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We demonstrate the synthesis of layered anisotropic semiconductor GeSe and GeSe2 nanomaterials through low temperature (∼400 °C) and atmospheric pressure chemical vapor deposition using halide based precursors. Results show that GeI2 and H2Se precursors successfully react in the gas-phase and nucleate on a variety of target substrates including sapphire, Ge, GaAs, or HOPG. Layer-by-layer growth takes place after nucleation to form layered anisotropic materials. Detailed SEM, EDS, XRD, and Raman spectroscopy measurements together with systematic CVD studies reveal that the substrate temperature, selenium partial pressure, and the substrate type ultimately dictate the resulting stoichiometry and phase of these materials. Results from this work introduce the phase control of Ge and Se based nanomaterials (GeSe and GeSe2) using halide based CVD precursors at ATM pressures and low temperatures. Overall findings also extend our fundamental understanding of their growth by making the first attempt to correlate growth parameters to resulting competing phases of Ge-Se based materials.

Transition-metal monochalcogenides comprise a class of two-dimensional materials with electronic band gaps that are highly sensitive to material thickness and chemical composition. Here, we explore the tunability of the electronic excitation spectrum in GaSe by using angle-resolved photoemission spectroscopy. The electronic structure of the material is modified by in situ potassium deposition as well as by forming GaSxSe1-x alloy compounds. We find that potassium-dosed samples exhibit a substantial change of the dispersion around the valence-band maximum (VBM). The observed band dispersion resembles that of a single tetralayer and is consistent with a transition from the direct-gap character of the bulk to the indirect-gap character expected for monolayer GaSe. Upon alloying with sulfur, we observe a phase transition from AB to AA′ stacking. Alloying also results in a rigid energy shift of the VBM towards higher binding energies, which correlates with a blueshift in the luminescence. The increase of the band gap upon sulfur alloying does not appear to change the dispersion or character of the VBM appreciably, implying that it is possible to engineer the gap of these materials while maintaining their salient electronic properties.

Owing to their low dimensionality, two-dimensional semiconductors, such as monolayer molybdenum disulfide, have a range of properties that make them valuable in the development of nanoelectronics. For example, the electronic bandgap of these semiconductors is not an intrinsic physical parameter and can be engineered by manipulating the dielectric environment around the monolayer. Here we show that this dielectric-dependent electronic bandgap can be used to engineer a lateral heterojunction within a homogeneous MoS 2 monolayer. We visualize the heterostructure with Kelvin probe force microscopy and examine its influence on electrical transport experimentally and theoretically. We observe a lateral heterojunction with an approximately 90 meV band offset due to the differing degrees of bandgap renormalization of monolayer MoS 2 when it is placed on a substrate in which one segment is made from an amorphous fluoropolymer (Cytop) and another segment is made of hexagonal boron nitride. This heterostructure leads to a diode-like electrical transport with a strong asymmetric behaviour.

Black phosphorus (BP) is a layered semiconductor with a high mobility of up to ∼1000 cm2 V-1s-1 and a narrow bandgap of ∼0.3 eV, and shows potential applications in thermoelectrics. In stark contrast to most other layered materials, electrical and thermoelectric properties in the basal plane of BP are highly anisotropic. To elucidate the mechanism for such anisotropy, we fabricated BP nanoribbons (∼100 nm thick) along the armchair and zigzag directions, and measured the transport properties. It is found that both the electrical conductivity and Seebeck coefficient increase with temperature, a behavior contradictory to that of traditional semiconductors. The three-dimensional variable range hopping model is adopted to analyze this abnormal temperature dependency of electrical conductivity and Seebeck coefficient. The hopping transport of the BP nanoribbons, attributed to high density of trap states in the samples, provides a fundamental understanding of the anisotropic BP for potential thermoelectric applications.

Optical dipole moment is the key parameter of optical transitions, as it directly determines the strength of light–matter interaction such as intrinsic radiative lifetime. However, experimental determination of these fundamental properties of excitons in monolayer WSe2 is largely limited, because the commonly used measurement, such as (time-resolved) photoluminescence, is inherently difficult to probe the intrinsic properties. For example, dark states below bright exciton can change the photoluminescence emission rate by orders of magnitude and gives an “effective” radiative lifetime distinctive from the intrinsic one. On the other hand, such “effective” radiative lifetime becomes important itself because it describes how dark states affect exciton dynamics. Unfortunately, the “effective” radiative lifetime in monolayer WSe2 is also not determined as it requires photoluminescence measurement with resonant excitation, which is technically difficult. These difficulties are overcome here to obtain both the “intrinsic” and “effective” radiative lifetime experimentally. A framework is developed to determine the dipole moment and “intrinsic” radiative lifetime of delocalized excitons in monolayer WSe2 from the absorption measurements. In addition, the “effective” radiative lifetime in WSe2 is obtained through time-resolved photoluminescence and absolute quantum-yield measurement at resonant excitation. These results provide helpful information for fundamental understanding of exciton light–matter interaction in WSe2.

Engineering layer-layer interactions provides a powerful way to realize novel and designable quantum phenomena in van der Waals heterostructures. Interlayer electron-electron interactions, for example, have enabled fascinating physics that is difficult to achieve in a single material, such as the Hofstadter's butterfly in graphene/boron nitride (hBN) heterostructures. In addition to electron-electron interactions, interlayer electron-phonon interactions allow for further control of the physical properties of van der Waals heterostructures. Here we report an interlayer electron-phonon interaction in WSe 2 /hBN heterostructures, where optically silent hBN phonons emerge in Raman spectra with strong intensities through resonant coupling to WSe 2 electronic transitions. Excitation spectroscopy reveals the double-resonance nature of such enhancement, and identifies the two resonant states to be the A exciton transition of monolayer WSe 2 and a new hybrid state present only in WSe 2 /hBN heterostructures. The observation of an interlayer electron-phonon interaction could open up new ways to engineer electrons and phonons for device applications.