Influence of magnetic field on electron beam-induced Coulomb explosion of gold microparticles in transmission electron microscopy.

In this work we instigated the fragmentation of Au microparticles supported on a thin amorphous carbon film by irradiating them with a gradually convergent electron beam inside the Transmission Electron Microscope. This phenomenon has been generically labeled as "electron beam-induced fragmentation" or EBIF and its physical origin remains contested. On the one hand, EBIF has been primarily characterized as a consequence of beam-induced heating. On the other, EBIF has been attributed to beam-induced charging eventually leading to Coulomb explosion. To test the feasibility of the charging framework for EBIF, we instigated the fragmentation of Au particles under two different experimental conditions. First, with the magnetic objective lens of the microscope operating at full capacity, i.e. background magnetic field B=2 T, and with the magnetic objective lens switched off (Lorenz mode), i.e. B=0 T. We observe that the presence or absence of the magnetic field noticeably affects the critical current density at which EBIF occurs. This strongly suggests that magnetic field effects play a crucial role in instigating EBIF on the microparticles. The dependence of the value of the critical current density on the absence or presence of an ambient magnetic field cannot be accounted for by the beam-induced heating model. Consequently, this work presents robust experimental evidence suggesting that Coulomb explosion driven by electrostatic charging is the root cause of EBIF.

Evolution of the pentacene exciton band width in pentacene-tetracene blends.

Pentacene is one of the most investigated organic semiconductors. It is well known that the motion of excitons in pentacene and other organic semiconductors is determined by inter-molecular exciton coupling based on charge-transfer processes. In the present study, we demonstrate the impact of the admixture of tetracene, which has a larger band gap and interrupts the pentacene-pentacene interaction, on the exciton behavior in pentacene. Using a combination of optical absorption and electron energy-loss spectroscopy, we show that both the Davydov splitting and the exciton band width in pentacene strongly decrease with increasing tetracene concentration, while the decrease of the exciton band width is substantially larger.

Covalency versus magnetic axiality in Nd molecular magnets: Nd-photoluminescence, strong ligand-field, and unprecedented nephelauxetic effect in fullerenes NdM2N@C80 (M = Sc, Lu, Y).

Nd-based nitride clusterfullerenes NdM2N@C80 with rare-earth metals of different sizes (M = Sc, Y, Lu) were synthesized to elucidate the influence of the cluster composition, shape and internal strain on the structural and magnetic properties. Single crystal X-ray diffraction revealed a very short Nd-N bond length in NdSc2N@C80. For Lu and Y analogs, the further shortening of the Nd-N bond and pyramidalization of the NdM2N cluster are predicted by DFT calculations as a result of the increased cluster size and a strain caused by the limited size of the fullerene cage. The short distance between Nd and nitride ions leads to a very large ligand-field splitting of Nd3+ of 1100-1200 cm-1, while the variation of the NdM2N cluster composition and concomitant internal strain results in the noticeable modulation of the splitting, which could be directly assessed from the well-resolved fine structure in the Nd-based photoluminescence spectra of NdM2N@C80 clusterfullerenes. Photoluminescence measurements also revealed an unprecedentedly strong nephelauxetic effect, pointing to a high degree of covalency. The latter appears detrimental to the magnetic axiality despite the strong ligand field. As a result, the ground magnetic state has considerable transversal components of the pseudospin g-tensor, and the slow magnetic relaxation of NdSc2N@C80 could be observed by AC magnetometry only in the presence of a magnetic field. A combination of the well-resolved magneto-optical states and slow relaxation of magnetization suggests that Nd clusterfullerenes can be useful building blocks for magneto-photonic quantum technologies.

Evidence of superconducting Fermi arcs.

An essential ingredient for the production of Majorana fermions for use in quantum computing is topological superconductivity1,2. As bulk topological superconductors remain elusive, the most promising approaches exploit proximity-induced superconductivity3, making systems fragile and difficult to realize4-7. Due to their intrinsic topology8, Weyl semimetals are also potential candidates1,2, but have always been connected with bulk superconductivity, leaving the possibility of intrinsic superconductivity of their topological surface states, the Fermi arcs, practically without attention, even from the theory side. Here, by means of angle-resolved photoemission spectroscopy and ab initio calculations, we identify topological Fermi arcs on two opposing surfaces of the non-centrosymmetric Weyl material trigonal PtBi2 (ref. 9). We show these states become superconducting at temperatures around 10 K. Remarkably, the corresponding coherence peaks appear as the strongest and sharpest excitations ever detected by photoemission from solids. Our findings indicate that superconductivity in PtBi2 can occur exclusively at the surface, rendering it a possible platform to host Majorana modes in intrinsically topological superconductor-normal metal-superconductor Josephson junctions.

Tunable positions of Weyl nodes via magnetism and pressure in the ferromagnetic Weyl semimetal CeAlSi.

The noncentrosymmetric ferromagnetic Weyl semimetal CeAlSi with simultaneous space-inversion and time-reversal symmetry breaking provides a unique platform for exploring novel topological states. Here, by employing multiple experimental techniques, we demonstrate that ferromagnetism and pressure can serve as efficient parameters to tune the positions of Weyl nodes in CeAlSi. At ambient pressure, a magnetism-facilitated anomalous Hall/Nernst effect (AHE/ANE) is uncovered. Angle-resolved photoemission spectroscopy (ARPES) measurements demonstrated that the Weyl nodes with opposite chirality are moving away from each other upon entering the ferromagnetic phase. Under pressure, by tracing the pressure evolution of AHE and band structure, we demonstrate that pressure could also serve as a pivotal knob to tune the positions of Weyl nodes. Moreover, multiple pressure-induced phase transitions are also revealed. These findings indicate that CeAlSi provides a unique and tunable platform for exploring exotic topological physics and electron correlations, as well as catering to potential applications, such as spintronics.

Facile one-pot hydrothermal synthesis of a zinc oxide/curcumin nanocomposite with enhanced toxic activity against breast cancer cells.

Zinc oxide/Curcumin (Zn(CUR)O) nanocomposites were prepared via hydrothermal treatment of Zn(NO3)2 in the presence of hexamethylenetetramine as a stabilizing agent and CUR as a bioactive element. Three ZnO : CUR ratios were investigated, namely 57 : 43 (Zn(CUR)O-A), 60 : 40 (Zn(CUR)O-B) and 81 : 19 (Zn(CUR)O-C), as assessed by thermogravimetric analyses, with an average hydrodynamic diameter of nanoaggregates in the range of 223 to 361 nm. The interaction of CUR with ZnO via hydroxyl and ketoenol groups (as proved by X-ray photoelectron spectroscopy analyses) was found to significantly modify the key properties of ZnO nanoparticles with the obtainment of a bilobed shape (as shown by scanning electron microscopy), and influenced the growth process of the composite nanoparticles as indicated by the varying particle sizes determined by powder X-ray diffraction. The efficacy of Zn(CUR)O as anticancer agents was evaluated on MCF-7 and MDA-MB-231 cancer cells, obtaining a synergistic activity with a cell viability depending on the CUR amount within the nanocomposite. Finally, the determination of reactive oxygen species production in the presence of Zn(CUR)O was used as a preliminary evaluation of the mechanism of action of the nanocomposites.

Hybrid tungsten-carbon 2D nanostructures viain situgasification of carbon substrates driven by ebeam irradiation of WO2.9microparticles.

Since the transmission electron microscope (TEM) has the capacity to observe the atomic structure of materials,in situTEM synthesis methods are uniquely suited to advance our fundamental understanding of the bottom-up dynamics that drive the formation of nanostructures. E-beam induced fragmentation (potentially identified as a manifestation of Coulomb explosion) and electron stimulated desorption are phenomena that have received attention because they trigger chemical and physical reactions that can lead to the production of various nanostructures. Here we report a simple TEM protocol implemented on WO2.9microparticles supported on thin amorphous carbon substrates. The method produces various nanostructures such as WC nanoparticles, WC supported films and others. Nevertheless, we focus on the gradual graphitization and gasification of the C substrate as it interacts with the material expelled from the WO2.9microparticles. The progressive gasification transforms the substrate from amorphous C down to hybrid graphitic nanoribbons incorporating W nanoparticles. We think these observations open interesting possibilities for the synthesis of 2D nanomaterials in the TEM.

Chirality coupling in topological magnetic textures with multiple magnetochiral parameters.

Chiral effects originate from the lack of inversion symmetry within the lattice unit cell or sample's shape. Being mapped onto magnetic ordering, chirality enables topologically non-trivial textures with a given handedness. Here, we demonstrate the existence of a static 3D texture characterized by two magnetochiral parameters being magnetic helicity of the vortex and geometrical chirality of the core string itself in geometrically curved asymmetric permalloy cap with a size of 80 nm and a vortex ground state. We experimentally validate the nonlocal chiral symmetry breaking effect in this object, which leads to the geometric deformation of the vortex string into a helix with curvature 3 µm-1 and torsion 11 µm-1. The geometric chirality of the vortex string is determined by the magnetic helicity of the vortex texture, constituting coupling of two chiral parameters within the same texture. Beyond the vortex state, we anticipate that complex curvilinear objects hosting 3D magnetic textures like curved skyrmion tubes and hopfions can be characterized by multiple coupled magnetochiral parameters, that influence their statics and field- or current-driven dynamics for spin-orbitronics and magnonics.

Intermixing-Driven Surface and Bulk Ferromagnetism in the Quantum Anomalous Hall Candidate MnBi6 Te10.

The recent realizations of the quantum anomalous Hall effect (QAHE) in MnBi2 Te4 and MnBi4 Te7 benchmark the (MnBi2 Te4 )(Bi2 Te3 )n family as a promising hotbed for further QAHE improvements. The family owes its potential to its ferromagnetically (FM) ordered MnBi2 Te4 septuple layers (SLs). However, the QAHE realization is complicated in MnBi2 Te4 and MnBi4 Te7 due to the substantial antiferromagnetic (AFM) coupling between the SLs. An FM state, advantageous for the QAHE, can be stabilized by interlacing the SLs with an increasing number n of Bi2 Te3 quintuple layers (QLs). However, the mechanisms driving the FM state and the number of necessary QLs are not understood, and the surface magnetism remains obscure. Here, robust FM properties in MnBi6 Te10 (n = 2) with Tc ≈ 12 K are demonstrated and their origin is established in the Mn/Bi intermixing phenomenon by a combined experimental and theoretical study. The measurements reveal a magnetically intact surface with a large magnetic moment, and with FM properties similar to the bulk. This investigation thus consolidates the MnBi6 Te10 system as perspective for the QAHE at elevated temperatures.

Berezinskii-Kosterlitz-Thouless Transition in the Type-I Weyl Semimetal PtBi2.

Symmetry breaking in topological matter has become in recent years a key concept in condensed matter physics to unveil novel electronic states. In this work, we predict that broken inversion symmetry and strong spin-orbit coupling in trigonal PtBi2 lead to a type-I Weyl semimetal band structure. Transport measurements show an unusually robust low dimensional superconductivity in thin exfoliated flakes up to 126 nm in thickness (with Tc ∼ 275-400 mK), which constitutes the first report and study of unambiguous superconductivity in a type-I Weyl semimetal. Remarkably, a Berezinskii-Kosterlitz-Thouless transition with TBKT ∼ 310 mK is revealed in up to 60 nm thick flakes, which is nearly an order of magnitude thicker than the rare examples of two-dimensional superconductors exhibiting such a transition. This makes PtBi2 an ideal platform to study low dimensional and unconventional superconductivity in topological semimetals.

Spinon Heat Transport in the Three-Dimensional Quantum Magnet PbCuTe_{2}O_{6}.

Quantum spin liquids (QSLs) are novel phases of matter which remain quantum disordered even at the lowest temperature. They are characterized by emergent gauge fields and fractionalized quasiparticles. Here we show that the sub-kelvin thermal transport of the three-dimensional S=1/2 hyperhyperkagome quantum magnet PbCuTe_{2}O_{6} is governed by a sizeable charge-neutral fermionic contribution which is compatible with the itinerant fractionalized excitations of a spinon Fermi surface. We demonstrate that this hallmark feature of the QSL state is remarkably robust against sample crystallinity, large magnetic field, and field-induced magnetic order, ruling out the imitation of QSL features by extrinsic effects. Our findings thus reveal the characteristic low-energy features of PbCuTe_{2}O_{6} which qualify this compound as a true QSL material.

Correction to: Optical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals.

[This corrects the article DOI: 10.1021/acsomega.2c01987.].

Metamagnetic transition and a loss of magnetic hysteresis caused by electron trapping in monolayers of single-molecule magnet Tb2@C79N.

Realization of stable spin states in surface-supported magnetic molecules is crucial for their applications in molecular spintronics, memory storage or quantum information processing. In this work, we studied the surface magnetism of dimetallo-azafullerene Tb2@C79N, showing a broad magnetic hysteresis in a bulk form. Surprisingly, monolayers of Tb2@C79N exhibited a completely different behavior, with the prevalence of a ground state with antiferromagnetic coupling at low magnetic field and a metamagnetic transition in the magnetic field of 2.5-4 T. Monolayers of Tb2@C79N were deposited onto Cu(111) and Au(111) by evaporation in ultra-high vacuum conditions, and their topography and electronic structure were characterized by scanning tunneling microscopy and spectroscopy (STM/STS). X-ray photoelectron spectroscopy (XPS), in combination with DFT studies, revealed that the nitrogen atom of the azafullerene cage tends to avoid metallic surfaces. Magnetic properties of the (sub)monolayers were then studied by X-ray magnetic circular dichroism (XMCD) at the Tb-M4,5 absorption edge. While in bulk powder samples Tb2@C79N behaves as a single-molecule magnet with ferromagnetically coupled magnetic moments and blocking of magnetization at 28 K, its monolayers exhibited a different ground state with antiferromagnetic coupling of Tb magnetic moments. To understand if this unexpected behavior is caused by a strong hybridization of fullerenes with metallic substrates, XMCD measurements were also performed for Tb2@C79N adsorbed on h-BN|Rh(111) and MgO|Ag(100). The co-existence of two forms of Tb2@C79N was found on these substrates as well, but magnetization curves showed narrow magnetic hysteresis detectable up to 25 K. The non-magnetic state of Tb2@C79N in monolayers is assigned to anionic Tb2@C79N- species with doubly-occupied Tb-Tb bonding orbital and antiferromagnetic coupling of the Tb moments. A charge transfer from the substrate or trapping of secondary electrons are discussed as a plausible origin of these species.

Synthesis of micro- and nanosheets of CrCl3-RuCl3 solid solution by chemical vapour transport.

Solid solutions of 2D transition metal trihalides are rapidly growing in interest for the search for new 2D materials with novel properties at nanoscale dimensions. In this regard, we present a synthesis method for the Cr1-xRuxCl3 solid solution and describe the behaviour of the unit cell parameters over the whole composition range, which in general follows Vegard's law in the range of a = 5.958(6)CrCl3 … 5.9731(5)RuCl3 Å, b = 10.3328(20)CrCl3 … 10.34606(21)RuCl3 Å, c = 6.110(5)CrCl3 … 6.0385(5)RuCl3 Å and ß = 108.522(15)CrCl3 … 108.8314(14)RuCl3 °. The synthesized solid solution powder was subsequently used to deposit micro- and nanosheets directly on a substrate by applying chemical vapour transport in a temperature gradient of 575 °C → 525 °C for 2 h and 650 °C → 600 °C for 0.5 h as a bottom-up approach without the need for an external transport agent. The observed chromium chloride enrichment of the deposited crystals is predicted by thermodynamic simulation. The results allow for a nanostructure synthesis of this solid solution with a predictable composition down to about 30 nm in height and lateral size of several µm. When applying a quick consecutive delamination step, it is possible to obtain few- and monolayer structures, which could be used for further studies of downscaling effects for the CrCl3-RuCl3 solid solution. X-ray photoelectron spectroscopy, transmission electron microscopy and Raman spectroscopy were used to confirm the purity and quality of the synthesized crystals.

Fermi surface tomography.

Fermi surfaces are essential for predicting, characterizing and controlling the properties of crystalline metals and semiconductors. Angle-resolved photoemission spectroscopy (ARPES) is the only technique directly probing the Fermi surface by measuring the Fermi momenta (kF) from energy- and angular distribution of photoelectrons dislodged by monochromatic light. Existing apparatus is able to determine a number of kF -vectors simultaneously, but direct high-resolution 3D Fermi surface mapping remains problematic. As a result, no such datasets exist, strongly limiting our knowledge about the Fermi surfaces. Here we show that using a simpler instrumentation it is possible to perform 3D-mapping within a very short time interval and with very high resolution. We present the first detailed experimental 3D Fermi surface as well as other experimental results featuring advantages of our technique. In combination with various light sources our methodology and instrumentation offer new opportunities for high-resolution ARPES in the physical and life sciences.

Optical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals.

High-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure-unknown before-was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes.

Determination of Cleavage Energy and Efficient Nanostructuring of Layered Materials by Atomic Force Microscopy.

A method is presented to use atomic force microscopy to measure the cleavage energy of van der Waals materials and similar quasi-two-dimensional materials. The cleavage energy of graphite is measured to be 0.36 J/m2, in good agreement with literature data. The same method yields a cleavage energy of 0.6 J/m2 for MoS2 as a representative of the dichalcogenides. In the case of the weak topological insulator Bi14Rh3I9 no cleavage energy is obtained, although cleavage is successful with an adapted approach. The cleavage energies of these materials are evaluated by means of density-functional calculations and literature data. This further validates the presented method and sets an upper limit of about 0.7 J/m2 to the cleavage energy that can be measured by the present setup. In addition, this method can be used as a tool for manipulating exfoliated flakes, prior to or after contacting, which may open a new route for the fabrication of nanostructures.

Curcumin and Graphene Oxide Incorporated into Alginate Hydrogels as Versatile Devices for the Local Treatment of Squamous Cell Carcinoma.

With the aim of preparing hybrid hydrogels suitable for use as patches for the local treatment of squamous cell carcinoma (SCC)-affected areas, curcumin (CUR) was loaded onto graphene oxide (GO) nanosheets, which were then blended into an alginate hydrogel that was crosslinked by means of calcium ions. The homogeneous incorporation of GO within the polymer network, which was confirmed through morphological investigations, improved the stability of the hybrid system compared to blank hydrogels. The weight loss in the 100-170 °C temperature range was reduced from 30% to 20%, and the degradation of alginate chains shifted to higher temperatures. Moreover, GO enhanced the stability in water media by counteracting the de-crosslinking process of the polymer network. Cell viability assays showed that the loading of CUR (2.5% and 5% by weight) was able to reduce the intrinsic toxicity of GO towards healthy cells, while higher amounts were ineffective due to the antioxidant/prooxidant paradox. Interestingly, the CUR-loaded systems were found to possess a strong cytotoxic effect in SCC cancer cells, and the sustained CUR release (~50% after 96 h) allowed long-term anticancer efficiency to be hypothesized.

Highly efficient modulation doping: A path toward superior organic thermoelectric devices.

We investigate the charge and thermoelectric transport in modulation-doped large-area rubrene thin-film crystals with different crystal phases. We show that modulation doping allows achieving superior doping efficiencies even for high doping densities, when conventional bulk doping runs into the reserve regime. Modulation-doped orthorhombic rubrene achieves much improved thermoelectric power factors, exceeding 20 µW m-1 K-2 at 80°C. Theoretical studies give insight into the energy landscape of the heterostructures and its influence on qualitative trends of the Seebeck coefficient. Our results show that modulation doping together with high-mobility crystalline organic semiconductor films is a previosly unexplored strategy for achieving high-performance organic thermoelectrics.

Charge-Density-Wave-Induced Peak-Dip-Hump Structure and the Multiband Superconductivity in a Kagome Superconductor CsV_{3}Sb_{5}.

The entanglement of charge density wave (CDW), superconductivity, and topologically nontrivial electronic structure has recently been discovered in the kagome metal AV_{3}Sb_{5} (A=K, Rb, Cs) family. With high-resolution angle-resolved photoemission spectroscopy, we study the electronic properties of CDW and superconductivity in CsV_{3}Sb_{5}. The spectra around K[over ¯] is found to exhibit a peak-dip-hump structure associated with two separate branches of dispersion, demonstrating the isotropic CDW gap opening below E_{F}. The peak-dip-hump line shape is contributed by linearly dispersive Dirac bands in the lower branch and a dispersionless flat band close to E_{F} in the upper branch. The electronic instability via Fermi surface nesting could play a role in determining these CDW-related features. The superconducting gap of ∼0.4 meV is observed on both the electron band around Γ[over ¯] and the flat band around K[over ¯], implying the multiband superconductivity. The finite density of states at E_{F} in the CDW phase is most likely in favor of the emergence of multiband superconductivity, particularly the enhanced density of states associated with the flat band. Our results not only shed light on the controversial origin of the CDW, but also offer insights into the relationship between CDW and superconductivity.