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The rapidly increasing use of sensors throughout different research disciplines and the demand for more efficient devices with less power consumption depends critically on the emergence of new sensor materials and novel sensor concepts. Atomically thin transition metal dichalcogenides have a huge potential for sensor development within a wide range of applications. Their optimal surface-to-volume ratio combined with strong light–matter interaction results in a high sensitivity to changes in their surroundings. Here, we present a highly efficient sensing mechanism to detect molecules based on dark excitons in these materials. We show that the presence of molecules with a dipole moment transforms dark states into bright excitons, resulting in an additional pronounced peak in easy accessible optical spectra. This effect exhibits a huge potential for sensor applications, since it offers an unambiguous optical fingerprint for the detection of molecules—in contrast to common sensing schemes relying on small peak shifts and intensity changes., Two-dimensional materials have shown great promise as efficient chemical sensors. Here, the authors present a sensing mechanism to allow the detection of molecules based on dark excitons in atomically thin transition metal dichalcogenides.

The recent emergence of atomically thin two-dimensional (2D) materials has opened up possibilities for the design of ultrathin and flexible nanoelectronic devices. As truly 2D materials, they exhibit an optimal surface-to-volume ratio, which results in an extremely high sensitivity to external changes which can not be achieved by conventional semiconductors. This makes these materials optimal candidates for sensing applications. Here, we propose a dark exciton based concept for ultrasensitive strain sensors. By investigating both dark and bright excitons in tungsten-based monolayer transition metal dichalcogenides, we demonstrate that the dark-bright-exciton separation can be controlled by strain, which has a crucial impact on the activation of dark excitonic states. The predicted opposite strain-induced shifts for dark and bright excitons result in a pronounced change in photoluminescence stemming from dark excitons even at very small strain values. The predicted high optical gauge factors of up to 8000 are promising for the design of optical strain sensors.

The presence of impurities and disorder has an important impact on the optical response of monolayer transition metal dichalcogenides (TMDs). Here, we investigate elastic exciton-impurity scattering and its influence on the linewidth of excitonic resonances in different TMD materials. We derive an analytic expression for the linewidth broadening within the density matrix formalism. We find that the exciton linewidth increases for states up to the 3s exciton due to the scattering with impurities. For higher states, the impurity contribution decreases, reflecting the reduced scattering cross section. Furthermore, we reveal that the scattering efficiency is the largest for transitions between s and p exciton states. Finally, different TMDs show generally a similar behavior. The quantitatively smaller broadening in tungsten-based TMDs can be ascribed to their smaller effective masses resulting in a less efficient scattering.

Monolayer transition metal dichalcogenides (TMDs) have been in focus of current research, among others due to their remarkable exciton landscape consisting of bright and dark excitonic states. Although dark excitons are not directly visible in optical spectra, they have a large impact on exciton dynamics and hence their understanding is crucial for potential TMD-based applications. Here, we study brightening mechanisms of dark excitons via interaction with phonons and in-plane magnetic fields. We show clear signatures of momentum- and spin-dark excitons in WS$_2$, WSe$_2$ and MoS$_2$, while the photoluminescence of MoSe$_2$ is only determined by the bright exciton. In particular, we reveal the mechanism behind the brightening of states that are both spin- \textit{and} momentum-dark in MoS$_2$. Our results are in good agreement with recent experiments and contribute to a better microscopic understanding of the exciton landscape in TMDs., Comment: 7 pages, 4 figures

Monolayer transition metal dichalcogenides (TMDs) are known to be highly sensitive to externally applied tensile or compressive strain. In particular, strain can be exploited as a tool to control the optical response of TMDs. However, the role of excitonic effects under strain has not been fully understood yet. Utilizing the strain-induced modification of electron and phonon dispersion obtained by first principle calculations, we present in this work microscopic insights into the strain-dependent optical response of various TMD materials. In particular, we explain recent experiments on the change of excitonic linewidths in strained TMDs and predict their behavior for tensile and compressive strain at low temperatures., 7 pages, 7 figures

Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap, since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a non-direct gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

Monolayer transition metal dichalcogenides (TMDs) show an optimal surface-to-volume ratio and are thus promising candidates for novel molecule sensor devices. It was recently predicted that a certain class of molecules exhibiting a large dipole moment can be detected through the activation of optically inaccessible (dark) excitonic states in absorption spectra of tungsten-based TMDs. In this paper, we investigate the molecule signatures in photoluminescence spectra in dependence of a number of different experimentally accessible quantities, such as excitation density, temperature, as well as molecular characteristics including the dipole moment and its orientation, molecule-TMD distance, molecular coverage, and distribution. We show that under certain optimal conditions even room-temperature detection of molecules can be achieved.

Chemical functionalization of atomically thin nanostructures presents a promising strategy to create new hybrid nanomaterials with remarkable and externally controllable properties. Here, we review our research in the field of theoretical modeling of carbon nanotubes, graphene, and transition metal dichalcogenides located in molecular dipole fields. In particular, we provide a microscopic view on the change of the optical response of these technologically promising nanomaterials due to the presence of photo-active spiropyran molecules. The feature article presents a review of recent theoretical work providing microscopic view on the optical response of chemically functionalized carbon nanotubes, graphene, and monolayered transition metal dichalcogenides. In particular, we propose a novel sensor mechanism based on the molecule-induced activation of dark excitons. This results in a pronounced additional peak presenting an unambiguous optical fingerprint for the attached molecules.

Point defects, local strain or impurities can crucially impact the optical response of atomically thin two-dimensional materials as they offer trapping potentials for excitons. These trapped excitons appear in photoluminescence spectra as new resonances below the bright exciton that can even be exploited for single photon emission. While large progress has been made in deterministically introducing defects, only little is known about their impact on the optical fingerprint of 2D materials. Here, based on a microscopic approach we reveal direct signatures of localized bright excitonic states as well as indirect phonon-assisted side bands of localized momentum-dark excitons. The visibility of localized excitons strongly depends on temperature and disorder potential width. This results in different regimes, where either the bright or dark localized states are dominant in optical spectra. We trace back this behavior to an interplay between disorder-induced exciton capture and intervalley exciton-phonon scattering processes., 7 pages main text, including 4 figures, 2 pages supplementary material

Strain presents a straightforward tool to tune electronic properties of atomically thin nanomaterials that are highly sensitive to lattice deformations. While the influence of strain on the electronic band structure has been intensively studied, there are only a few works on its impact on optical properties of monolayer transition-metal dichalcogenides (TMDs). Combining microscopic theory based on Wannier and Bloch equations with nearest-neighbor tight-binding approximation, we present an analytical view on how uni- and biaxial strain influences the optical fingerprint of TMDs, including their excitonic binding energy, oscillator strength, optical selection rules, and the radiative broadening of excitonic resonances. We show that the impact of strain can be reduced to changes in the lattice structure (geometric effect) and in the orbital functions (overlap effect). In particular, we demonstrate that the valley-selective optical selection rule is softened in the case of uniaxial strain due to the introduced asymmetry in the lattice structure. Furthermore, we reveal a considerable increase of the radiative dephasing due to strain-induced changes in the optical matrix element and the excitonic wave functions.

Atomically thin transition metal dichalcogenides (TMDs) hold promising potential for applications in optoelectronics. Due to their direct band gap and the extraordinarily strong Coulomb interaction, TMDs exhibit efficient light-matter coupling and tightly bound excitons. Moreover, large spin orbit coupling in combination with circular dichroism allows for spin and valley selective optical excitation. As atomically thin materials, they are very sensitive to changes in the surrounding environment. This motivates a functionalization approach, where external molecules are adsorbed to the materials surface to tailor its optical properties. Here, we apply the density matrix theory to investigate the potential of non-covalently functionalized TMDs. Considering exemplary spiropyran molecules with a strong dipole moment, we predict spectral redshifts and the appearance of an additional side peak in the absorption spectrum of functionalized TMDs. We show that the molecular characteristics, e.g. coverage, orientation and dipole moment, crucially influence the optical properties of TMDs, leaving a unique optical fingerprint in the absorption spectrum. Furthermore, we find that the molecular dipole moments open a channel for coherent intervalley coupling between the high-symmetry K and K' points which may open new possibilities for spin-valleytronics application., 6 pages, 5 figures