontaneously breaks time reversal symmetry.) Much less common are examples where proximity to a continuous phase transition leads to an increase in symmetry. Here, we find an emergent tetragonal symmetry close to an apparent charge density wave (CDW) bicritical point in a fundamentally orthorhombic material, ErTe$_3$, for which the CDW phase transitions are tuned via anisotropic strain. The underlying structure of the material remains orthorhombic for all applied strains, including at the bicritical point, due to a glide plane symmetry in the crystal structure. Nevertheless, the observation of a divergence in the anisotropy of the in-plane elastoresistivity reveals an emergent electronic tetragonality near the bicritical point.

Abstract: We investigate the effect of surface reconstruction and strain on diffusion of adsorbed Ge atoms on Ge$(111)\textrm{-}5\times5$ and Ge$(111)\textrm{-}7\times7$ surfaces by means of first principles calculations. Stable adsorption sites, their energies, diffusion paths, and corresponding activation barriers are reported. We demonstrate that the decisive migration path is located near the corner holes of surface structures, and they are associated with formation of weak bonds between the adsorbed Ge atom and surface dimers (within the $5\times5$ or $7\times7$ structures). The results show that Ge diffusion rates on $5\times5$ and $7\times7$ reconstructed Ge$(111)$ surfaces should be similar. Conversely, the diffusion barrier on a compressively strained Ge$(111)$ surface is considerably higher than that on a strain-free surface, thus explaining previous experimental results. Comparable diffusion rates on $5\times5$ and $7\times7$ reconstructed surfaces are explained by the identical local atomic arrangements of these structures. The increase of the migration barrier on a strained surface is explained by dimer bond strengthening upon surface compression, along with a weakening of bonds between the adsorbed Ge and dimer atoms.

Abstract: We report the successful synthesis of a new 4$d$ based polycrystalline inverse Heusler alloy Fe$_2$RuGe by an arc melting process and have studied in detail its structural, magnetic and transport properties complemented with first principle calculations. X-ray and neutron diffraction, Extended X-ray Absorption Fine Structure and $^{57}$Fe M\"{o}ssbauer spectroscopic studies confirm the single phase nature of the system where the Fe and Ru atoms are randomly distributed in the 4$c$ and 4$d$ Wyckoff positions in a ratio close to 50:50. The formation of the disordered structure is also confirmed by the theoretical energy minimization calculation. Despite the random cross-site disorder of Fe and Ru atoms, magnetic measurements suggest not only a high Curie temperature of $\sim$860\,K, but also a large saturation magnetic moment $\sim$4.9\,$\mu_B$ per formula unit at 5\,K, considerably exceeding the theoretical limit (4\,$\mu_B$ per formula unit) predicted by the Slater-Pauling rule. Only a few Fe-based inverse Heusler alloys are known to exhibit such high Curie temperatures. Neutron diffraction analysis coupled with the isothermal magnetization value indicates that the magnetic moments in Fe$_2$RuGe are associated with Fe-atoms only, which is also confirmed by M\"ossbauer spectrometry. Interestingly, in comparison to the cubic or hexagonal phase of the parent compound, Fe$_3$Ge, the Curie temperature of Fe$_2$RuGe has increased significantly despite the substitution of the nonmagnetic, yet isoelectronic element Ru in this structurally disordered compound. Our theoretical calculation reveals that the large Fe moment ($\sim2.8\mu_B$/Fe) on the 4$b$ site can be attributed to a charge transfer from this Fe site towards its Ru neighbours. Such a substantial increase in magnetic moment due to electron charge transfer has not previously been reported in a Heusler alloy system.

Abstract: The half-Heusler alloy RuMnGa having valence electron count (VEC) 18 has recently been theoretically proposed to exhibit compensated ferrimagnetic (CFiM) character instead of the expected nonmagnetic ground state. On the other hand, a preliminary experimental study proposed ferromagnetic (FM) ordering. As no half-Heusler system with VEC 18 is known to exhibit magnetic ordering, we have investigated the details of crystal structure and magnetic properties of RuMnGa using a combination of experimental tools, viz., x-ray and neutron diffraction techniques, dc and ac susceptibility, isothermal magnetisation, heat capacity, resistivity and neutron depolarisation measurements. Rietveld refinements of x-ray and neutron diffraction data suggest single phase nature of the compound with elemental composition RuMn$_{0.86}$Ga$_{1.14}$. We have shown that the system exhibits FM-type ordering owing to the inherent presence of this minor off-stoichiometry, showing very low magnetic moment. The system also exhibits reentrant canonical spin-glass behaviour, which is rarely observed in half-Heusler alloys. The temperature coefficient of resistivity changes its sign from negative to positive and further to negative as the temperature decreases.

Abstract: Twisted bilayer (t-BL) transition metal dichalcogenides (TMDCs) attracted considerable attention in recent years due to their distinctive electronic properties, which arise due to the moire superlattices that lead to the emergence of flat bands and correlated electron phenomena. Also, these materials can exhibit interesting thermal properties, including a reduction in thermal conductivity. In this article, we report the thermal conductivity of monolayer (1L) and t-BL MoSe2 at some specific twist angles around two symmetric stacking AB (0 degree) and AB' (60 degree) and one intermediate angle 31 (degree) using the optothermal Raman technique. The observed thermal conductivity values are found to be 13, 23, and 30 W m-1K-1 for twist angle = 58 (degree), 31 (degree) and, 3 (degree) respectively, which is well supported by our first-principles calculation results. The reduction in thermal conductivity in t-BL MoSe2 compared to monolayer (38 W m-1K-1) can be explained by the occurrence of phonon scattering caused by the formation of a moire super-lattice. Herein, the emergence of multiple folded phonon branches and modification in the Brillouin zone caused by in-plane rotation are also accountable for the decrease in thermal conductivity observed in t-BL MoSe2. The theoretical phonon lifetime study and electron localization function (ELF) analysis further reveals the origin of angle-dependent thermal conductivity in t-BL MoSe2. This work paves the way towards tuning the angle-dependent thermal conductivity for any bilayer TMDCs system.