Pseudoheterodyne interferometry for multicolor near-field imaging.

We report the development and characterization of a detection technique for scattering-type scanning near-field optical microscopy (s-SNOM) that enables near-field amplitude and phase imaging at two or more wavelengths simultaneously. To this end, we introduce multispectral pseudoheterodyne (PSH) interferometry, where infrared lasers are combined to form a beam with a discrete spectrum of laser lines and a time-multiplexing scheme is employed to allow for the use of a single infrared detector. We first describe and validate the implementation of multispectral PSH into a commercial s-SNOM instrument. We then demonstrate its application for the real-time correction of the negative phase contrast (NPC), which provides reliable imaging of weak IR absorption at the nanoscale. We anticipate that multispectral PSH could improve data throughput, reduce effects of sample and interferometer drift, and help to establish multicolor s-SNOM imaging as a regular imaging modality, which could be particularly interesting as new infrared light sources become available.

Identification of weak molecular absorption in single-wavelength s-SNOM images.

Scattering-type scanning near-field optical microscopy (s-SNOM) allows for nanoscale optical mapping of manifold material properties. It is based on interferometric recording of the light scattered at a scanning probe tip. For dielectric samples such as biological materials or polymers, the near-field amplitude and phase signals of the scattered field reveal the local reflectivity and absorption, respectively. Importantly, absorption in s-SNOM imaging corresponds to a positive phase contrast relative to a non-absorbing reference sample. Here, we describe that in certain conditions (weakly or non- absorbing material placed on a highly reflective substrate), a slight negative phase contrast may be observed, which can hinder the recognition of materials exhibiting a weak infrared absorption. We first document this effect and explore its origin using representative test samples. We then demonstrate straightforward simple correction methods that remove the negative phase contrast and that allow for the identification of weak absorption contrasts.

Dark exciton anti-funneling in atomically thin semiconductors.

Transport of charge carriers is at the heart of current nanoelectronics. In conventional materials, electronic transport can be controlled by applying electric fields. Atomically thin semiconductors, however, are governed by excitons, which are neutral electron-hole pairs and as such cannot be controlled by electrical fields. Recently, strain engineering has been introduced to manipulate exciton propagation. Strain-induced energy gradients give rise to exciton funneling up to a micrometer range. Here, we combine spatiotemporal photoluminescence measurements with microscopic theory to track the way of excitons in time, space and energy. We find that excitons surprisingly move away from high-strain regions. This anti-funneling behavior can be ascribed to dark excitons which possess an opposite strain-induced energy variation compared to bright excitons. Our findings open new possibilities to control transport in exciton-dominated materials. Overall, our work represents a major advance in understanding exciton transport that is crucial for technological applications of atomically thin materials.

Strain tuning of the Stokes shift in atomically thin semiconductors.

Atomically thin layers of transition metal dichalcogenides (TMDC) have exceptional optical properties, exhibiting a characteristic absorption and emission at excitonic resonances. Due to their extreme flexibility, strain can be used to alter the fundamental exciton energies and line widths of TMDCs. Here, we report on the Stokes shift, i.e. the energetic difference of light absorption and emission, of the A exciton in TMDC mono- and bilayers. We demonstrate that mechanical strain can be used to tune the Stokes shift. We perform optical transmission and photoluminescence (PL) experiments on mono- and bilayers and apply uniaxial tensile strain of up to 1.2% in MoSe2 and WS2 bilayers. An A exciton red shift of -38 meV/% and -70 meV/% is found in transmission in MoSe2 and WS2, while smaller values of -27 meV/% and -62 meV/% are measured in PL, respectively. Therefore, a reduction of the Stokes shift is observed under increasing tensile strain. At the same time, the A exciton PL line widths narrow significantly with -14 meV/% (MoSe2) and -21 meV/% (WS2), demonstrating a drastic change in the exciton-phonon interaction. By comparison with ab initio calculations, we can trace back the observed shifts of the excitons to changes in the electronic band structure of the materials. Variations of the relative energetic positions of the different excitons lead to a decrease of the exciton-phonon coupling. Furthermore, we identify the indirect exciton emission in bilayer WS2 as the ΓK transition by comparing the experimental and theoretical gauge factors.

Supercontinuum second harmonic generation spectroscopy of atomically thin semiconductors.

Two-dimensional semiconductors have recently emerged as promising materials for novel optoelectronic devices. In particular, they exhibit favorable nonlinear optical properties. Potential applications include broadband and ultrafast light sources, optical signal processing, and generation of nonclassical light states. The prototypical nonlinear process second harmonic generation (SHG) is a powerful tool to gain insight into nanoscale materials because of its dependence on crystal symmetry. Material resonances also play an important role in the nonlinear response. Notably, excitonic resonances critically determine the magnitude and spectral dependence of the nonlinear susceptibility. We perform ultrabroadband SHG spectroscopy of atomically thin semiconductors by using few-cycle femtosecond infrared laser pulses. The spectrum of the second harmonic depends on the investigated material, MoS2 or WS2, and also on the spectral and temporal shape of the fundamental laser pulses used for excitation. Here, we present a method to remove the influence of the laser by normalization with the flat SHG response of thin hexagonal boron nitride crystals. Moreover, we exploit the distinct angle dependence of the second harmonic signal to suppress two-photon photoluminescence from the semiconductor monolayers. Our experimental technique provides the calibrated frequency-dependent nonlinear susceptibility χ(2)(ω) of atomically thin materials. It allows for the identification of the prominent A and B exciton resonances, as well as excited exciton states.

Interlayer excitons in bilayer MoS2 under uniaxial tensile strain.

Atomically thin semiconducting transition metal dichalcogenides (TMDCs) have unique mechanical and optical properties. They are extremely flexible and exhibit a strong optical absorption at their excitonic resonances. Excitons in TMDC monolayers are strongly influenced by mechanical strain. Their energy shifts and even their line widths change. In bilayers, intralayer excitons with electrons and holes residing in the same layer also shift their energy with the applied strain. Recently, interlayer excitons with electrons and holes in different layers have been observed in bilayer MoS2 at room temperature. Here, we report on the behavior of interlayer excitons in bilayer MoS2 under uniaxial tensile strain of up to 1.6%. By recording the differential transmission spectra for different strain values, we derive a gauge factor of -47 meV per % for the energy shift of the interlayer exciton, which is similar to -49 meV per % for the intralayer A and B excitons. Our finding confirms the origin of the interlayer exciton at the K point in the Brillouin zone, with the electron located in one layer and the hole delocalized over two layers. Furthermore, our work paves the way for future straintronic devices based on interlayer excitons.

Inverted valley polarization in optically excited transition metal dichalcogenides.

Large spin-orbit coupling in combination with circular dichroism allows access to spin-polarized and valley-polarized states in a controlled way in transition metal dichalcogenides. The promising application in spin-valleytronics devices requires a thorough understanding of intervalley coupling mechanisms, which determine the lifetime of spin and valley polarizations. Here we present a joint theory-experiment study shedding light on the Dexter-like intervalley coupling. We reveal that this mechanism couples A and B excitonic states in different valleys, giving rise to an efficient intervalley transfer of coherent exciton populations. We demonstrate that the valley polarization vanishes and is even inverted for A excitons, when the B exciton is resonantly excited and vice versa. Our theoretical findings are supported by energy-resolved and valley-resolved pump-probe experiments and also provide an explanation for the recently measured up-conversion in photoluminescence. The gained insights might help to develop strategies to overcome the intrinsic limit for spin and valley polarizations.

Strain Control of Exciton-Phonon Coupling in Atomically Thin Semiconductors.

Semiconducting transition metal dichalcogenide (TMDC) monolayers have exceptional physical properties. They show bright photoluminescence due to their unique band structure and absorb more than 10% of the light at their excitonic resonances despite their atomic thickness. At room temperature, the width of the exciton transitions is governed by the exciton-phonon interaction leading to strongly asymmetric line shapes. TMDC monolayers are also extremely flexible, sustaining mechanical strain of about 10% without breaking. The excitonic properties strongly depend on strain. For example, exciton energies of TMDC monolayers significantly redshift under uniaxial tensile strain. Here, we demonstrate that the width and the asymmetric line shape of excitonic resonances in TMDC monolayers can be controlled with applied strain. We measure photoluminescence and absorption spectra of the A exciton in monolayer MoSe2, WSe2, WS2, and MoS2 under uniaxial tensile strain. We find that the A exciton substantially narrows and becomes more symmetric for the selenium-based monolayer materials, while no change is observed for atomically thin WS2. For MoS2 monolayers, the line width increases. These effects are due to a modified exciton-phonon coupling at increasing strain levels because of changes in the electronic band structure of the respective monolayer materials. This interpretation based on steady-state experiments is corroborated by time-resolved photoluminescence measurements. Our results demonstrate that moderate strain values on the order of only 1% are already sufficient to globally tune the exciton-phonon interaction in TMDC monolayers and hold the promise for controlling the coupling on the nanoscale.

Phonon Sidebands in Monolayer Transition Metal Dichalcogenides.

Excitons dominate the optical properties of monolayer transition metal dichalcogenides (TMDs). Besides optically accessible bright exciton states, TMDs exhibit also a multitude of optically forbidden dark excitons. Here, we show that efficient exciton-phonon scattering couples bright and dark states and gives rise to an asymmetric excitonic line shape. The observed asymmetry can be traced back to phonon-induced sidebands that are accompanied by a polaron redshift. We present a joint theory-experiment study investigating the microscopic origin of these sidebands in different TMD materials taking into account intra- and intervalley scattering channels opened by optical and acoustic phonons. The gained insights contribute to a better understanding of the optical fingerprint of these technologically promising nanomaterials.

Nanoscale Positioning of Single-Photon Emitters in Atomically Thin WSe2.

Single-photon emitters in monolayer WSe2 are created at the nanoscale gap between two single-crystalline gold nanorods. The atomically thin semiconductor conforms to the metal nanostructure and is bent at the position of the gap. The induced strain leads to the formation of a localized potential well inside the gap. Single-photon emitters are localized there with a precision better than 140 nm.