Resonant Tip-Enhanced Raman Spectroscopy of a Single-Molecule Kondo System.

Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. TERS capability of reflecting spin states in open-shell molecular configurations is yet unexplored. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state. These findings highlight the potential of TERS in capturing complex interactions between charge, spin, and photophysical properties in nanoscale molecular systems and suggest a pathway for designing single-molecule spin-optical devices.

Light-Controlled Multiconfigurational Conductance Switching in a Single 1D Metal-Organic Wire.

Precise control of multiple spin states on the atomic scale presents a promising avenue for designing and realizing magnetic switches. Despite substantial progress in recent decades, the challenge of achieving control over multiconfigurational reversible switches in low-dimensional nanostructures persists. Our work demonstrates multiple, fully reversible plasmon-driven spin-crossover switches in a single π-d metal-organic chain suspended between two electrodes. The plasmonic nanocavity stimulated by external visible light allows for reversible spin crossover between low- and high-spin states of different cobalt centers within the chain. We show that the distinct spin configurations remain stable for minutes under cryogenic conditions and can be nonperturbatively detected by conductance measurements. This multiconfigurational plasmon-driven spin-crossover demonstration extends the available toolset for designing optoelectrical molecular devices based on SCO compounds.

Single-Molecule Time-Resolved Spectroscopy in a Tunable STM Nanocavity.

Spontaneous fluorescence rates of single-molecule emitters are typically on the order of nanoseconds. However, coupling them with plasmonic nanostructures can substantially increase their fluorescence yields. The confinement between a tip and sample in a scanning tunneling microscope creates a tunable nanocavity, an ideal platform for exploring the yields and excitation decay rates of single-molecule emitters, depending on their coupling strength to the nanocavity. With such a setup, we determine the excitation lifetimes from the direct time-resolved measurements of phthalocyanine fluorescence decays, decoupled from the metal substrates by ultrathin NaCl layers. We find that when the tip is approached to single molecules, their lifetimes are reduced to the picosecond range due to the effect of coupling with the tip-sample nanocavity. On the other hand, ensembles of the adsorbed molecules measured without the nanocavity manifest nanosecond-range lifetimes. This approach overcomes the drawbacks associated with the estimation of lifetimes for single molecules from their respective emission line widths.

Kinetics of Nickel Diffusion into Austenitic Stainless Steels AISI 304 and 316L and Calculation of Diffusion Coefficients.

Diffusion bonding has many advantages, but it also has its specifics. When creating heterogeneous joints, problems arise with the creation of intermetallic phases. For this reason, an interlayer is needed to prevent the creation of these unfavorable phases. It is important to ensure that the interlayer is of sufficient thickness to prevent the elements from diffusing through the entire interlayer and the intermetallic phases from being formed again. Conversely, too thick an interlayer causes an increase in the heterogeneity of the bond properties. The creation of the initial diffusion bonds in a heterogeneous diffusion joint of AISI 304 and AISI 316L steel with a 0.2 mm thick nickel interlayer was made in a Gleeble 3500. The experiments to determine the diffusion kinetics were carried out in a vacuum furnace, with subsequent evaluation by EDX (Energy Dispersive X-ray Spectroscopy) analysis. Subsequently, the diffusion coefficients of nickel into both steels were determined, and generalized equations were formulated to calculate the diffusion coefficients for temperatures in the range of 950 to 1150 °C and holding times in the range of 3600 to 18,000 s. Equations are also given to determine the width of the diffused zone between each steel and the Ni interlayer.

Comparison of the Structure, Mechanical Properties and Effect of Heat Treatment on Alloy Inconel 718 Produced by Conventional Technology and by Additive Layer Manufacturing.

The nickel-iron-based alloy Inconel 718 is a progressive material with very good mechanical properties at elevated and lower temperatures. It is used both as wrought and cast alloys as well as material for additive manufacturing technologies. This is the reason why it has received so much attention, as supported by numerous publications. However, these are almost exclusively focused on a specific type of production and processing, and thus only report differences in the mechanical properties between samples prepared by different technologies. Therefore, the major aim of this research was to show how the structure and mechanical properties differ between samples produced by conventional production (wrought alloy) and additively manufactured SLM (Selective Laser Melting). It is shown that by applying appropriate heat treatment, similar strength properties at room and elevated temperatures can be achieved for SLM samples as for wrought samples. In addition, the mechanical properties are also tested up to a temperature of 900 °C, in contrast to the results published so far. Furthermore, it is proven that the microstructures of the wrought (here rolled) and SLM alloys differ significantly both in terms of grain shape and the size and distribution of precipitates.

Gate-Tunable Renormalization of Spin-Correlated Flat-Band States and Bandgap in a 2D Magnetic Insulator.

Emergent quantum phenomena in two-dimensional van der Waal (vdW) magnets are largely governed by the interplay between exchange and Coulomb interactions. The ability to precisely tune the Coulomb interaction enables the control of spin-correlated flat-band states, band gap, and unconventional magnetism in such strongly correlated materials. Here, we demonstrate a gate-tunable renormalization of spin-correlated flat-band states and bandgap in magnetic chromium tribromide (CrBr3) monolayers grown on graphene. Our gate-dependent scanning tunneling spectroscopy (STS) studies reveal that the interflat-band spacing and bandgap of CrBr3 can be continuously tuned by 120 and 240 meV, respectively, via electrostatic injection of carriers into the hybrid CrBr3/graphene system. This can be attributed to the self-screening of CrBr3 arising from the gate-induced carriers injected into CrBr3, which dominates over the weakened remote screening of the graphene substrate due to the decreased carrier density in graphene. Precise tuning of the spin-correlated flat-band states and bandgap in 2D magnets via electrostatic modulation of Coulomb interactions not only provides effective strategies for optimizing the spin transport channels but also may exert a crucial influence on the exchange energy and spin-wave gap, which could raise the critical temperature for magnetic order.

Surface-Mediated Spin Locking and Thermal Unlocking in a 2D Molecular Array.

Molecule-based functional devices may take advantage of surface-mediated spin state bistability. Whereas different spin states in conventional spin crossover complexes are only accessible at temperatures well below room temperature, and the lifetimes of the high-spin state are relatively short, a different behavior exhibited by prototypical nickel phthalocyanine is shown here. Direct interaction of the organometallic complex with a copper metal electrode mediates the coexistence of a high spin and a low spin state within the 2D molecular array. The spin state bistability is extremely non-volatile, since no external stimuli are required to preserve it. It originates from the surface-induced axial displacement of the functional nickel cores, which generates two stable local minima. Spin state unlocking and the full conversion to the low spin state are only possible by a high temperature stimulus. This spin state transition is accompanied by distinct changes in the molecular electronic structure that might facilitate the state readout at room temperature, as evidenced by valence spectroscopy. The non-volatility of the high spin state up to elevated temperatures and the controllable spin bistability render the system extremely intriguing for applications in molecule-based information storage devices.

Determination of Grain Growth Kinetics of S960MC Steel.

Fine-grained high-strength low-alloyed (HSLA) steels are used for their advantageous combination of mechanical properties such as high yield strength, tensile strength, ductility, and good formability. These properties are mainly based on applied grain boundary strengthening, which as the only strengthening mechanism allows for the yield strength to increase without a decrease in ductility. Therefore, any changes in grain size lead to irreversible changes in material properties. Such changes also occur during welding in the heat-affected zone (HAZ), where there is a significant change in austenitic grain. In coarse-grain HAZ, this leads to a decrease in yield strength, ductility, toughness, and fatigue strength. The paper experimentally determines the growth kinetics of austenitic grain for fine-grained HSLA steel S960MC. As a result, the values of the activation energy required for grain growth Q and the proportional constant K0 are determined. Knowing these values is important for numerical predictions of austenitic grain size in the HAZ. Based on these predictions, the changes in yield strength, ductility, toughness, and fatigue strength can be estimated.

Role of the Magnetic Anisotropy in Atomic-Spin Sensing of 1D Molecular Chains.

One-dimensional metal-organic chains often possess a complex magnetic structure susceptible to modification by alteration of their chemical composition. The possibility to tune their magnetic properties provides an interesting playground to explore quasi-particle interactions in low-dimensional systems. Despite the great effort invested so far, a detailed understanding of the interactions governing the electronic and magnetic properties of the low-dimensional systems is still incomplete. One of the reasons is the limited ability to characterize their magnetic properties at the atomic scale. Here, we provide a comprehensive study of the magnetic properties of metal-organic one-dimensional (1D) coordination polymers consisting of 2,5-diamino-1,4-benzoquinonediimine ligands coordinated with Co or Cr atoms synthesized under ultrahigh-vacuum conditions on a Au(111) surface. A combination of integral X-ray spectroscopy with local-probe inelastic electron tunneling spectroscopy corroborated by multiplet analysis, density functional theory, and inelastic electron tunneling simulations enables us to obtain essential information about their magnetic structures, including the spin magnitude and orientation at the magnetic atoms, as well as the magnetic anisotropy.

Evidence of exciton-libron coupling in chirally adsorbed single molecules.

Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy.

Fe-Al-Si-Type Iron Aluminides: On the Strengthening by Refractory Metals Borides.

The effect of boron addition into Fe-28Al-5Si-X (X = -, 2Mo, or 2Ti) on the structure and high-temperature yield stress was investigated. Generally, the alloying of binary Fe3Al-type iron aluminides by silicon significantly improves high-temperature mechanical properties by solid-solution strengthening. On the other hand, the workability and ductile properties at room or slightly elevated temperatures get worse with the increasing silicon content. Boron alloying together with titanium or molybdenum alloying is one of the ways to improve the workability of this type of alloy and, at the same time, ensure the formation of a sufficient amount of secondary phase particles required for effective strengthening. In this paper, the influence of 1 at. % of boron on high-temperature yield stress is evaluated in response to structural changes and compared with results obtained previously on the same type of alloy (Fe-28Al-5Si-2X, X= -, Mo, or Ti) but without boron alloying. It can be concluded that the network structure of borides of refractory metals formed due to boron alloying works more effectively for alloy hardening at higher temperatures than a mixture of silicides and carbides present in the boron-free alloy of the same composition.

Determination of CCT Diagram by Dilatometry Analysis of High-Strength Low-Alloy S960MC Steel.

High-strength steels are used more than general structural steel due to their combination of properties such as high strength, good toughness and weldability. They are mainly used in the manufacture of heavy vehicles for the mining industry, cranes, transportation, etc. However, welding these grades of steel brings new challenges. Also, a simulation for welding high-strength steel is required more often. To insert a material database into the simulation program, it is necessary to conduct investigations using CCT (Continuous Cooling Transformation) diagrams, welded joints research, and more. To investigate the behavior of S960MC steel during heating and cooling, we used dilatometry analysis supported by EBSD (Electron Backscatter Diffraction) analysis. A CCT diagram was constructed. The transformation temperatures of Ac1 and Ac3 increase with increasing heating rate. The Ac1 temperature increased by 54 °C and the Ac3 temperatures by 24 °C as the heating rate increased from 0.1 °C/s to 250 °C/s. The austenite decomposition temperatures have a decreasing trend in the cooling phase with increasing cooling rate. As the cooling rate changes from 0.03 °C/s to 100 °C/s, the initial transformation temperature drops from 813 °C to 465 °C. An increase in the cooling rate means a higher proportion of bainite and martensite. At the same time, the hardness increases from 119 HV10 to 362 HV10.

Real Space Visualization of Entangled Excitonic States in Charged Molecular Assemblies.

Entanglement of excitons holds great promise for the future of quantum computing, which would use individual molecular dyes as building blocks of their circuitry. Studying entangled excitonic eigenstates emerging in coupled molecular assemblies in the near-field with submolecular resolution has the potential to bring insight into the photophysics of these fascinating quantum phenomena. In contrast to far-field spectroscopies, near-field spectroscopic mapping permits direct identification of the individual eigenmodes, type of exciton coupling, including excited states otherwise inaccessible in the far field (dark states). Here we combine tip-enhanced spectromicroscopy with atomic force microscopy to inspect delocalized single-exciton states of charged molecular assemblies engineered from individual perylenetetracarboxylic dianhydride (PTCDA) molecules. Hyperspectral mapping of the eigenstates and comparison with calculated many-body optical transitions reveals a second low-lying excited state of the anion monomers and its role in the exciton entanglement within the assemblies. We demonstrate control over the exciton coupling by switching the assembly charge states. Our results reveal the possibility of tailoring excitonic properties of organic dye aggregates for advanced functionalities and establish the methodology to address them individually at the nanoscale.

Possibilities to Use Physical Simulations When Studying the Distribution of Residual Stresses in the HAZ of Duplex Steels Welds.

Dual phase steels combine very good corrosion resistance with relatively high values of mechanical properties. In addition, they can maintain good plastic properties and toughness at both room temperature and lower temperatures as well. Despite all the advantages mentioned above, their utility properties can be reduced by technological processing, especially by the application of the temperature cycles. As a result, in the material remain residual stresses with local stress peaks, which are quite problematic especially during cyclic loading. Moreover, determining the level and especially the distribution of such residual stresses is very difficult for duplex steels both due to the structure duality and in light of the very small width of the heat-affected zone (HAZ). This is why the paper presents the possibilities of using physical simulations to study the effect of temperature cycles in residual stresses' magnitude and distribution, where it is possible to study the HAZ in more detail as well as on a much larger sample width due to the utilization of special samples. In the thermal-mechanical simulator Gleeble 3500, temperature-stress cycles were applied to testing samples, generating stress fields with local peaks in the testing samples. In addition, the supplied steel X2CrMnNiN21-5-1 had different phase rations in the individual directions. Therefore, as the residual stresses were measured in several directions and at the same time, it was possible to safely confirm the suitability of the used measurement method. Moreover, the effect of the stress and strain on the change of partial phases' ratios was observed. It has been experimentally confirmed that annealing temperatures of at least 700 °C are required to eliminate local stress peaks after welding. However, an annealing temperature of 550 °C seems to be optimal to maintain sufficient mechanical properties.

Characteristics of Porous Aluminium Materials Produced by Pressing Sodium Chloride into Their Melts.

The paper deals with research related to the production of metal cellular aluminium systems, in which production is based on the application of sodium chloride particles. In this paper, the properties of porous aluminium materials that were produced by an unconventional method-by pressing salt particles into the melt of aluminium alloy-are described. The new methodology was developed and verified for the production of these materials. The main feature of this methodology is a hydraulic forming press and a simple-shaped foundry mould. For these purposes, four different groups of sodium chloride particle sizes (1 to 3, 3 to 5, 5 to 7 and 8 to 10 mm) were applied. The preferred aluminium foundry alloy (AlSi12) was used to produce the porous aluminium samples. Based upon this developed methodology, samples of porous aluminium materials were produced and analysed. Their weight and volume were monitored, their density and relative density were calculated, and their porosity was determined. In addition, the porosity of samples and continuity of their air cells were monitored as well. An industrial computed tomograph and a scanning electron microscope were applied for these purposes.

Resolving Ambiguity of the Kondo Temperature Determination in Mechanically Tunable Single-Molecule Kondo Systems.

Determination of the molecular Kondo temperature (TK) poses a challenge in most cases when the experimental temperature cannot be tuned to a sufficient extent. We show how this ambiguity can be resolved if additional control parameters are present, such as magnetic field and mechanical gating. We record the evolution of the differential conductance by lifting an individual molecule from the metal surface with the tip of a scanning tunneling microscope. By fitting the measured conductance spectra with the single impurity Anderson model we are able to demonstrate that the lifting tunes the junction continuously from the strongly correlated Kondo-singlet to the free spin-1/2 ground state. In the crossover regime, where TK is similar to the temperature of experiment, the fitting yields ambiguous estimates of TK varying by an order of magnitude. We show that analysis of the conductance measured in two distinct external magnetic fields can be used to resolve this problem.

Constant amplitude driving of a radiofrequency excited plasmonic tunnel junction.

Constant-amplitude bias modulation over a broad range of microwave frequencies is a prerequisite for application in high-resolution spectroscopic techniques in a tunneling junction as e.g. electron spin resonance spectroscopy or optically detected paramagnetic resonance. Here, we present an optical method for determining the frequency-dependent magnitude of the transfer function of a dedicated high-frequency line integrated with a scanning probe microscope. The method relies on determining the energy cutoff of the plasmonic electroluminescence spectrum, which is linked to the energies of the electrons inelastically tunneling across the junction. We develop an easy-to-implement procedure for effective compensation of an RF line and determination of the transfer function magnitude in the GHz range. We test our method with conventional electronic calibration and find a perfect agreement.

Effect of Higher Silicon Content and Heat Treatment on Structure Evolution and High-Temperature Behaviour of Fe-28Al-15Si-2Mo Alloy.

This paper describes the structure and properties of cast Fe3Al-based alloy doped with 15 at. % of silicon and 2 at. % of molybdenum. The higher content of silicon is useful for the enhancement of high-temperature mechanical properties or corrosion resistance of iron aluminides but deteriorates their workability due to increased brittleness. It was found that the presence of both alloying elements leads to an increase of values of the high-temperature yield stress in compression. The heat treatment (annealing at 800 °C for 100 h) used for the achievement of phase stability causes the grain coarsening, so the values of the high-temperature yield stress in compression are lower at 600 °C and 700 °C in comparison to values measured for the as-cast state. This stabilization annealing significantly improves the workability/machinability of alloy. Furthermore, the higher silicon content positively affects the values of the thermal expansion coefficient that was found to be lower in the temperature range up to 600 °C compared to alloys with lower content of silicon.

Significance Of Nuclear Quantum Effects In Hydrogen Bonded Molecular Chains.

In hydrogen-bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implications remains elusive, leaving opportunities for deeper understanding to harness their fascinating properties. We studied hydrogen-bonded one-dimensional quinonediimine molecular networks which may adopt two isomeric electronic configurations via proton transfer. Herein, we demonstrate that concerted proton transfer promotes a delocalization of π-electrons along the molecular chain, which enhances the cohesive energy between molecular units, increasing the mechanical stability of the chain and giving rise to distinctive electronic in-gap states localized at the ends. These findings demonstrate the identification of a class of isomeric hydrogen-bonded molecular systems where nuclear quantum effects play a dominant role in establishing their chemical and physical properties. This identification is a step toward the control of mechanical and electronic properties of low-dimensional molecular materials via concerted proton tunneling.

Exciton-Trion Conversion Dynamics in a Single Molecule.

Charged optical excitations (trions) generated by charge carrier injection are crucial for emerging optoelectronic technologies as they can be produced and manipulated by electric fields. Trions and neutral excitons can be efficiently induced in single molecules by means of tip-enhanced spectromicroscopic techniques. However, little is known of the exciton-trion dynamics at single molecule level as this requires methods permitting simultaneous subnanometer and subnanosecond characterization. Here, we investigate exciton-trion dynamics by phase fluorometry, combining radio frequency modulated scanning tunnelling luminescence with time-resolved single photon detection. We generate excitons and trions in single Zinc Phthalocyanine (ZnPc) molecules on NaCl/Ag(111), and trace the evolution of the system in the picosecond range. We explore the dependence of effective lifetimes on bias voltage and describe the conversion mechanism from neutral excitons to trions, via charge capture, as the primary pathway to trion formation. We corroborate the dynamics of the system by a causally deterministic four-state model.