Exchange scaling of ultrafast angular momentum transfer in 4f antiferromagnets.

Ultrafast manipulation of magnetism bears great potential for future information technologies. While demagnetization in ferromagnets is governed by the dissipation of angular momentum1-3, materials with multiple spin sublattices, for example antiferromagnets, can allow direct angular momentum transfer between opposing spins, promising faster functionality. In lanthanides, 4f magnetic exchange is mediated indirectly through the conduction electrons4 (the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction), and the effect of such conditions on direct spin transfer processes is largely unexplored. Here, we investigate ultrafast magnetization dynamics in 4f antiferromagnets and systematically vary the 4f occupation, thereby altering the magnitude of the RKKY coupling energy. By combining time-resolved soft X-ray diffraction with ab initio calculations, we find that the rate of direct transfer between opposing moments is directly determined by this coupling. Given the high sensitivity of RKKY to the conduction electrons, our results offer a useful approach for fine tuning the speed of magnetic devices.

Exchange-Striction Driven Ultrafast Nonthermal Lattice Dynamics in NiO.

We use femtosecond electron diffraction to study ultrafast lattice dynamics in the highly correlated antiferromagnetic (AFM) semiconductor NiO. Using the scattering vector (Q) dependence of Bragg diffraction, we introduce Q-resolved effective temperatures describing the transient lattice. We identify a nonthermal lattice state with preferential displacement of O compared to Ni ions, which occurs within ∼0.3 ps and persists for 25 ps. We associate this with transient changes to the AFM exchange striction-induced lattice distortion, supported by the observation of a transient Q asymmetry of Friedel pairs. Our observation highlights the role of spin-lattice coupling in routes towards ultrafast control of spin order.

Resonant plasmon enhancement of light emission from CdSe/CdS nanoplatelets on Au nanodisk arrays.

Semiconducting nanoplatelets (NPLs) have attracted great attention due to the superior photophysical properties compared to their quantum dot analogs. Understanding and tuning the optical and electronic properties of NPLs in a plasmonic environment is a new paradigm in the field of optoelectronics. Here, we report on the resonant plasmon enhancement of light emission including Raman scattering and photoluminescence from colloidal CdSe/CdS nanoplatelets deposited on arrays of Au nanodisks fabricated by electron beam lithography. The localized surface plasmon resonance (LSPR) of the Au nanodisk arrays can be tuned by varying the diameter of the disks. In the case of surface-enhanced Raman scattering (SERS), the Raman intensity profile follows a symmetric Gaussian shape matching the LSPR of the Au nanodisk arrays. The surface-enhanced photoluminescence (SEPL) profile of NPLs, however, follows an asymmetric Gaussian distribution highlighting a compromise between the excitation and emission enhancement mechanisms originating from energy transfer and Purcell effects. The SERS and SEPL enhancement factors depend on the nanodisk size and reach maximal values at 75 and 7, respectively, for the sizes, for which the LSPR energy of Au nanodisks coincides with interband transition energies in the semiconductor platelets. Finally, to explain the origin of the resonant enhancement behavior of SERS and SEPL, we apply a numerical simulation to calculate plasmon energies in Au nanodisk arrays and emission spectra from NPLs in such a plasmonic environment.

Momentum-Resolved View of Electron-Phonon Coupling in Multilayer WSe_{2}.

We investigate the interactions of photoexcited carriers with lattice vibrations in thin films of the layered transition metal dichalcogenide (TMDC) WSe_{2}. Employing femtosecond electron diffraction with monocrystalline samples and first-principles density functional theory calculations, we obtain a momentum-resolved picture of the energy transfer from excited electrons to phonons. The measured momentum-dependent phonon population dynamics are compared to first-principles calculations of the phonon linewidth and can be rationalized in terms of electronic phase-space arguments. The relaxation of excited states in the conduction band is dominated by intervalley scattering between Σ valleys and the emission of zone boundary phonons. Transiently, the momentum-dependent electron-phonon coupling leads to a nonthermal phonon distribution, which, on longer time scales, relaxes to a thermal distribution via electron-phonon and phonon-phonon collisions. Our results constitute a basis for monitoring and predicting out of equilibrium electrical and thermal transport properties for nanoscale applications of TMDCs.

Molecular dynamics simulations of phosphonic acid-aluminum oxide self-organization and their evolution into ordered monolayers.

We outline an unprejudiced molecular dynamics simulation approach to study the mechanisms of self-organization encompassing the evolution of surfactant-surface interactions to the growth of self-assembled monolayers (SAMs). Therein, the time-length scale problem is tackled by combining an efficient docking-type procedure for implementing surfactant-by-surfactant association with detailed molecular simulations to explore structural relaxation. For this, nanosecond-scale molecular dynamics simulations unravel ordering processes during the gradual assembly of the monolayer. Along this line, different packing motifs of octadecyl phosphonic acid (ODPA) on the (0001) surface of α-alumina and implications for the final density and ordering of the resulting monolayers are elucidated. Moreover, the role of the solvent is discriminated by comparing SAM formation in 2-propanol, hexane and in a vacuum.

Surface- and tip-enhanced resonant Raman scattering from CdSe nanocrystals.

Surface- and tip-enhanced resonant Raman scattering (resonant SERS and TERS) by optical phonons in a monolayer of CdSe quantum dots (QDs) is demonstrated. The SERS enhancement was achieved by employing plasmonically active substrates consisting of gold arrays with varying nanocluster diameters prepared by electron-beam lithography. The magnitude of the SERS enhancement depends on the localized surface plasmon resonance (LSPR) energy, which is determined by the structural parameters. The LSPR positions as a function of nanocluster diameter were experimentally determined from spectroscopic micro-ellipsometry, and compared to numerical simulations showing good qualitative agreement. The monolayer of CdSe QDs was deposited by the Langmuir-Blodgett-based technique on the SERS substrates. By tuning the excitation energy close to the band gap of the CdSe QDs and to the LSPR energy, resonant SERS by longitudinal optical (LO) phonons of CdSe QDs was realized. A SERS enhancement factor of 2 × 10(3) was achieved. This allowed the detection of higher order LO modes of CdSe QDs, evidencing the high crystalline quality of QDs. The dependence of LO phonon mode intensity on the size of Au nanoclusters reveals a resonant character, suggesting that the electromagnetic mechanism of the SERS enhancement is dominant. Finally, the resonant TERS spectrum from CdSe QDs was obtained using electrochemically etched gold tips providing an enhancement on the order of 10(4). This is an important step towards the detection of the phonon spectrum from a single QD.

Colloidal ZnO nanocrystals in dimethylsulfoxide: a new synthesis, optical, photo- and electroluminescent properties.

Stable colloidal solutions of zinc oxide in dimethylsulfoxide were synthesized via interaction between zinc(II) acetate and tetraalkylammonium hydroxides (alkyl-ethyl, propyl, butyl, and pentyl). Colloids of ZnO emit photoluminescence in a broad band with a maximum at 2.3-2.4 eV with quantum yields of up to 9-10% at room temperature and 15-16% at 80 K. The photoluminescence is supposed to originate from the radiative recombination of conduction band electrons with holes captured by deep traps having corresponding states in the band gap 1.0-1.2 eV above the valence band edge. The size of colloidal ZnO nanocrystals depends on the duration and temperature of the post-synthesis treatment and varies in the range of 3-6 nm. Growth of the ZnO nanocrystals can be terminated at any moment of the thermal treatment by freezing the colloidal solution or by addition of tetraethyl orthosilicate which hydrolyses forming core-shell ZnO@SiO2 particles. ZnO nanocrystals introduced into polyethyleneimine films can be used as an active component of an LED emitting at an applied voltage higher than 13 V.

Resonant Raman scattering on graphene: SERS and gap-mode TERS.

Nanoscale deformations and corrugations occur in graphene-like two-dimensional materials during their incorporation into hybrid structures and real devices, such as sensors based on surface-enhanced Raman scattering (SERS-based sensors). The structural features mentioned above are known to affect the electronic properties of graphene, thus highly sensitive and high-resolution techniques are required to reveal and characterize arising local defects, mechanical deformations, and phase transformations. In this study, we demonstrate that gap-mode tip-enhanced Raman Scattering (gm-TERS), which offers the benefits of structural and chemical analytical methods, allows variations in the structure and mechanical state of a two-dimensional material to be probed with nanoscale spatial resolution. In this work, we demonstrate locally enhanced gm-TERS on a monolayer graphene film placed on a plasmonic substrate with specific diameter gold nanodisks. SERS measurements are employed to determine the optimal disk diameter and excitation wavelength for further realization of gm-TERS. A significant local plasmonic enhancement of the main vibrational modes in graphene by a factor of 100 and a high spatial resolution of 10 nm are achieved in the gm-TERS experiment, making gm-TERS chemical mapping possible. By analyzing the gm-TERS spectra of the graphene film in the local area of a nanodisk, the local tensile mechanical strain in graphene was detected, resulting in a split of the G mode into two components, G+ and G-. Using the frequency split in the positions of G+ and G- modes in the TERS spectra, the stress was estimated to be up to 1.5%. The results demonstrate that gap-mode TERS mapping allows rapid and precise characterization of local structural defects in two-dimensional materials on the nanoscale.

Electronic states and the influence of oxygen addition on the optical absorption behaviour of manganese phthalocyanine.

The effects of electronic states and air exposure on the spectroscopic properties of manganese phthalocyanine (MnPc) have been examined. The observed features of the Q-band in the absorption spectra can be explained by intrinsic electronic properties of MnPc, i.e., the formation of singly charged molecules by charge transfer excitations. However, the reaction of MnPc with atmospheric molecular oxygen leads to deviations in peak intensities but does not change the fundamental characteristics of the spectra. Nevertheless, the reaction with oxygen changes the spin state from S = 3/2 to S = 1/2. X-ray diffraction measurements also indicate a slow diffusion process of the oxygen into the MnPc crystal. We discuss both influences to explain the behaviour of MnPc in various spectroscopic methods (EELS, ellipsometry, PES). Furthermore, we support the experimental investigations by detailed ab-initio calculations of spectroscopic properties using methods of the density functional theory framework.

Two-color synchrotron X-ray spectroscopy based on transverse resonance island buckets.

We report on a novel multi-color method of X-ray spectroscopy at a Synchrotron radiation source that uses two simultaneously filled electron orbits in an electron storage ring to generate multiple soft or tender X-ray beams of different wavelength. To establish the second orbit, we use nonlinear beam dynamics in the so called TRIBs-transverse resonance island buckets-mode of the BESSY II storage ring, where a second electron orbit winds around the regular one leading to transversely separated source points. X-ray beams of multiple colors are generated by imaging the individual source points via different pathways through a monochromator. The particular colors can be varied by changing the traversal electron beam positions through storage-ring parameters and/or via the monochromator dispersion. As a proof of principle, X-ray absorption spectroscopy is performed on thin Fe films in transmission as well as a scanning transmission measurement on a Fe3GeTe2 sample of inhomogeneous thickness normalizing resonant signals with the pre-edge intensity. Using the extraordinary pointing fidelity of successive X-ray macro-pulses arriving at MHz repetition rates, a detection of tiny contrasts in diluted systems, contrast enhancement in X-ray microscopy as well as fast dynamics studies come into reach.

Quantum device designing (QDD) for future semiconductor engineering.

In semiconductor device history, a trend is observed where narrowing and increasing the number of material layers improve device functionality, with diodes, transistors, thyristors, and superlattices following this trend. While superlattices promise unique functionality, they are not widely adopted due to a technology barrier, requiring advanced fabrication, such as molecular beam epitaxy and lattice-matched materials. Here, a method to design quantum devices using amorphous materials and physical vapor deposition is presented. It is shown that the multiplication gain M depends on the number of layers of the superlattice, N, as M = kN, with k as a factor indicating the efficiency of multiplication. This M is, however, a trade-off with transit time, which also depends on N. To demonstrate, photodetector devices are fabricated on Si, with the superlattice of Se and As2Se3, and characterized using current-voltage (I-V) and current-time (I-T) measurements. For superlattices with the total layer thicknesses of 200 nm and 2 µm, the results show that k200nm = 0.916 and k2µm = 0.384, respectively. The results confirm that the multiplication factor is related to the number of superlattice layers, showing the effectiveness of the design approach.

Heat dissipation in Sm3+ and Zn2+ co-substituted magnetite (Zn0.1SmxFe2.9-xO4) nanoparticles coated with citric acid and pluronic F127 for hyperthermia application.

In this work, Sm3+ and Zn2+ co-substituted magnetite Zn0.1SmxFe2.9-xO4 (x = 0.0, 0.01, 0.02, 0.03, 0.04 and 0.05) nanoparticles, have been prepared via co-precipitation method and were electrostatically and sterically stabilized by citric acid and pluronic F127 coatings. The coated nanoparticles were well dispersed in an aqueous solution (pH 5.5). Magnetic and structural properties of the nanoparticles and their ferrofluids were studied by different methods. XRD studies illustrated that all as-prepared nanoparticles have a single phase spinel structure, with lattice constants affected by samarium cations substitution. The temperature dependence of the magnetization showed that Curie temperatures of the uncoated samples monotonically increased from 430 to 480 °C as Sm3+ content increased, due to increase in A-B super-exchange interactions. Room temperature magnetic measurements exhibited a decrease in saturation magnetization of the uncoated samples from 98.8 to 71.9 emu/g as the Sm3+ content increased, which is attributed to substitution of Sm3+ (1.5 µB) ions for Fe3+ (5 µB) ones in B sublattices. FTIR spectra confirmed that Sm3+ substituted Zn0.1SmxFe2.9-xO4 nanoparticles were coated with both citric acid and pluronic F127 properly. The mean particle size of the coated nanoparticles was 40 nm. Calorimetric measurements showed that the maximum SLP and ILP values obtained for Sm3+ substituted nanoparticles were 259 W/g and 3.49 nHm2/kg (1.08 mg/ml, measured at f = 290 kHz and H = 16kA/m), respectively, that are related to the sample with x = 0.01. Magnetic measurements revealed coercivity, which indicated that hysteresis loss may represent a substantial portion in heat generation. Our results show that these ferrofluids are potential candidates for magnetic hyperthermia applications.

Surface-modified magnetite nanoparticles affect lysozyme amyloid fibrillization.

BACKGROUND: The surface of nanoparticles (NPs) is an important factor affecting the process of poly/peptides' amyloid aggregation. We have investigated the in vitro effect of trisodium citrate (TC), gum arabic (GA) and citric acid (CA) surface-modified magnetite nanoparticles (COAT-MNPs) on hen egg-white lysozyme (HEWL) amyloid fibrillization and mature HEWL fibrils. METHODS: Dynamic light scattering (DLS) was used to characterize the physico-chemical properties of studied COAT-MNPs and determine the adsorption potential of their surface towards HEWL. The anti-amyloid properties were studied using thioflavin T (ThT) and tryptophan (Trp) intrinsic fluorescence assays, and atomic force microscopy (AFM). The morphology of amyloid aggregates was analyzed using Gwyddion software. The cytotoxicity of COAT-MNPs was determined utilizing Trypan blue (TB) assay. RESULTS: Agents used for surface modification affect the COAT-MNPs physico-chemical properties and modulate their anti-amyloid potential. The results from ThT and intrinsic fluorescence showed that the inhibitory activities result from the more favorable interactions of COAT-MNPs with early pre-amyloid species, presumably reducing nuclei and oligomers formation necessary for amyloid fibrillization. COAT-MNPs also possess destroying potential, which is presumably caused by the interaction with hydrophobic residues of the fibrils, resulting in the interruption of an interface between ß-sheets stabilizing the amyloid fibrils. CONCLUSION: COAT-MNPs were able to inhibit HEWL fibrillization and destroy mature fibrils with different efficacy depending on their properties, TC-MNPs being the most potent nanoparticles. GENERAL SIGNIFICANCE: The study reports findings regarding the general impact of nanoparticles' surface modifications on the amyloid aggregation of proteins.

APTES monolayer coverage on self-assembled magnetic nanospheres for controlled release of anticancer drug Nintedanib.

The use of an appropriate delivery system capable of protecting, translocating, and selectively releasing therapeutic moieties to desired sites can promote the efficacy of an active compound. In this work, we have developed a nanoformulation which preserves its magnetization to load a model anticancerous drug and to explore the controlled release of the drug in a cancerous environment. For the preparation of the nanoformulation, self-assembled magnetic nanospheres (MNS) made of superparamagnetic iron oxide nanoparticles were grafted with a monolayer of (3-aminopropyl)triethoxysilane (APTES). A direct functionalization strategy was used to avoid the loss of the MNS magnetization. The successful preparation of the nanoformulation was validated by structural, microstructural, and magnetic investigations. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) were used to establish the presence of APTES on the MNS surface. The amine content quantified by a ninhydrin assay revealed the monolayer coverage of APTES over MNS. The monolayer coverage of APTES reduced only negligibly the saturation magnetization from 77 emu/g (for MNS) to 74 emu/g (for MNS-APTES). Detailed investigations of the thermoremanent magnetization were carried out to assess the superparamagnetism in the MNS. To make the nanoformulation pH-responsive, the anticancerous drug Nintedanib (NTD) was conjugated with MNS-APTES through the acid liable imine bond. At pH 5.5, which mimics a cancerous environment, a controlled release of 85% in 48 h was observed. On the other hand, prolonged release of NTD was found at physiological conditions (i.e., pH 7.4). In vitro cytotoxicity study showed dose-dependent activity of MNS-APTES-NTD for human lung cancer cells L-132. About 75% reduction in cellular viability for a 100 µg/mL concentration of nanoformulation was observed. The nanoformulation designed using MNS and monolayer coverage of APTES has potential in cancer therapy as well as in other nanobiological applications.

Index matching in multilayered organic waveguides.

Index matching of guided modes in birefringent multilayered organic waveguides opens new prospects for the design of mode coupling and mode switching devices. We demonstrate index matching of guided modes in two multilayered structures, in (a) a PTCDA-Alq3-PTCDA three-layer and (b) a PTCDA-Alq3 effective medium multilayer waveguide. The optical waveguides were grown on a Pyrex substrate by organic molecular beam deposition. The occurrence of index matching was investigated both experimentally by measuring the effective refractive index dispersion of transverse electric and magnetic modes using the m-line technique and theoretically by modelling the index dispersion with a transfer matrix algorithm.

Pulsed laser deposited CoFe2O4 thin films as supercapacitor electrodes.

The influence of the substrate temperature on pulsed laser deposited (PLD) CoFe2O4 thin films for supercapacitor electrodes was thoroughly investigated. X-ray diffractometry and Raman spectroscopic analyses confirmed the formation of CoFe2O4 phase for films deposited at a substrate temperature of 450 °C. Topography and surface smoothness was measured using atomic force microscopy. We observed that the films deposited at room temperature showed improved electrochemical performance and supercapacitive properties compared to those of films deposited at 450 °C. Specific capacitances of about 777.4 F g-1 and 258.5 F g-1 were obtained for electrodes deposited at RT and 450 °C, respectively, at 0.5 mA cm-2 current density. The CoFe2O4 films deposited at room temperature exhibited an excellent power density (3277 W kg-1) and energy density (17 W h kg-1). Using electrochemical impedance spectroscopy, the series resistance and charge transfer resistance were found to be 1.1 Ω and 1.5 Ω, respectively. The cyclic stability was increased up to 125% after 1500 cycles due to the increasing electroactive surface of CoFe2O4 along with the fast electron and ion transport at the surface.

Resonant tip-enhanced Raman scattering by CdSe nanocrystals on plasmonic substrates.

Tip-enhanced Raman scattering (TERS) has recently emerged as a powerful technique for studying the local properties of low dimensional materials. Being a plasmon driven system, a dramatic enhancement of the TERS sensitivity can be achieved by an appropriate choice of the plasmonic substrate in the so-called gap-mode configuration. Here, we investigate the phonon properties of CdSe nanocrystals (NCs) utilizing gap-mode TERS. Using the Langmuir-Blodgett technique, we homogeneously deposited submonolayers of colloidal CdSe NCs on two different nanostructured plasmonic substrates. Amplified by resonant gap-mode TERS, the scattering by the optical phonon modes of CdSe NCs is markedly enhanced making it possible to observe up to the third overtone of the LO mode reliably. The home-made plasmonic substrates and TERS tips allow the analysis of the TERS images of CdSe phonon modes with nanometer spatial resolution. The CdSe phonon scattering intensity is strongly correlated with the local electromagnetic field distribution across the plasmonic substrates.

The influence of shell parameters on phonons in core-shell nanoparticles: a resonant Raman study.

The effect of shells of various thicknesses on the vibrational resonant Raman spectra of CdSe/ZnS core-shell nanoparticles is studied. The dependence of the core-shell structure on the method of shell deposition is derived from a comparison of the vibrational and photoluminescence spectra of nanoparticles. Along with the appearance of peaks attributed to the shell, the phonon spectrum of the core undergoes significant changes upon shell growth. The change of the CdSe LO peak lineshape in core-shell nanoparticles is discussed with respect to possible changes in the spectrum of both optical and acoustical phonons upon shell formation. Based on the observed decrease of the CdSe 2LO/LO peak intensity ratio, a weakening of exciton coupling to the CdSe LO phonon upon ZnS shell deposition is supposed. The change in the carrier localization volumes upon shell formation is discussed as a possible reason for the reduced coupling.

Localized surface curvature artifacts in tip-enhanced nanospectroscopy imaging.

Tip-enhanced Raman spectroscopy (TERS) allows the chemical analysis with a spatial resolution at the nanoscale, well beyond what the diffraction limit of light makes possible. We can further boost the TERS sensitivity by using a metallic substrate in the so-called gap-mode TERS. In this context, the goal of this work is to provide a generalized view of imaging artifacts in TERS and near-field imaging that occur due to tip-sample coupling. Contrary to the case of gap-mode with a flat substrate where the size of the enhanced region is smaller than the tip size when visualizing 3D nanostructures the tip convolution effect may broaden the observed dimensions due to the local curvature of the sample. This effect is particularly critical considering that most works on gap-mode TERS consider a perfectly flat substrate which is rarely the case in actual experiments. We investigate a range of substrates to evidence these geometrical effects and to obtain an understanding of the nanoscale curvature role in TERS imaging. Our experimental results are complemented by numerical simulations and an analogy with atomic force microscopy artifacts is introduced. As a result, this work offers a useful analysis of gap-mode TERS imaging with tip- and substrate-related artifacts furthering our understanding and the reliability of near-field optical nanospectroscopy.

Identification of potentially mobile and persistent transformation products of REACH-registered chemicals and their occurrence in surface waters.

Transformation of industrial chemicals might be a significant source of hitherto unknown persistent and mobile organic contaminants (PMOC, PM chemicals) present in the aquatic environment. Herein we depicted a three-step strategy consisting of (I) the prioritization of potential PMOC precursors among REACH-registered chemicals, (II) their lab scale transformation through hydrolysis, photolysis, MnO2 oxidation, and biotransformation and subsequent structural elucidation of derived transformation products, and finally (III) the assessment of their environmental relevance. The proposed procedure was utilized to investigate eleven chemicals, for nine of which a concentration reduction was observed. For six of these chemicals transformation products were at least tentatively identified and partially confirmed with a commercially available reference standard. Retrospective assessment of high-performance liquid chromatography - high-resolution mass spectrometry data as well as a target screening method for the identified TPs and some of the prioritized REACH chemicals revealed the widespread presence of the following chemicals in the environment: 2-pyrrolidone (hydrolysis product of vinylpyrrolidone), TP 216 (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-acetic acid, biotransformation product of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-ethanol), and 1,3-diphenylguanidine (prioritized chemical with experimental evidence of environmental stability). 2-Pyrrolidone was detected in 23/25 investigated surface water samples and present in concentrations of up to 400 ng/L. TP 216 was detected in 20/25 surface water samples and an additional sampling of a waste water treatment plant and the receiving surface water confirmed that TP 216 is formed in waste water treatment plants. The vulcanisation agent 1,3-diphenylguanidine was present in all investigated samples. A leaching experiment with a tire suggested that tires and thus tire wear particles are a potential source of 1,3-diphenylguanidine. With these data the depicted approach was proven successful and suitable for true unknowns like TP 216, and thus an alternative to non-target screenings or suspect-screenings with predicted TPs to identify environmentally relevant transformation products.