Albert F. Rigosi

Measurement of the optical dielectric function of transition metal dichalcogenide monolayers: MoS2, MoSe2, WS2 and WSe2

This chapter presents the complex in-plane dielectric function from 1.5 to 3 eV for monolayers of four transition metal dichalcogenides: MoSe2, WSe2, MoS2, and WS2. The results were obtained from optical reflection spectra using a Kramers–Kronig constrained variational analysis. From the inferred dielectric functions, we obtain the absolute absorbance of the monolayers. We also provide a comparison of the dielectric function for the monolayers with the respective bulk materials [1].

Observation of Excitonic Rydberg States in Monolayer MoS2 and WS2 by Photoluminescence Excitation Spectroscopy

We have identified excited exciton states in monolayers of MoS2 and WS2 supported on fused silica by means of photoluminescence excitation spectroscopy. In monolayer WS2, the positions of the excited A exciton states imply an exciton binding energy of 0.32 eV. In monolayer MoS2, excited exciton transitions are observed at energies of 2.24 and 2.34 eV. Assigning these states to the B exciton Rydberg series yields an exciton binding energy of 0.44 eV.

Electrical Tuning of Exciton Binding Energies in Monolayer WS2

We demonstrate continuous tuning of the exciton binding energy in monolayer WS_{2} by means of an externally applied voltage in a field-effect transistor device. Using optical spectroscopy, we monitor the ground and excited excitonic states as a function of gate voltage and track the evolution of the quasiparticle band gap. The observed decrease of the exciton binding energy over the range of about 100 meV, accompanied by the renormalization of the quasiparticle band gap, is associated with screening of the Coulomb interaction by the electrically injected free charge carriers at densities up to 8×10^{12} cm^{-2}. Complete ionization of the excitons due to the electrical doping is estimated to occur at a carrier density of several 10^{13} cm^{-2}.

Probing Interlayer Interactions in Transition Metal Dichalcogenide Heterostructures by Optical Spectroscopy: MoS2/WS2 and MoSe2/WSe2

We have applied optical absorption spectroscopy to investigate van der Waals heterostructures formed of pairs of monolayer transition metal dichalcogenide crystals, choosing MoS2/WS2 and MoSe2/WSe2 as test cases. In the heterostructure spectra, we observe a significant broadening of the excitonic transitions compared to the corresponding features in the isolated layers. The broadening is interpreted as a lifetime effect arising from decay of excitons initially created in either layer through charge transfer processes expected for a staggered band alignment. The measured spectral broadening of 20 meV - 35 meV implies lifetimes for charge separation of the near band-edge A and B excitons in the range of 20-35 fs. Higher-lying transitions exhibit still greater broadening.

Coulomb engineering of the bandgap and excitons in two-dimensional materials

The ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS2 and WSe2 by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as an initial step towards the creation of diverse lateral junctions with nanoscale resolution.

Band Alignment in MoS2/WS2 Transition Metal Dichalcogenide Heterostructures Probed by Scanning Tunneling Microscopy and Spectroscopy

Using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), we examine the electronic structure of transition metal dichalcogenide heterostructures (TMDCHs) composed of monolayers of MoS2 and WS2. STS data are obtained for heterostructures of varying stacking configuration as well as the individual monolayers. Analysis of the tunneling spectra includes the influence of finite sample temperature, yield information about the quasi-particle bandgaps, and the band alignment of MoS2 and WS2. We report the band gaps of MoS2 (2.16 ± 0.04 eV) and WS2 (2.38 ± 0.06 eV) in the materials as measured on the heterostructure regions and the general type II band alignment for the heterostructure, which shows an interfacial band gap of 1.45 ± 0.06 eV.

The Role of Electronic and Phononic Excitation in the Optical Response of Monolayer WS2 after Ultrafast Excitation

Transient changes of the optical response of WS2 monolayers are studied by femtosecond broadband pump-probe spectroscopy. Time-dependent absorption spectra are analyzed by tracking the line width broadening, bleaching, and energy shift of the main exciton resonance as a function of time delay after the excitation. Two main sources for the pump-induced changes of the optical response are identified. Specifically, we find an interplay between modifications induced by many-body interactions from photoexcited carriers and by the subsequent transfer of the excitation to the phonon system followed by cooling of the material through the heat transfer to the substrate.

Electrical Stabilization of Surface Resistivity in Epitaxial Graphene Systems by Amorphous Boron Nitride Encapsulation

Homogeneous monolayer epitaxial graphene (EG) is an ideal candidate for the development of millimeter-sized devices with single-crystal domains. A clean fabrication process was used to produce EG-based devices, with n-type doping level of the order of 1012 cm–2. Generally, electrical properties of EG, such as longitudinal resistivity, remain unstable when devices are exposed to air due to adsorption of molecular dopants, whose presence shifts the carrier density close to the Dirac point (<1010 cm–2) or into the p-type regime. Here, we report experimental results on the use of amorphous boron nitride (a-BN) as an encapsulation layer, whereby EG can maintain its longitudinal resistivity and have its carrier density modulated. Furthermore, we exposed 12 devices to controlled temperatures of up to 85 °C and relative humidity of up to 85% and reported that an approximately 20 nm a-BN encapsulation thickness is sufficient to preserve their longitudinal resistivity to within 10% of the previously measured value. We monitored the electronic properties of our encapsulated and nonencapsulated EG samples by magnetotransport measurements, using a neodymium iron boron magnet. Our results have essential importance in the mass production of millimeter-scale graphene devices, with stable electrical properties.

Observation of nonconventional spin waves in composite-fermion ferromagnets.

We find unexpected low energy excitations of fully spin-polarized composite-fermion ferromagnets in the fractional quantum Hall liquid, resulting from a complex interplay between a topological order manifesting through new energy levels and a magnetic order due to spin polarization. The lowest energy modes, which involve spin reversal, are remarkable in displaying unconventional negative dispersion at small momenta followed by a deep roton minimum at larger momenta. This behavior results from a nontrivial mixing of spin-wave and spin-flip modes creating a spin-flip excitonic state of composite-fermion particle-hole pairs. The striking properties of spin-flip excitons imply highly tunable mode couplings that enable fine control of topological states of itinerant two-dimensional ferromagnets.

Probing the dielectric response of the interfacial buffer layer in epitaxial graphene via optical spectroscopy

Monolayer epitaxial graphene (EG) is a suitable candidate for a variety of electronic applications. One advantage of EG growth on the Si face of SiC is that it develops as a single crystal, as does the layer below, referred to as the interfacial buffer layer (IBL), whose properties include an electronic band gap. Though much research has been conducted to learn about the electrical properties of the IBL, not nearly as much work has been reported on the optical properties of the IBL. In this work, we combine measurements from Mueller matrix ellipsometry, differential reflectance contrast, atomic force microscopy, and Raman spectroscopy, as well as calculations from Kramers-Kronig analyses and density functional theory (DFT), to determine the dielectric function of the IBL within the energy range of 1 eV to 8.5 eV.