Origin of Distinct Insulating Domains in the Layered Charge Density Wave Material 1T-TaS2.

Vertical charge order shapes the electronic properties in layered charge density wave (CDW) materials. Various stacking orders inevitably create nanoscale domains with distinct electronic structures inaccessible to bulk probes. Here, the stacking characteristics of bulk 1T-TaS2 are analyzed using scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations. It is observed that Mott-insulating domains undergo a transition to band-insulating domains restoring vertical dimerization of the CDWs. Furthermore, STS measurements covering a wide terrace reveal two distinct band insulating domains differentiated by band edge broadening. These DFT calculations reveal that the Mott insulating layers preferably reside on the subsurface, forming broader band edges in the neighboring band insulating layers. Ultimately, buried Mott insulating layers believed to harbor the quantum spin liquid phase are identified. These results resolve persistent issues regarding vertical charge order in 1T-TaS2, providing a new perspective for investigating emergent quantum phenomena in layered CDW materials.

Melting of Unidirectional Charge Density Waves across Twin Domain Boundaries in GdTe3.

Solids undergoing a transition from order to disorder experience a proliferation of topological defects. The melting process generates transient quantum states. However, their dynamic nature with a femtosecond lifetime hinders exploration with atomic precision. Here, we suggest an alternative approach to the dynamic melting process by focusing on the interface created by competing degenerate quantum states. We use a scanning tunneling microscope (STM) to visualize the unidirectional charge density wave (CDW) and its spatial progression ("static melting") across a twin domain boundary (TDB) in the layered material GdTe3. Combining the STM with a spatial lock-in technique, we reveal that the order parameter amplitude attenuates with the formation of dislocations and thus two different unidirectional CDWs coexist near the TDB, reducing the CDW anisotropy. Notably, we discovered a correlation between this anisotropy and the CDW gap. Our study provides valuable insight into the behavior of topological defects and transient quantum states.

Experimental signatures of nodeless multiband superconductivity in a [Formula: see text] single crystal.

In order to understand the superconducting gap nature of a [Formula: see text] single crystal with [Formula: see text], in-plane thermal conductivity [Formula: see text], in-plane London penetration depth [Formula: see text], and the upper critical fields [Formula: see text] have been investigated. At zero magnetic field, it is found that no residual linear term [Formula: see text] exists and [Formula: see text] follows a power-law [Formula: see text] (T: temperature) with n = 2.66 at [Formula: see text], supporting nodeless superconductivity. Moreover, the magnetic-field dependence of [Formula: see text]/T clearly shows a shoulder-like feature at a low field region. The temperature dependent [Formula: see text] curves for both in-plane and out-of-plane field directions exhibit clear upward curvatures near [Formula: see text], consistent with the shape predicted by the two-band theory and the anisotropy ratio between the [Formula: see text](T) curves exhibits strong temperature-dependence. All these results coherently suggest that [Formula: see text] is a nodeless, multiband superconductor.

Magnon bound states versus anyonic Majorana excitations in the Kitaev honeycomb magnet α-RuCl3.

The pure Kitaev honeycomb model harbors a quantum spin liquid in zero magnetic fields, while applying finite magnetic fields induces a topological spin liquid with non-Abelian anyonic excitations. This latter phase has been much sought after in Kitaev candidate materials, such as α-RuCl3. Currently, two competing scenarios exist for the intermediate field phase of this compound (B = 7 - 10 T), based on experimental as well as theoretical results: (i) conventional multiparticle magnetic excitations of integer quantum number vs. (ii) Majorana fermionic excitations of possibly non-Abelian nature with a fractional quantum number. To discriminate between these scenarios a detailed investigation of excitations over a wide field-temperature phase diagram is essential. Here, we present Raman spectroscopic data revealing low-energy quasiparticles emerging out of a continuum of fractionalized excitations at intermediate fields, which are contrasted by conventional spin-wave excitations. The temperature evolution of these quasiparticles suggests the formation of bound states out of fractionalized excitations.

Raman spectroscopic diagnostic of quantum spin liquids.

Quantum spin liquids are outstanding examples of highly quantum entangled phases of matter and serve as a testbed to gauge central concepts of strongly correlated materials. Enormous research efforts in the past few decades have brought an in-depth understanding of these novel phases, although their conundrums have not yet been solved completely. In this review, we give an overview of the three different classes of spin-liquid materials: (i) a one-dimensional spin chain system KCuF3, (ii) a kagome antiferromagnet ZnCu3(OH)6Cl2, and (iii) a Kitaev honeycomb material [Formula: see text]-RuCl3. The emphasis is on demonstrating the success of the Raman scattering technique for probing fractionalized excitations in the aforementioned spin-liquid compounds, complementing a well-established neutron scattering method. Irrespective of dimensionality, spin topology, and spin-exchange type, the three materials share several common features in the spectral shape and temperature dependence of magnetic excitations, which can be taken as Raman spectroscopic fingerprints of quantum spin liquids.

Preparation of silver nanoparticles coated ZnO/Fe3O4 composites using chemical reduction method for sensitive detection of uric acid via surface-enhanced Raman spectroscopy.

In this study, silver nanostructures decorated magnetic nanoparticles for surface-enhanced Raman scattering (SERS) measurements were prepared via heat induced catalytic activity of ZnO nanostructures. The ZnO/Fe3O4 composite was first prepared by dispersing pre-formed magnetic nanoparticles into alkaline zinc nitrate solutions. After annealing of the precipitates, the formed ZnO/Fe3O4 composites were successfully decorated with silver nanostructures by dispersing the composites into silver nitrate/ethylene glycol solution at 95 °C in water bath. To find the optimal condition when preparing Ag/ZnO/Fe3O4 composites for SERS measurements, factors such as reaction time and concentration of silver nitrate were studied. Results indicated that the formation of silver nanoparticles (AgNPs) on ZnO/Fe3O4 was significantly improved with the assistance of ZnO. The concentration of silver nitrate and reaction time affected the morphologies and sizes of the formed composites and optimal condition in preparation of the composites for SERS measurement was found using 100 mM of silver nitrate with a reaction time of 20 min. Under optimized conditions, the obtained SERS intensities were highly reproducible. The substrates were applied for quantitative analysis of uric acid in aqueous solution and a linear response for concentrations up to 10 µM was obtained. Successful application of these prepared composites to determine uric acid in urine sample without any pretreatment of the urine sample was done.

Nano MOF Entrapping Hydrophobic Photosensitizer for Dual-Stimuli-Responsive Unprecedented Therapeutic Action against Drug-Resistant Bacteria.

Multidrug resistance (MDR) of bacteria is a major threat to public health globally and its unprecedented increase calls for immediate alternative medical strategies. Antimicrobial photodynamic therapy (aPDT) offers alternative modalities to combat the growing MDR typically by means of targeted cellular internalization of a photosensitizer (PS) capable of producing photoinduced reactive oxygen species (ROS). However, aPDT is severely limited by the self-aggregation behavior and hydrophobicity of PS molecules, which significantly curbs its viability for clinical application. The present study reports the use of modified nanoscale metal-organic frameworks (NMOFs) encapsulating a hydrophobic PS drug squaraine (SQ) to enhance aPDT efficacy against drug-resistant planktonic bacteria and its biofilm for the first time. Zeolitic imidazolate framework (ZIF-8) NMOF nanocrystals are attached postsynthetically with SQ (designated as ZIF8-SQ) and the resultant drug-doped NMOF is characterized by TEM, FESEM, PXRD, Raman spectroscopy, UV-vis spectroscopy, and steady-state and time-resolved fluorescence techniques. The microporous structures of ZIF-8 behave as molecular cages ceasing the self-aggregation of hydrophobic SQ. In addition, the formulated ZIF8-SQ produces cytotoxic ROS under red-light irradiation (650 nm) in a pH sensitive way primarily due to molecular level interaction and charge separation between ZIF-8 and SQ depicting a dual-stimuli-responsive nature. Most notably, ZIF8-SQ provides unparalleled aPDT action against methicillin-resistant Staphylococcus aureus (MRSA) and leads to complete loss of adherence of structurally robust bacterial biofilms. Finally, the nontoxic nature of the nanoconjugate toward human cells holds great promise for effective treatment of MRSA and other detrimental antibiotic-resistant microbes in clinical models.

Screw- Type Motion and Its Impact on Cooperativity in BaNa2Fe[VO4]2.

BaNa2Fe[VO4]2 contains a Jahn-Teller active ion (FeII, 3d6, high-spin) in an octahedral coordination. On the basis of a combination of temperature-dependent X-ray diffraction and Mössbauer and Raman spectroscopies, we demonstrate the coupling of lattice dynamics with the electronic ground state of FeII. We identify three lattice modes combined to an effective canted screw- type motion that drives the structural transition around room temperature from the high-temperature ( P3̅) via intermediate phases to the low-temperature phase ( C2/ c). The dynamics of the electronic ground state of Fe(II) are evident from Mössbauer data with signatures of a motion-narrowed doublet above 320 K, a gradual evolution of the 5Eg electronic state below 293 K, and finally the signature of the thermodynamically preferred orbitally nondegenerate ground state (5Ag) of Fe(II) below 100 K. The continuous nature of the transition is associated with the temperature-dependent phonon parameters derived from Raman spectroscopy, which point out the presence of strong electron-phonon coupling in this compound. We present a microscopic mechanism and evaluate the collective component leading to the structural phase transition.

Construction of a ³He magnetic force microscope with a vector magnet.

We constructed a (3)He magnetic force microscope operating at the base temperature of 300 mK under a vector magnetic field of 2-2-9 T in the x-y-z direction. Fiber optic interferometry as a detection scheme is employed in which two home-built fiber walkers are used for the alignment between the cantilever and the optical fiber. The noise level of the laser interferometer is close to its thermodynamic limit. The capabilities of the sub-Kelvin and vector field are demonstrated by imaging the coexistence of magnetism and superconductivity in a ferromagnetic superconductor (ErNi2B2C) at T = 500 mK and by probing a dipole shape of a single Abrikosov vortex with an in-plane tip magnetization.

Softened magnetic excitations in the s = 3/2 distorted triangular antiferromagnet α-CaCr2O4.

The spin dynamics and magnetic excitations of the slightly distorted triangular s = 3/2 system α-CaCr (2)O (4) are investigated by means of Raman spectroscopy and electron spin resonance (ESR) to elucidate its peculiar magnetic properties. Two-magnon excitations in circular RL symmetry show a multi-maximum structure with a dominant spectral weight at low energies. The temperature dependence of the ESR linewidth is described by a critical broadening ΔH(pp)(T) is proportional to (T-T(N ))(-p) with the exponent p = 0.38(5) - 0.48(3) for temperatures above T(N) = 42.6 K. The exponent is much smaller than that of other s = 3/2 triangular lattices. This is ascribed to soft roton-like modes, indicative of the instability of a helical 120° phase. As an origin we discuss a complex spin topology formed by four inequivalent nearest neighbor and sizable next-nearest neighbor interactions.

Ultrafast excited state deactivation of doped porous anodic alumina membranes.

Free-standing, bi-directionally permeable and ultra-thin anodic aluminum oxide (AAO) membranes establish attractive templates (host) for the synthesis of nano-dots and rods of various materials (guest). This is due to their chemical and structural integrity and high periodicity on length scales of 5-150 nm which are often used to host photoactive nano-materials for various device applications including dye-sensitized solar cells. In the present study, AAO membranes are synthesized by using electrochemical methods and a detailed structural characterization using FEG-SEM, XRD and TGA confirms the porosity and purity of the material. Defect-mediated photoluminescence quenching of the porous AAO membrane in the presence of an electron accepting guest organic molecule (benzoquinone) is studied by means of steady-state and picosecond/femtosecond-resolved luminescence measurements. Using time-resolved luminescence transients, we have also revealed light harvesting of complexes of porous alumina impregnated with inorganic quantum dots (Maple Red) or gold nanowires. Both the Förster resonance energy transfer and the nano-surface energy transfer techniques are employed to examine the observed quenching behavior as a function of the characteristic donor-acceptor distances. The experimental results will find their relevance in light harvesting devices based on AAOs combined with other materials involving a decisive energy/charge transfer dynamics.

Synthesis, crystal structure, and magnetic properties of the copper selenite chloride Cu5(SeO3)4Cl2.

A new copper selenite chloride Cu(5)(SeO(3))(4)Cl(2) has been prepared by chemical vapor transport reactions. Its crystal structure was determined by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group P2(1)/c with the unit cell parameters a = 10.9104(8) Å, b = 8.3134(6) Å, c = 7.5490(6) Å, ß = 90.715(6)°, Z = 2, and R(1) = 0.0383. Bond valence sum calculations indicate that the cations have the oxidation state Cu(II) and Se(IV), respectively. Three crystallographic different copper atoms, having different coordination polyhedra, [CuO(5)], [CuO(6)], and [CuO(3)Cl(2)], are connected by corner and edge sharing to form a framework that can be described as metal-oxygen slabs connected by Cl atoms via edge sharing [CuO(3)Cl(2)] polyhedra. The two crystallographic different selenium atoms both have [SeO(3)E] coordination, where E is the 4s(2) lone pair on Se(IV); they are isolated from each other and do bond to the Cu-coordination polyhedra only. The magnetic properties of the Cu(2+) ions with effective spin S = 1/2 moments are dominated by antiferromagnetic interactions. For temperatures T < T(c) ∼45 K, Néel magnetic ordering is observed with small ferromagnetic canted moments. We attribute these to antisymmetric Dzyaloshinskii-Moriya (DM) spin exchange which is allowed by the low symmetry spin exchange paths along the distorted transition metal oxyhalide coordinations.

A molecular magnet confined in the nanocage of a globular protein.

The effect of confinement and energy transfer on the dynamics of a molecular magnet, known as a model system to study quantum coherence, is investigated. For this purpose the well-known polyoxovanadate [V(15)As(6)O(42)(H(2)O)](6-) (V(15)) is incorporated into a protein (human serum albumin, HSA) cavity. Due to a huge overlap of the optical absorption spectrum of V(15) with the emission spectrum of a fluorescence center of HSA (containing a single tryptophan residue), energy transfer is induced and probed by steady-state and time-resolved fluorescence. The geometrical coordination and the distance of the confined V(15) to the tryptophan moiety of HSA are investigated at various temperatures. This effect is used as a local probe for the thermal denaturation of the protein at elevated temperatures.

Separation of the oxide and halide part in the oxohalide Fe3Te3O10Cl due to high Lewis acidity of the cations.

A new iron tellurite halide Fe(3)Te(3)O(10)Cl has been identified that crystallizes in the monoclinic space group P2(1)/c. The crystal structure comprises channels where the Cl ions and also the stereochemically active lone-pair electrons on Te(4+) are located. The Cl-atoms rather act as counterions than being part of the covalent/ionic network. The magnetic susceptibility indicates antiferromagnetic ordering below T(N) approximately 100 K with a marked splitting of the field cooled (fc) and the zero-field cooled (zfc) susceptibility at low magnetic fields; the splitting disappears at higher magnetic fields. Heat capacity measurements confirm the long-range ordering at below this temperature. Only moderate shifts are observed with Raman spectroscopy at the magnetic transition.