The article overviews experimental results obtained by applying Internal PhotoEmission (IPE) spectroscopy methods to characterize electron states in single-or few-monolayer twodimensional (2D) materals and at their interfaces. Several conducting (graphene) and semiconducting (transitional metal dichalcogenides MoS2, WS2, MoSe2, and WSe2) films have been analyzed by IPE, which reveals significant sensitivity of interface band offsets and barriers to the details of the material and interface fabrication indicating violation of the Schottky-Mott rule. This variability is associated with charges and dipoles formed at the interfaces with van der Waals bonding as opposed to the chemically bonded interfaces of three-dimensional semiconductors and metals. Chemical modification of the underlying SiO2 surface is shown to be a significant factor, affecting interface barriers due to violation of the interface electroneutrality.

Spectral measurements of illumination-induced displacement currents related to trapping of charge carriers optically excited in semiconductor electrodes are shown to deliver information regarding energy onsets of electron transitions at the interface. Presented examples include determination of the conduction band offset at the GaN/Al2O3 interface and determination of charge carrier excitation spectra of two-dimensional (2D) semiconductors MoS2 and WS2 at the interface with insulating SiO2.

Internal photoemission of electrons was used to determine the energy position of the top valence band of mono- and few-layer WS2 on an SiO2/Si substrate. It was found, contrary to density functional theory calculations, that the valence band top in WS2 shifts up in energy with respect to the conduction band minimum of SiO2 with decreasing number of monolayers. At the same time, the band alignment of WS2 with SiO2 appears to be less sensitive to the WS2 synthesis route than in the previously studied case of the MoS2/SiO2 interface, indicating less extrinsic WS2 variability.

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Internal photoemission spectroscopy was used to determine the valence band top energy position in few-monolayer WS2 and WSe2 films directly synthesized on top of the SiO2 insulator. It is found that in WS2 the valence band top edge lies systematically higher (by 0.4–0.7 eV) in energy than that in WSe2. This unexpected trend is seen for several synthesis methods suggesting it to be the intrinsic property of these W-based layered dichalcogenides. At the same time, a change in the WS2 synthesis method from metal sulfurization to chemical vapor deposition leads to a ≈0.3 eV barrier change indicating a non-negligible impact of interface charges or dipoles. The influence of synthesis chemistry on the WSe2/SiO2 interface barrier appears to be marginal at least for the selenization and molecular-beam epitaxy growth methods.