We explore the zero-phonon line of single photon emitters in helium-ion treated monolayer MoS2, which are currently understood in terms of single sulfur-site vacancies. By comparing the linewidths of the zero-phonon line as extracted directly from optical spectra with values inferred from the first-order autocorrelation function of the photoluminescence, we quantify bounds of the homogeneous broadening and of phonon-assisted contributions. The results are discussed in terms of both the independent boson model and ab-initio results as computed from GW and Bethe-Salpeter equation approximations.

We highlight recent advances in the controlled creation of single-photon emitters in van der Waals materials and in the understanding of their atomistic origin. We focus on quantum emitters created in monolayer transition-metal dichalcogenide semiconductors, which provide spectrally sharp single-photon emission at cryogenic temperatures, and the ones in insulating hBN, which provide bright and stable single-photon emission up to room temperature. After introducing the different classes of quantum emitters in terms of band-structure properties, we review the defect creation methods based on electron and ion irradiation as well as local strain engineering and plasma treatments. A main focus of the review is put on discussing the microscopic origin of the quantum emitters as revealed by various experimental platforms, including optical and scanning probe methods.

Hexagonal boron nitride (hBN) hosts luminescent defects possessing spin qualities compatible with quantum sensing protocols at room temperature. Vacancies, in particular, are readily obtained via exposure to high-energy ion beams. While the defect creation mechanism via such irradiation is well understood, the occurrence rate of optically active negatively charged vacancies (V-B) is still an open question. In this work, we exploit focused helium ions to systematically create optically active vacancy defects in hBN flakes at varying densities. By comparing the density-dependent spin splitting measured by magnetic resonance to calculations based on a microscopic charge model, in which we introduce a correction term due to a constant background charge, we are able to quantify the number of V-B defects created by the ion irradiation. We find a lower bound for the fraction (0.2%) of all vacancies in the optically active, negatively charged state. Our results provide a protocol for measuring the creation efficiency of V-B , which is necessary for understanding and optimizing luminescent centers in hBN.

Polarized optical contrast spectroscopy is a simple and non-destructive approach to characterize the crystalline anisotropy and orientation of two-dimensional materials. Here, we develop a 3D-printed motorized polarization module, which is compatible with typical microscope platforms and enables to perform broadband polarization-resolved reflectance spectroscopy. As proof of principle, we investigate the in-plane birefringence of exfoliated \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {MoO}_3$$\end{document} thin films and few-layer \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {WTe}_2$$\end{document} crystals. We compare the measured spectra to a model based on a transfer matrix formalism. Compared to other polarization sensitive approaches, such as Raman or second harmonic generation spectroscopy, optical contrast measurements require orders of magnitude less excitation power densities, which is particularly advantageous to avoid degradation of delicate van der Waals layers.

"Molecular self-assembly offers an effective and scalable way to design nanostructured materials with tunable optoelectronic properties. In the past 30 years, organic chemistry has delivered a plethora of metal-organic structures based on the combination of organic groups, chalcogens, and a broad range of metals. Among these, several layered metal-organic chalcogenides (MOCs)-including ""mithrene"" (AgSePh)-recently emerged as interesting platforms to host 2D physics embedded in 3D crystals. Their combination of broad tunability, easy processability, and promising optoelectronic performance is driving a renewed interest in the more general material group of ""low-dimensional"" hybrids. In addition, the covalent MOC lattice provides higher stability compared with polar materials in operating devices. Here, we provide a perspective on the rise of 2D MOCs in terms of their synthesis approaches, 2D quantum confined exciton physics, and potential future applications in UV and X-ray photodetection, chemical sensors, and electrocatalysis."

We explore the optical dipole orientation of single photon emitters in monolayer MoS2 as produced by a focused helium ion beam. The single photon emitters can be understood as single-sulfur vacancies. The corresponding far-field luminescence spectra reveal several photoluminescence lines below the dominating luminescence of the exciton in MoS2. These sub-bandgap emission lines were predicted by ab initio theory, but they have never been resolved in luminescence experiments because of their small amplitude. We reveal the lines by their dependence as a function of the photon energy and momentum as measured in the back focal plane of the optical circuitry. The agreement between theory and experiment suggests that the defect states interact strongly within the Brillouin zone.

We investigate the interplay between vertical tunneling and lateral transport phenomena in electrically contacted van der Waals heterostructures made from monolayer MoS2, hBN, and graphene. We compare data taken by low-temperature scanning tunneling spectroscopy to results from room-temperature conductive atomic force spectroscopy on monolayer MoS2 with sulfur vacancies and with varying hBN layers. We show that for thick hBN barrier layers, where tunneling currents into the conductive substrate are suppressed, a side-contact still enables addressing the defect states in the scanning tunneling microscopy via the lateral current flow. Few-layer hBN realizes an intermediate regime in which the competition between vertical tunneling and lateral transport needs to be considered. The latter is relevant for device structures with both a thin tunneling barrier and a side-contact to the semiconducting layers.

We demonstrate that graphene-based two-terminal devices allow autocorrelating femtosecond mid-infrared pulses with a pulse duration of about 100 fs in the wavelength regime of 5.5-14 mu m. The results suggest that the underlying ultrafast detection principle relies on an electric field dominated autocorrelation in combination with the optoelectronic dynamics at the metal-graphene interfaces. The demonstrated scheme excels because of the ease in nanofabrication of two-terminal graphene-based optoelectronic devices and their robustness.

In van der Waals materials, external strain is an effective tool to manipulate and control electronic responses by changing the electronic bands upon lattice deformation. In particular, the band gap of the layered transition metal pentatelluride HfTe5 is sufficiently small to be inverted by subtle changes of the lattice parameters resulting in a strain-tunable topological phase transition. In that case, knowledge about the spatial homogeneity of electronic properties becomes crucial, especially for the microfabricated thin film circuits used in typical transport measurements. Here, we reveal the homogeneity of exfoliated HfTe5 thin films by spatially resolved Raman microscopy. Comparing the Raman spectra under applied external strain to unstrained bulk references, we pinpoint local variations of Raman signatures to inhomogeneous strain profiles in the sample. Importantly, our results demonstrate that microfabricated contacts can act as sources of significant inhomogeneities. To mitigate the impact of unintentional strain and its corresponding modifications of the electronic structure, careful Raman microscopy constitutes a valuable tool for quantifying the homogeneity of HfTe5 films and circuits fabricated thereof.

The quantum geometric Berry curvature results in an anomalous correction to the band velocity of crystal electrons with a corresponding transverse (thermo)electric conductivity. However, time-reversal symmetry typically constrains the direct observation and exploitation of anomalous transport to magnetic compounds. Here, it is demonstrated the anomalous Hall and Nernst conductivities are essential for describing the optoelectronic transport in thin films of the non-magnetic, weakly gapped semimetal HfTe5 subject to an external magnetic field. A focused photoexcitation adresses the symmetries of the local Nernst conductivity, which unveils a hitherto hidden, anomalous photo-Nernst effect of three-dimensional (3D) massive Dirac fermions. The experimental temperature and density dependencies are compared with a semiclassical Boltzmann transport model. For HfTe5 thin films with the Fermi level close to the gap, the model suggests that the anomalous photo-Nernst currents originate from an intrinsic Berry curvature mechanism, where the Zeeman interaction effectively breaks time-reversal symmetry of the massive Dirac fermions already at moderate external magnetic fields.

We report on the optical absorption characteristics of selectively positioned sulfur vacancies in monolayer MoS2, as observed by photovoltage and photocurrent experiments in an atomistic vertical tunneling circuit at cryogenic and room temperature. Charge carriers are resonantly photoexcited within the defect states before they tunnel through an hBN tunneling barrier to a graphene-based drain contact. Both photovoltage and photocurrent characteristics confirm the optical absorption spectrum as derived from ab initio GW and Bethe-Salpeter equation approximations. Our results reveal the potential of single-vacancy tunneling devices as atomic-scale photodiodes.

The two-dimensional material hexagonal boron nitride (hBN) hosts luminescent centres with emission energies of ~2 eV which exhibit pronounced phonon sidebands. We investigate the microscopic origin of these luminescent centres by combining ab initio calculations with non-perturbative open quantum system theory to study the emission and absorption properties of 26 defect transitions. Comparing the calculated line shapes with experiments we narrow down the microscopic origin to three carbon-based defects: C2CB, C2CN, and VNCB. The theoretical method developed enables us to calculate so-called photoluminescence excitation (PLE) maps, which show excellent agreement with our experiments. The latter resolves higher-order phonon transitions, thereby confirming both the vibronic structure of the optical transition and the phonon-assisted excitation mechanism with a phonon energy ~170 meV. We believe that the presented experiments and polaron-based method accurately describe luminescent centres in hBN and will help to identify their microscopic origin.

Single spin-defects in 2D transition-metal dichalcogenides are natural spin-photon interfaces for quantum applications. Here we report high-field magneto-photoluminescence spectroscopy from three emission lines (Q1, Q2, and Q*) of He-ion induced sulfur vacancies in monolayer MoS2. Analysis of the asymmetric PL lineshapes in combination with the diamagnetic shift of Q1 and Q2 yields a consistent picture of localized emitters with a wave function extent of similar to 3.5 nm. The distinct valley-Zeeman splitting in out-of-plane B-fields and the brightening of dark states through in-plane B-fields necessitates spin-valley selectivity of the defect states and lifted spin-degeneracy at zero field. Comparing our results to ab initio calculations identifies the nature of Q1 and Q2 and suggests that Q* is the emission from a chemically functionalized defect. Analysis of the optical degree of circular polarization reveals that the Fermi level is a parameter that enables the tunability of the emitter. These results show that defects in 2D semiconductors may be utilized for quantum technologies.

We utilize cavity-enhanced extinction spectroscopy to directly quantify the optical absorption of defects in MoS2 generated by helium ion bombardment. We achieve hyperspectral imaging of specific defect patterns with a detection limit below 0.01% extinction, corresponding to a detectable defect density below 1 x 10(11) cm(-2). The corresponding spectra reveal a broad subgap absorption, being consistent with theoretical predictions related to sulfur vacancy-bound excitons in MoS2. Our results highlight cavity-enhanced extinction spectroscopy as efficient means for the detection of optical transitions in nanoscale thin films with weak absorption, applicable to a broad range of materials.

We demonstrate that optically active emitters can be locally generated by focusing a He-ion beam onto monolayer WS2 encapsulated in hBN. The emitters show a low-temperature photoluminescence spectrum, which is well described by an independent Boson model for localized emitters. Consistently, the photoluminescence intensity of the emitters saturates at low excitation intensities, which is distinct to the photoluminescence of excitonic transitions in the investigated WS2 monolayers. The demonstrated method allows us to position defect emitters in WS2 monolayers on demand. A statistical analysis suggests the generation yield of individual emitters to be as high as 11% at the highest investigated He-ion doses.

The ability to dope transition metal dichalcogenides such as tungsten diselenide (WSe2) with magnetic transition metal atoms in a controlled manner has motivated intense research with the aim of generating dilute magnetic semiconductors. In this work, semiconducting WSe2 monolayers, substitutionally doped with vanadium atoms, are investigated using low-temperature luminescence and optoelectronic spectroscopy. V-dopants lead to a p-type doping character and an impurity-related emission approximate to 160 meV below the neutral exciton, both of which scale with the nominal percentage of V-dopants. Measurements using field-effect devices of 0.3% V-doped WSe2 demonstrate bipolar carrier tunability. The doped monolayers display a clear magnetic hysteresis in transport measurements both under illumination and without illumination, whereas the valley polarization of the excitons reveals a nonlinear g-factor without a magnetic hysteresis within the experimental uncertainty. Hence, this work on V-doped WSe2 provides crucial insights concerning suitable characterization methods on magnetic properties of doped 2D materials.

van der Waals heterostructures made from graphene and three-dimensional topological insulators promise very high electron mobilities, a nontrivial spin texture, and a gate-tunability of electronic properties. Such a combination of advantageous electronic characteristics can only be achieved through proximity effects in heterostructures, as graphene lacks a large enough spin-orbit interaction. In turn, the heterostructures are promising candidates for all-electrical control of proximity -induced spin phenomena. Here, we explore epitaxially grown interfaces between graphene and the lattice-matched topological insulator Bi2Te2Se. For this heterostructure, spin-orbit coupling proximity has been predicted to impart an anisotropic and electronically tunable spin texture. Polarization-resolved second -harmonic generation, Raman spectroscopy, and time-resolved magneto-optic Kerr microscopy are combined to demonstrate that the atomic interfaces align in a commensurate symmetry with characteristic interlayer vibrations. By polarization-resolved photocurrent measurements, we find a circular photogalvanic effect which is drastically enhanced at the Dirac point of the proximitized graphene. We attribute the peculiar gate-tunability to the proximity-induced interfacial spin structure, which could be exploited for, e.g., spin filters.

Transition metal dichalcogenides (TMDs) receive significant attention due to their outstanding electronic and optical properties. In this study, we investigate the electronic, optical, and thermoelectric properties of single and few layer WTe2 in detail utilizing first-principles methods based on the density functional theory (DFT). Within the scope of both PBE and HSE06 including spin orbit coupling (SOC), the simulations predict the electronic band gap values to decrease as the number of layers increases. Moreover, spin-polarized DFT calculations combined with the semi-classical Boltzmann transport theory are applied to estimate the anisotropic thermoelectric power factor (Seebeck coefficient, S) for WTe2 in both the monolayer and multilayer limit, and S is obtained below the optimal value for practical applications. The optical absorbance of WTe2 monolayer is obtained to be slightly less than the values reported in literature for 2H TMD monolayers of MoS2, MoSe2, and WS2. Furthermore, we simulate the impact of defects, such as vacancy, antisite and substitution defects, on the electronic, optical and thermoelectric properties of monolayer WTe2. Particularly, the Te- O-2 substitution defect in parallel orientation yields negative formation energy, indicating that the relevant defect may form spontaneously under relevant experimental conditions. We reveal that the electronic band structure of WTe2 monolayer is significantly influenced by the presence of the considered defects. According to the calculated band gap values, a lowering of the conduction band minimum gives rise to metallic characteristics to the structure for the single Te(1) vacancy, a diagonal Te line defect, and the Te(1)-O-2 substitution, while the other investigated defects cause an opening of a small positive band gap at the Fermi level. Consequently, the real ( epsilon(1)(omega)) and imaginary ( epsilon(2)(omega)) parts of the dielectric constant at low frequencies are very sensitive to the applied defects, whereas we find that the absorbance (A) at optical frequencies is less significantly affected. We also predict that certain point defects can enhance the otherwise moderate value of S in pristine WTe2 to values relevant for thermoelectric applications. The described WTe2 monolayers, as functionalized with the considered defects, offer the possibility to be applied in optical, electronic, and thermoelectric devices.

Experimental control of local spin-charge interconversion is of primary interest for spintronics. Van der Waals (vdW) heterostructures combining graphene with a strongly spin-orbit coupled two-dimensional (2D) material enable such functionality by design. Electric spin valve experiments have thus far provided global information on such devices, while leaving the local interplay between symmetry breaking, charge flow across the heterointerface and aspects of topology unexplored. Here, we probe the gate-tunable local spin polarisation in current-driven graphene/WTe2 heterostructures through magneto-optical Kerr microscopy. Even for a nominal in-plane transport, substantial out-of-plane spin accumulation is induced by a corresponding out-of-plane current flow. We present a theoretical model which fully explains the gate- and bias-dependent onset and spatial distribution of the intense Kerr signal as a result of a non-linear anomalous Hall effect in the heterostructure, which is enabled by its reduced point group symmetry. Our findings unravel the potential of 2D heterostructure engineering for harnessing topological phenomena for spintronics, and constitute an important step toward nanoscale, electrical spin control. Spin-based electronics offers significantly improved efficiency, but a major challenge is the electric manipulation of spin. Here, Powalla et al find a large gate induced spinpolarization in graphene/WTe2 heterostructures, illustrating the potential of such heterostructures for spintronics.

We address the impact of crystal phase disorder on the generation of helicity-dependent photocurrents in layered MoTe2, which is one of the van der Waals materials to realize the topological type-II Weyl semimetal phase. Using scanning photocurrent microscopy, we spatially probe the phase transition and its hysteresis between the centrosymmetric, monoclinic 1T' phase to the symmetry-broken, orthorhombic Td phase as a function of temperature. We find a highly disordered photocurrent response in the intermediate temperature regime. Moreover, we demonstrate that helicity-dependent and ultrafast photocurrents in MoTe2 arise most likely from a local breaking of the electronic symmetries. Our results highlight the prospects of local domain morphologies and ultrafast relaxation dynamics on the optoelectronic properties of low-dimensional van der Waals circuits.

For two-dimensional (2D) layered semiconductors, control over atomic defects and understanding of their electronic and optical functionality represent major challenges towards developing a mature semiconductor technology using such materials. Here, we correlate generation, optical spectroscopy, atomic resolution imaging, and ab initio theory of chalcogen vacancies in monolayer MoS2. Chalcogen vacancies are selectively generated by in-vacuo annealing, but also focused ion beam exposure. The defect generation rate, atomic imaging and the optical signatures support this claim. We discriminate the narrow linewidth photoluminescence signatures of vacancies, resulting predominantly from localized defect orbitals, from broad luminescence features in the same spectral range, resulting from adsorbates. Vacancies can be patterned with a precision below 10nm by ion beams, show single photon emission, and open the possibility for advanced defect engineering of 2D semiconductors at the ultimate scale. The relation between the microscopic structure and the optical properties of atomic defects in 2D semiconductors is still debated. Here, the authors correlate different fabrication processes, optical spectroscopy and electron microscopy to identify the optical signatures of chalcogen vacancies in monolayer MoS2.

We demonstrate the on-demand creation and positioning of photon emitters in atomically thin MoS2 with very narrow ensemble broadening and negligible background luminescence. Focused helium-ion beam irradiation creates 100s to 1000s of such mono-typical emitters at specific positions in the MoS2 monolayers. Individually measured photon emitters show anti-bunching behavior with a g(2)(0) similar to 0.23 and 0.27. From a statistical analysis, we extract the creation yield of the He-ion induced photon emitters in MoS2 as a function of the exposed area, as well as the total yield of single emitters as a function of the number of He ions when single spots are irradiated by He ions. We reach probabilities as high as 18% for the generation of individual and spectrally clean photon emitters per irradiated single site. Our results firmly establish 2D materials as a platform for photon emitters with unprecedented control of position as well as photophysical properties owing to the all-interfacial nature.

We demonstrate electrostatic switching of individual, site-selectively generated matrices of single photon emitters (SPEs) in MoS2 van der Waals heterodevices. We contact monolayers of MoS2 in field-effect devices with graphene gates and hexagonal boron nitride as the dielectric and graphite as bottom gates. After the assembly of such gate-tunable heterodevices, we demonstrate how arrays of defects, that serve as quantum emitters, can be site-selectively generated in the monolayer MoS2 by focused helium ion irradiation. The SPEs are sensitive to the charge carrier concentration in the MoS2 and switch on and off similar to the neutral exciton in MoS2 for moderate electron doping. The demonstrated scheme is a first step for producing scalable, gate-addressable, and gate-switchable arrays of quantum light emitters in MoS2 heterostacks.

Recently, topological insulators (TIs) were discovered as a new class of materials representing a subset of topological quantum matter. While a TI possesses a bulk band gap similar to an ordinary insulator, it exhibits gapless states at the surface featuring a spin-helical Dirac dispersion. Due to this unique surface band structure, TIs may find use in (opto)spintronic applications. Herein, optoelectronic methods are discussed to characterize, control, and read-out surface state charge and spin transport of 3D TIs. In particular, time- and spatially-resolved photocurrent microscopy at near-infrared excitation can give fundamental insights into charge carrier dynamics, local electronic properties, and the interplay between bulk and surface currents. Furthermore, possibilities of applying such ultrafast optoelectronic methods to study Berry curvature-related transport phenomena in topological semimetals are discussed.

This review aims to provide an overview over recent developments of light-driven currents with a focus on their application to layered van der Waals materials. In topological and spin-orbit dominated van der Waals materials helicity-driven and light-field-driven currents are relevant for nanophotonic applications from ultrafast detectors to onchip current generators. The photon helicity allows addressing chiral and non-trivial surface states in topological systems, but also the valley degree of freedom in two-dimensional van der Waals materials. The underlying spinorbit interactions break the spatiotemporal electrodynamic symmetries, such that directed currents can emerge after an ultrafast laser excitation. Equally, the light-field of few-cycle optical pulses can coherently drive the transport of charge carriers with sub-cycle precision by generating strong and directed electric fields on the atomic scale. Ultrafast light-driven currents may open up novel perspectives at the interface between photonics and ultrafast electronics.

Precisely positioned and scalable single-photon emitters (SPEs) are highly desirable for applications in quantum technology. This Perspective discusses single-photon-emitting atomistic defects in monolayers of MoS2 that can be generated by focused He-ion irradiation with few nanometers positioning accuracy. We present the optical properties of the emitters and the possibilities to implement them into photonic and optoelectronic devices. We showcase the advantages of the presented emitters with respect to atomistic positioning, scalability, long (microsecond) lifetime, and a homogeneous emission energy within ensembles of the emitters. Moreover, we demonstrate that the emitters are stable in energy on a timescale exceeding several weeks and that temperature cycling narrows the ensembles' emission energy distribution.

Structuring materials with atomic precision is the ultimate goal of nanotechnology and is becoming increasingly relevant as an enabling technology for quantum electronics/spintronics and quantum photonics. Here, we create atomic defects in monolayer MoS2 by helium ion (He-ion) beam lithography with a spatial fidelity approaching the single-atom limit in all three dimensions. Using low-temperature scanning tunneling microscopy (STM), we confirm the formation of individual point defects in MoS2 upon He-ion bombardment and show that defects are generated within 9 nm of the incident helium ions. Atom-specific sputtering yields are determined by analyzing the type and occurrence of defects observed in high-resolution STM images and compared with with Monte Carlo simulations. Both theory and experiment indicate that the He-ion bombardment predominantly generates sulfur vacancies.

Using Hall photovoltage measurements, we demonstrate that a linear transverse Hall voltage can be induced in few-layer WTe2 under circularly polarized light illumination. By applying a bias voltage along different crystal axes, we find that the photon-helicity induced Hall effect coincides with a particular crystal axis. Our results are consistent with the underlying Berry curvature exhibiting a dipolar distribution due to the breaking of crystal inversion symmetry. Using time-resolved optoelectronic autocorrelation spectroscopy, we find that the decay time of the detected Hall voltage exceeds the electron-phonon scattering time by orders of magnitude but is consistent with the comparatively long spin lifetime of carriers in the momentum-indirect electron and hole pockets in WTe2. Our observation suggests that a helicity induced nonequilibrium spin density on the Fermi surface after the initial charge carrier relaxation gives rise to a linear Hall effect.

Crystals with symmetry-protected topological order, such as topological insulators, promise coherent spin and charge transport phenomena even in the presence of disorder at room temperature. We demonstrate how to image and read out the local conductance of helical surface modes in the prototypical topological insulators Bi2Se3 and BiSbTe3. We apply the so-called Shockley-Ramo theorem to design an optoelectronic probe circuit for the gapless surface states, and we find a well-defined conductance quantization at le(2)/h within the experimental error without any external magnetic field. The unprecedented response is a clear signature of local spin-polarized transport, and it can be switched on and off via an electrostatic field effect. The macroscopic, global readout scheme is based on an electrostatic coupling from the local excitation spot to the readout electrodes, and it does not require coherent transport between electrodes, in contrast to the conventional Landauer-Biittiker description. It provides a generalizable platform for studying further nontrivial gapless systems such as Weyl semimetals and quantum spin-Hall insulators.