Electroluminescence from pure resonant states in hBN-based vertical tunneling junctions.

Defect centers in wide-band-gap crystals have garnered interest for their potential in applications among optoelectronic and sensor technologies. However, defects embedded in highly insulating crystals, like diamond, silicon carbide, or aluminum oxide, have been notoriously difficult to excite electrically due to their large internal resistance. To address this challenge, we realized a new paradigm of exciting defects in vertical tunneling junctions based on carbon centers in hexagonal boron nitride (hBN). The rational design of the devices via van der Waals technology enabled us to raise and control optical processes related to defect-to-band and intradefect electroluminescence. The fundamental understanding of the tunneling events was based on the transfer of the electronic wave function amplitude between resonant defect states in hBN to the metallic state in graphene, which leads to dramatic changes in the characteristics of electrons due to different band structures of constituent materials. In our devices, the decay of electrons via tunneling pathways competed with radiative recombination, resulting in an unprecedented degree of tuneability of carrier dynamics due to the significant sensitivity of the characteristic tunneling times on the thickness and structure of the barrier. This enabled us to achieve a high-efficiency electrical excitation of intradefect transitions, exceeding by several orders of magnitude the efficiency of optical excitation in the sub-band-gap regime. This work represents a significant advancement towards a universal and scalable platform for electrically driven devices utilizing defect centers in wide-band-gap crystals with properties modulated via activation of different tunneling mechanisms at a level of device engineering.

Electroluminescent vertical tunneling junctions based on WSe2 monolayer quantum emitter arrays: Exploring tunability with electric and magnetic fields.

We experimentally demonstrate the creation of defects in monolayer WSe2 via nanopillar imprinting and helium ion irradiation. Based on the first method, we realize atomically thin vertical tunneling light-emitting diodes based on WSe2 monolayers hosting quantum emitters at deterministically specified locations. We characterize these emitters by investigating the evolution of their emission spectra in external electric and magnetic fields, as well as by inducing electroluminescence at low temperatures. We identify qualitatively different types of quantum emitters and classify them according to the dominant electron-hole recombination paths, determined by the mechanisms of intervalley mixing occurring in fundamental conduction and/or valence subbands.

Resonant Raman scattering of few layers CrBr3.

We investigate the vibrational and magnetic properties of thin layers of chromium tribromide (CrBr3) with a thickness ranging from three to twenty layers (3-20 L) revealed by the Raman scattering (RS) technique. Systematic dependence of the RS process efficiency on the energy of the laser excitation is explored for four different excitation energies: 1.96 eV, 2.21 eV, 2.41 eV, and 3.06 eV. Our characterization demonstrates that for 12 L CrBr3, 3.06 eV excitation could be considered resonant with interband electronic transitions due to the enhanced intensity of the Raman-active scattering resonances and the qualitative change in the Raman spectra. Polarization-resolved RS measurements for 12 L CrBr3 and first-principles calculations allow us to identify five observable phonon modes characterized by distinct symmetries, classified as the A g and E g modes. The evolution of phonon modes with temperature for a 16 L CrBr3 encapsulated in hexagonal boron nitride flakes demonstrates alterations of phonon energies and/or linewidths of resonances indicative of a transition between the paramagnetic and ferromagnetic state at Curie temperature ( T C ≈ 50  K). The exploration of the effects of thickness on the phonon energies demonstrated small variations pronounces exclusively for the thinnest layers in the vicinity of 3-5 L. We propose that this observation can be due to the strong localization in the real space of interband electronic excitations, limiting the effects of confinement for resonantly excited Raman modes to atomically thin layers.

Topological Spin Textures in an Insulating van der Waals Ferromagnet.

Generation and control of topological spin textures constitutes one of the most exciting challenges of modern spintronics given their potential applications in information storage technologies. Of particular interest are magnetic insulators, which due to low damping, absence of Joule heating and reduced dissipation can provide energy-efficient spin-textures platform. Here, it is demonstrated that the interplay between sample thickness, external magnetic fields, and optical excitations can generate a prolific paramount of spin textures, and their coexistence in insulating CrBr3 van der Waals (vdW) ferromagnets. Using high-resolution magnetic force microscopy and large-scale micromagnetic simulation methods, the existence of a large region in T-B phase diagram is demonstrated where different stripe domains, skyrmion crystals, and magnetic domains exist and can be intrinsically selected or transformed to each-other via a phase-switch mechanism. Lorentz transmission electron microscopy unveils the mixed chirality of the magnetic textures that are of Bloch-type at given conditions but can be further manipulated into Néel-type or hybrid-type via thickness-engineering. The topological phase transformation between the different magnetic objects can be further inspected by standard photoluminescence optical probes resolved by circular polarization indicative of an existence of exciton-skyrmion coupling mechanism. The findings identify vdW magnetic insulators as a promising framework of materials for the manipulation and generation of highly ordered skyrmion lattices relevant for device integration at the atomic level.

Dielectric Environment Sensitivity of Carbon Centers in Hexagonal Boron Nitride.

A key advantage of utilizing van-der-Waals (vdW) materials as defect-hosting platforms for quantum applications is the controllable proximity of the defect to the surface or the substrate allowing for improved light extraction, enhanced coupling with photonic elements, or more sensitive metrology. However, this aspect results in a significant challenge for defect identification and characterization, as the defect's properties depend on the the atomic environment. This study explores how the environment can influence the properties of carbon impurity centers in hexagonal boron nitride (hBN). It compares the optical and electronic properties of such defects between bulk-like and few-layer films, showing alteration of the zero-phonon line energies and their phonon sidebands, and enhancements of inhomogeneous broadenings. To disentangle the mechanisms responsible for these changes, including the atomic structure, electronic wavefunctions, and dielectric screening, it combines ab initio calculations with a quantum-embedding approach. By studying various carbon-based defects embedded in monolayer and bulk hBN, it demonstrates that the dominant effect of the change in the environment is the screening of density-density Coulomb interactions between the defect orbitals. The comparative analysis of experimental and theoretical findings paves the way for improved identification of defects in low-dimensional materials and the development of atomic scale sensors for dielectric environments.

The effect of temperature and excitation energy on Raman scattering in bulkHfS2.

Raman scattering (RS) in bulk hafnium disulfide (HfS2) is investigated as a function of temperature (5 K - 350 K) with polarization resolution and excitation of several laser energies. An unexpected temperature dependence of the energies of the main Raman-active (A1gand Eg) modes with the temperature-induced blueshift in the low-temperature limit is observed. The low-temperature quenching of a modeω1(134 cm-1) and the emergence of a new mode at approx. 184 cm-1, labeledZ, is reported. The optical anisotropy of the RS inHfS2is also reported, which is highly susceptible to the excitation energy. The apparent quenching of the A1gmode atT = 5 K and of the Egmode atT= 300 K in the RS spectrum excited with 3.06 eV excitation is also observed. We discuss the results in the context of possible resonant character of light-phonon interactions. Analyzed is also a possible effect of the iodine molecules intercalated in the van der Waals gaps between neighboringHfS2layers, which inevitably result from the growth procedure.

Temperature induced modulation of resonant Raman scattering in bilayer 2H-MoS2.

The temperature evolution of the resonant Raman scattering from high-quality bilayer 2H-MoS[Formula: see text] encapsulated in hexagonal BN flakes is presented. The observed resonant Raman scattering spectrum as initiated by the laser energy of 1.96 eV, close to the A excitonic resonance, shows rich and distinct vibrational features that are otherwise not observed in non-resonant scattering. The appearance of 1st and 2nd order phonon modes is unambiguously observed in a broad range of temperatures from 5 to 320 K. The spectrum includes the Raman-active modes, i.e. E[Formula: see text]([Formula: see text]) and A[Formula: see text]([Formula: see text]) along with their Davydov-split counterparts, i.e. E[Formula: see text]([Formula: see text]) and B[Formula: see text]([Formula: see text]). The temperature evolution of the Raman scattering spectrum brings forward key observations, as the integrated intensity profiles of different phonon modes show diverse trends. The Raman-active A[Formula: see text]([Formula: see text]) mode, which dominates the Raman scattering spectrum at T = 5 K quenches with increasing temperature. Surprisingly, at room temperature the B[Formula: see text]([Formula: see text]) mode, which is infrared-active in the bilayer, is substantially stronger than its nominally Raman-active A[Formula: see text]([Formula: see text]) counterpart.

Degradation Chemistry and Kinetic Stabilization of Magnetic CrI3.

The discovery of the intrinsic magnetic order in single-layer chromium trihalides (CrX3, X = I, Br, and Cl) has drawn intensive interest due to their potential application in spintronic devices. However, the notorious environmental instability of this class of materials under ambient conditions renders their device fabrication and practical application extremely challenging. Here, we performed a systematic investigation of the degradation chemistry of chromium iodide (CrI3), the most studied among CrX3 families, via a joint spectroscopic and microscopic analysis of the structural and composition evolution of bulk and exfoliated nanoflakes in different environments. Unlike other air-sensitive 2D materials, CrI3 undergoes a pseudo-first-order hydrolysis in the presence of pure water toward the formation of amorphous Cr(OH)3 and hydrogen iodide (HI) with a rate constant of kI = 0.63 day-1 without light. In contrast, a faster pseudo-first-order surface oxidation of CrI3 occurs in a pure O2 environment, generating CrO3 and I2 with a large rate constant of kCr = 4.2 day-1. Both hydrolysis and surface oxidation of CrI3 can be accelerated via light irradiation, resulting in its ultrafast degradation in air. The new chemical insights obtained allow for the design of an effective stabilization strategy for CrI3 with preserved optical and magnetic properties. The use of organic acid solvents (e.g., formic acid) as reversible capping agents ensures that CrI3 nanoflakes remain stable beyond 1 month due to the effective suppression of both hydrolysis and oxidation of CrI3.

Exposing the trion's fine structure by controlling the carrier concentration in hBN-encapsulated MoS2.

Atomically thin materials, like semiconducting transition metal dichalcogenides, are highly sensitive to the environment. This opens up an opportunity to externally control their properties by changing their surroundings. In this work, high-quality van der Waals heterostructures assembled from hBN-encapsulated monolayer MoS2 are studied with the aid of photoluminescence, photoluminescence excitation, and reflectance contrast experiments. We demonstrate that carrier concentration in MoS2 monolayers, arising from charge transfer from impurities in the substrate, can be significantly tuned within one order of magnitude by the modification of the bottom hBN flake thickness. The studied structures, characterized by spectral lines with linewidths approaching the narrow homogeneously broadened limit enabled observations of subtle optical and spin-valley properties of excitonic complexes. Our results allowed us to resolve three optically-active negatively charged excitons in MoS2 monolayers, which are assigned to the intravalley singlet, intervalley singlet, and intervalley triplet states.

Anisotropic Optical and Vibrational Properties of GeS.

The optical response of bulk germanium sulfide (GeS) is investigated systematically using different polarization-resolved experimental techniques, such as photoluminescence (PL), reflectance contrast (RC), and Raman scattering (RS). It is shown that while the low-temperature (T = 5 K) optical band-gap absorption is governed by a single resonance related to the neutral exciton, the corresponding emission is dominated by the disorder/impurity- and/or phonon-assisted recombination processes. Both the RC and PL spectra are found to be linearly polarized along the armchair direction. The measured RS spectra over a broad range from 5 to 300 K consist of six Raman peaks identified with the help of Density Functional Theory (DFT) calculations: Ag1, Ag2, Ag3, Ag4, B1g1, and B1g2, which polarization properties are studied under four different excitation energies. We found that the polarization orientations of the Ag2 and Ag4 modes under specific excitation energy can be useful tools to determine the GeS crystallographic directions: armchair and zigzag.

Excitonic Complexes in n-Doped WS2 Monolayer.

We investigate the origin of emission lines apparent in the low-temperature photoluminescence spectra of n-doped WS2 monolayer embedded in hexagonal BN layers using external magnetic fields and first-principles calculations. Apart from the neutral A exciton line, all observed emission lines are related to the negatively charged excitons. Consequently, we identify emissions due to both the bright (singlet and triplet) and dark (spin- and momentum-forbidden) negative trions as well as the phonon replicas of the latter optically inactive complexes. The semidark trions and negative biexcitons are distinguished. On the basis of their experimentally extracted and theoretically calculated g-factors, we identify three distinct families of emissions due to exciton complexes in WS2: bright, intravalley, and intervalley dark. The g-factors of the spin-split subbands in both the conduction and valence bands are also determined.

Charge transport in MBE-grown 2H-MoTe2 bilayers with enhanced stability provided by an AlOx capping layer.

Thin layers of transition metal dichalcogenides have been intensively studied over the last few years due to their novel physical phenomena and potential applications. One of the biggest problems in laboratory handling and moving on to application-ready devices lies in the high sensitivity of their physicochemical properties to ambient conditions. We demonstrate that novel, in situ capping with an ultra-thin, aluminum film efficiently protects thin MoTe2 layers stabilizing their electronic transport properties after exposure to ambient conditions. The experiments have been performed on bilayers of 2H-MoTe2 grown by molecular beam epitaxy on large area GaAs(111)B substrates. The crystal structure, surface morphology and thickness of the deposited MoTe2 layers have been precisely controlled in situ with a reflection high energy electron diffraction system. As evidenced by high resolution transmission electron microscopy, MoTe2 films exhibit perfect arrangement in the 2H phase and the epitaxial relation to the GaAs(111)B substrates. After the growth, the samples were in situ capped with a thin (3 nm) film of aluminum, which oxidizes after exposure to ambient conditions. This oxide serves as a protective layer to the underlying MoTe2. Resistivity measurements of the MoTe2 layers with and without the cap, exposed to low vacuum, nitrogen and air, revealed a huge difference in their stability. The significant rise of resistance is observed for the unprotected sample while the resistance of the protected one is constant. Wide range temperature resistivity studies showed that charge transport in MoTe2 is realized by hopping with an anomalous hopping exponent of x ≃ 0.66, reported also previously for ultra-thin, metallic layers.

Ultra-long-working-distance spectroscopy of single nanostructures with aspherical solid immersion microlenses.

In light science and applications, equally important roles are played by efficient light emitters/detectors and by the optical elements responsible for light extraction and delivery. The latter should be simple, cost effective, broadband, versatile and compatible with other components of widely desired micro-optical systems. Ideally, they should also operate without high-numerical-aperture optics. Here, we demonstrate that all these requirements can be met with elliptical microlenses 3D printed on top of light emitters. Importantly, the microlenses we propose readily form the collected light into an ultra-low divergence beam (half-angle divergence below 1°) perfectly suited for ultra-long-working-distance optical measurements (600 mm with a 1-inch collection lens), which are not accessible to date with other spectroscopic techniques. Our microlenses can be fabricated on a wide variety of samples, including semiconductor quantum dots and fragile van der Waals heterostructures made of novel two-dimensional materials, such as monolayer and few-layer transition metal dichalcogenides.

Narrow Excitonic Lines and Large-Scale Homogeneity of Transition-Metal Dichalcogenide Monolayers Grown by Molecular Beam Epitaxy on Hexagonal Boron Nitride.

Monolayer transition-metal dichalcogenides (TMDs) manifest exceptional optical properties related to narrow excitonic resonances. However, these properties have been so far explored only for structures produced by techniques inducing considerable large-scale inhomogeneity. In contrast, techniques which are essentially free from this disadvantage, such as molecular beam epitaxy (MBE), have to date yielded only structures characterized by considerable spectral broadening, which hinders most of the interesting optical effects. Here, we report for the first time on the MBE-grown TMD exhibiting narrow and resolved spectral lines of neutral and charged exciton. Moreover, our material exhibits unprecedented high homogeneity of optical properties, with variation of the exciton energy as small as ±0.16 meV over a distance of tens of micrometers. Our recipe for MBE growth is presented for MoSe2 and includes the use of atomically flat hexagonal boron nitride substrate. This recipe opens a possibility of producing TMD heterostructures with optical quality, dimensions, and homogeneity required for optoelectronic applications.