Table of contents

Photocatalysis attracts currently intense research since it can provide efficient routes for generating solar fuels and allows to apply sunlight for an environmentally friendly synthesis of valuable chemical compounds. Accordingly, in future photocatalysis may contribute significantly to a sustainable economy. However, up to now photocatalysis has made it only into some niche applications. The reasons are manifold including too low yields, insufficient stability, and scarce availability of the precious metals and rare earths used in most cases. The design of better systems is the goal of many research activities. They call for a detailed knowledge of the individual steps and the microscopic mechanisms.

Time-resolved spectroscopy is a powerful tool to improve our understanding of the individual steps of a photocatalytic process and of the efficiencies and losses associated with them. This allows to address specific weaknesses of the components of a photocatalytic system and to pursue a rational design of the corresponding compounds. In this review an overview is given about what insights can be gained by time-resolved spectroscopy referring mostly to our own results while it has to be stressed that many other groups are also highly successfully working in this area. We restrict ourselves to homogeneous systems which are often easier to analyze and focus on the primary steps occurring after optical excitation. This includes intramolecular relaxation and intersystem crossing in the photosensitizer as well as the first electron transfer step resulting from the interaction of the sensitizer with other components of the system. Ultrafast pump-probe spectroscopy turns out to be particularly helpful in analyzing new photosensitizers based on abundant metals, i.e. copper and iron. These sensitizers can suffer from short lifetimes of the metal-to-ligand charge transfer states which are typically involved in the intermolecular charge transfer processes. The latter are investigated on the pico- to microsecond timescale by quenching experiments making use of a streak camera and by pump-probe spectroscopy applying a YAG-laser system for excitation. The experiments with the streak camera allow to discriminate between oxidative and reductive pathways and to determine the corresponding bimolecular quenching rates which are compared to their diffusion limit to obtain a measure for the quenching efficiency. By applying transient absorption spectroscopy, it is furthermore possible to observe appearing charge transfer products and to determine their concentrations. In this way the efficiency of the electron transfer itself can be deduced and the relevance of lossy quenching events can be estimated.

The diversity of thermal transport properties in carbon nanomaterials enables them to be used in different thermal fields such as heat dissipation, thermal management, and thermoelectric conversion. In the past two decades, much effort has been devoted to study the thermal conductivities of different carbon nanomaterials. In this review, different theoretical methods and experimental techniques for investigating thermal transport in nanosystems are first summarized. Then, the thermal transport properties of various pure carbon nanomaterials including 1D carbon nanotubes, 2D graphene, 3D carbon foam, are reviewed in details and the associated underlying physical mechanisms are presented. Meanwhile, we discuss several important influences on the thermal conductivities of carbon nanomaterials, including size, structural defects, chemisorption and strain. Moreover, we introduce different nanostructuring pathways to manipulate the thermal conductivities of carbon-based nanocomposites and focus on the wave nature of phonons for controlling thermal transport. At last, we briefly review the potential applications of carbon nanomaterials in the fields of thermal devices and thermoelectric conversion.

The controlled generation of non-classical states of light is a challenging task at the heart of quantum optics. Aside from the mere spirit of science, the related research is strongly driven by applications in photonic quantum technologies, including the fields of quantum communication, quantum computation, and quantum metrology. In this context, the realization of integrated solid-state-based quantum-light sources is of particular interest, due to the prospects for scalability and device integration.

This topical review focuses on solid-state quantum-light sources which are fabricated in a deterministic fashion. In this framework we cover quantum emitters represented by semiconductor quantum dots, colour centres in diamond, and defect-/strain-centres in two-dimensional materials. First, we introduce the topic of quantum-light sources and non-classical light generation for applications in photonic quantum technologies, motivating the need for the development of scalable device technologies to push the field towards real-world applications. In the second part, we summarize material systems hosting quantum emitters in the solid-state. The third part reviews deterministic fabrication techniques and comparatively discusses their advantages and disadvantages. The techniques are classified in bottom–up approaches, exploiting the site-controlled positioning of the quantum emitters themselves, and top–down approaches, allowing for the precise alignment of photonic microstructures to pre-selected quantum emitters. Special emphasis is put on the progress achieved in the development of in situ techniques, which significantly pushed the performance of quantum-light sources towards applications. Additionally, we discuss hybrid approaches, exploiting pick-and-place techniques or wafer-bonding. The fourth part presents state-of-the-art quantum-dot quantum-light sources based on the fabrication techniques presented in the previous sections, which feature engineered functionality and enhanced photon collection efficiency. The article closes by highlighting recent applications of deterministic solid-state-based quantum-light sources in the fields of quantum communication, quantum computing, and quantum metrology, and by discussing future perspectives in the field of solid-state quantum-light sources.

A combined experimental and simulation study is carried out to compare the properties of amorphous Ni_100−xP_x alloys obtained by electroless deposition and rapid melt-quenching. The onset of crystallization of experimental electroless deposited amorphous films is measured by differential scanning calorimetry experiments. Classical molecular dynamics simulations using Embedded Atom Model-based interactions are performed to obtain glassy Ni–P by melt-quenching the liquid with various quenching rates, as well as via low-energy chemical deposition to mimic experimental electroless deposition. It is shown that the deposited amorphous and glassy states display similar short-range order. The amorphous deposit corresponds to a glassy state obtained with a cooling rate of 10⁹ K s⁻¹, indicating that deposition yields generally more relaxed amorphous structures. The appearance of phosphorus-enriched surface on the simulated deposited thin film, comparable to experimental observations, is discussed.

The precisely controlled growth of transition metal dichalcogenide (TMDC) monolayers requires sensitive and nondestructive techniques to monitor the morphology and coverage in situ and in real time. In the current work, differential reflectance spectroscopy (DRS) was applied to monitor the molecular beam epitaxy (MBE) growth of atomically thin MoSe₂ layers on mica. The optical evolution exhibits an oscillation with monolayer periodicity, revealing a two-dimensional (2D) layer-by-layer growth of the MoSe₂ thin films. The observed sensitivity of DRS to the step density is associated to the modified electronic structures at the edges of TMDC monolayers. As DRS works in any transparent ambient, we speculate that it could be of great use for realizing precisely controlled growth of TMDC monolayers using not only MBE but also chemical vapor deposition (CVD).

Various graphene morphologies (compact hexagonal, dendritic, and circular domains) have been observed during chemical vapor deposition (CVD) growth on Cu substrate. The existing all-atom kinetic Monte Carlo (kMC) models, however, are unable to reproduce all these graphene morphologies, suggesting that some crucial atomistic events that dictate the morphology are missing. In this work, we propose an all-atom kMC model to simulate the graphene CVD growth on Cu substrate. Besides the usual atomistic events, such as the deposition and diffusion of carbon species on the substrate, and their attachments to the edge, we further include three other important events, that is, the edge attachment of carbon species to form a kink, the diffusion of carbon species along the edge, and the rotation of dimers to form kinks. All the energetic parameters of these events are obtained from first-principles calculations. With this new model, we successfully predict the growth of various graphene morphologies, which are consistent with the morphology phase diagram. In addition to confirming that carbon dimers are the dominant feeding species, we also find that the dominance level depends on the growth flux and temperature. Therefore, the proposed model is able to capture the growth kinetics, providing a useful tool for controlled synthesis of graphene with desired morphologies.

The energy spectrum and local current patterns in graphene quantum dots (QD) are investigated for different geometries in the presence of an external perpendicular magnetic field. Our results demonstrate that, for specific geometries and edge configurations, the QD exhibits vortex and anti-vortex patterns in the local current density, in close analogy to the vortex patterns observed in the probability density current of semiconductor QD, as well as in the order parameter of mesoscopic superconductors.

The crucial role of magnetostatic interactions in tuning properties of storage devices based on magnetic nanowires (NWs) has recently been highlighted by advanced characterization techniques including the first-order reversal curve (FORC) analysis, evaluating physical entities constituting conventional 2D NW systems. Herein, FORC diagrams of ferromagnetic (FM)/non-magnetic (NM) multilayered NW arrays are simulated using Monte Carlo calculations, involving magnetostatic interactions between segments in 3D space. The FM length is constant to 6 µm whereas the NM length (L_NM) varies from 10 to 300 nm, significantly influencing interwire and intrasegment interactions of neighboring NWs and coupled segments along the NW length. Intriguingly, this is accompanied with the emergence of two new FORC diagram features in addition to the typical demagnetizing-type feature, indicating complex behavior of the 3D interacting NWs with the same anisotropy field for each FM segment. The FORC coercivity of the emerging features is tracked individually, presenting evolution as a function of L_NM. Our results also evidence an increase in interwire and intrasegment interactions when increasing NW diameter, being in accordance with total magnetostatic energy calculations.

The physical properties of itinerant ferromagnet -Co₅Ge₃ with both strong disorder and spin fluctuations was studied. The dc and ac susceptibility show that both spin fluctuations and disorder dominate the physical properties. In the spin glass phase, with a coexisting ferromagnetic state (30 K), both non-Fermi liquid behavior and large exponent of scaling relation of are observed and attributed to the spin fluctuations and disorder induced by cobalt defects. Upon the increase of external field, Fermi liquid behavior restores due to the suppression of spin fluctuations and disorder. In addition, a large anomalous Hall coefficient R_s is observed. Our results suggest that -Co₅Ge₃ is a typical itinerant ferromagnet to explore the interplay of disorder and spin fluctuations.

The magnetic glassy state is a fascinating phenomenon, which results from the kinetic arrest of the first order magnetic phase transition. Interesting properties, such as metastable magnetization and nonequilibrium magnetic phases, are naturally developed in the magnetic glassy state. Here, we report magnetic glass property in the low spin state of Co³⁺ in EuBaCo₂O_5+δ (δ  =  0.47) cobaltite at low temperature (T  <  60 K). The measurements of magnetization under the cooling and heating in unequal fields, magnetization relaxation and thermal cycling of magnetization show the kinetic arrest of low magnetization state below 60 K. The kinetically arrested low temperature magnetic phase is further supported through the study of isothermal magnetic entropy, which shows the significant entropy change. The present results will open a new window to search the microscopic relation between the spin state transitions and the kinetic arrest induced magnetic glassy phenomena in complex materials.

We systematically investigated the magnetic properties of a single crystal bulk Fe₃O₄ at low temperatures. Below Verwey transition, the magnetization versus temperature curves under zero-field cooling present anomalous behaviors for [1 0 0], [1 0 1] and [0 0 1] directions, respectively. Furthermore, at Verwey temperature, a high sensitivity of relative magnetization change (ΔM/M) to small magnetic field and, in particular, a reversal of ΔM/M at moderate magnetic field range for [0 0 1] direction is observed. Our work demonstrates a very important role of magnetic axis reorientation effect in low temperature magnetic properties of magnetite, which will stimulate further research on the intricate microscopic physics mechanisms in this classic material.

Density functional theory (DFT) has become a standard method for ab initio calculations of material properties. However, it has a number of shortcomings, particularly in predicting key properties, such as band gap and optical spectra, which are dependent on excited states. To treat such properties, more accurate approaches such as GW or DFT with hybrid functionals (including HSE, PBE0, and B3LYP, to name a few) can be employed; however, these approaches are unfeasible for many large and/or complex systems due to their high computational cost and large memory requirements. In this work, we investigate the ability to train neural networks of the traditional DFT charge density computed with a standard PBE functional to accurately predict HSE band gaps. We show that a single network PBE charge density functional can predict the HSE band gap of seven different materials—silicon, gallium arsenide, molybdenum disulfide, germanium, tin phosphate, titanium phosphate, and zirconium phosphate—under a wide variety of conditions with an RSME of 172.6 meV, which is 34% better accuracy than standard regression between the PBE and HSE band gaps. This approach, which, in principle, can be used to map PBE charge densities to band gaps or other properties computed with any higher accuracy method, has the potential to decrease computational costs, increase prediction accuracy, and enable accurate high-throughput screening for a wide variety of complex materials systems.

By processing graphene quantum dot, an ideal semiconductor material with suitable band gap and higher electron mobility can be obtained. Thus, it has a broad prospect in the application of photoelectric response materials. Here, a graphene defect with porphyrin-like structure is selected to achieve the controlable light absorption. The double five-membered-ring parallel vacancy are based on self-healing properties of popular graphene defects. Aimed to separate exciton and hole more effectively and achieve higher photoelectric conversion efficiency, the occupied orbital and unoccupied orbital of the quantum dot with objected defect structure is taken as orderly dispersion to form an obvious charge separation state under the demonstration with first principles calculation. Most importantly, a real time real space charge separation is calculated by time-dependent ab-initio quantum dynamics based on numerical atomic basis sets. The result shows the specific graphene defects can form an efficient pure graphene photoelectric response medium like porphyrin skeleton, and the vacancy will induce to adjust and control the specific wavelength of the response light and charge separated state manipulably with odevity of number of peripheral carbon rings by the calculation of ultrafast process.