Geometrical confinement effect in exfoliated sheets of layered materials leads to significant evolution of energy dispersion in mono- to few-layer thickness regime. Molybdenum disulfide (MoS(2)) was recently found to exhibit indirect-to-direct gap transition when the thickness is reduced to a single monolayer. Emerging photoluminescence (PL) from monolayer MoS(2) opens up opportunities for a range of novel optoelectronic applications of the material. Here we report differential reflectance and PL spectra of mono- to few-layer WS(2) and WSe(2) that indicate that the band structure of these materials undergoes similar indirect-to-direct gap transition when thinned to a single monolayer. The transition is evidenced by distinctly enhanced PL peak centered at 630 and 750 nm in monolayer WS(2) and WSe(2), respectively. Few-layer flakes are found to exhibit comparatively strong indirect gap emission along with direct gap hot electron emission, suggesting high quality of synthetic crystals prepared by a chemical vapor transport method. Fine absorption and emission features and their thickness dependence suggest a strong effect of Se p-orbitals on the d electron band structure as well as interlayer coupling in WSe(2).
We mechanically exfoliate mono- and few-layers of the transition metal dichalcogenides molybdenum disulfide, molybdenum diselenide, and tungsten diselenide. The exact number of layers is unambiguously determined by atomic force microscopy and high-resolution Raman spectroscopy. Strong photoluminescence emission is caused by the transition from an indirect band gap semiconductor of bulk material to a direct band gap semiconductor in atomically thin form.
Thickness is one of the fundamental parameters that define the electronic, optical, and thermal properties of two-dimensional (2D) crystals. Phonons in molybdenum disulfide (MoS2) were recently found to exhibit unique thickness dependence due to the interplay between short and long range interactions. Here we report Raman spectra of atomically thin sheets of WS2 and WSe2, isoelectronic compounds of MoS2, in the mono- to few-layer thickness regime. We show that, similar to the case of MoS2, the characteristic A1g and E2g(1) modes exhibit stiffening and softening with increasing number of layers, respectively, with a small shift of less than 3 cm(-1) due to large mass of the atoms. Thickness dependence is also observed in a series of multiphonon bands arising from overtone, combination, and zone edge phonons, whose intensity exhibit significant enhancement in excitonic resonance conditions. Some of these multiphonon peaks are found to be absent only in monolayers. These features provide a unique fingerprint and rapid identification for monolayer flakes.
Electronic devices based on organic semiconductors offer an attractive alternative to conventional inorganic devices due to potentially lower costs, simpler packaging and compatibility with flexible substrates. As is the case for silicon-based microelectronics, the use of complementary logic elements-requiring n- and p-type semiconductors whose majority charge carriers are electrons and holes, respectively-is expected to be crucial to achieving low-power, high-speed performance. Similarly, the electron-segregating domains of photovoltaic assemblies require both n- and p-type semiconductors. Stable organic p-type semiconductors are known, but practically useful n-type semiconductor materials have proved difficult to develop, reflecting the unfavourable electrochemical properties of known, electron-demanding polymers. Although high electron mobilities have been obtained for organic materials, these values are usually obtained for single crystals at low temperatures, whereas practically useful field-effect transistors (FETs) will have to be made of polycrystalline films that remain functional at room temperature. A few organic n-type semiconductors that can be used in FETs are known, but these suffer from low electron mobility, poor stability in air and/or demanding processing conditions. Here we report a crystallographically engineered naphthalenetetracarboxylic diimide derivative that allows us to fabricate solution-cast n-channel FETs with promising performance at ambient conditions. By integrating our n-channel FETs with solution-deposited p-channel FETs, we are able to produce a complementary inverter circuit whose active layers are deposited entirely from the liquid phase. We expect that other complementary circuit designs can be realized by this approach as well.
2D semiconducting metal phosphorus trichalcogenides, particularly the bulk crystals of MPS3 (M = Fe, Mn, Ni, Cd and Zn) sulfides and MPSe3 (M = Fe and Mn) selenides, have been synthesized, crystallized and exfoliated into monolayers. The Raman spectra of monolayer FePS3 and 3-layer FePSe3 show the strong intralayer vibrations and structural stability of the atomically thin layers under ambient condition. The band gaps can be adjusted by element choices in the range of 1.3-3.5 eV. The wide-range band gaps suggest their optoelectronic applications in a broad wavelength range. The calculated cleavage energies of MPS3 are smaller than that of graphite. Therefore, the monolayers used for building of heterostructures by van der Waals stacking could be considered as the candidates for artificial 2D materials with unusual ferroelectric and magnetic properties.
It has been well established that single layer MX 2 (M=Mo,W and X=S,Se) are direct gap semiconductors with band edges coinciding at the K point in contrast to their indirect gap multilayer counterparts. In few-layer MX 2 , there are two valleys along the Γ-K line with similar energy. There is little understanding on which of the two valleys forms the conduction band minimum (CBM) in this thickness regime. We investigate the conduction band valley structure in
Due to the novel optical and optoelectronic properties, two dimensional (2D) materials have received increasing interests for optoelectronics applications. Discovering new properties and functionalities of 2D materials are challenging yet promising. Here broadband polarization sensitive photodetectors based on few layer ReS 2 are demonstrated. The transistor based on few layer ReS 2 shows an n-type behavior with the mobility of about 40 cm 2 V -1 s -1 and on/off ratio of 10 5 . The polarization dependence of photoresponse is ascribed to the unique anisotropic in-plane crystal structure, consistent with the optical absorption 2 anisotropy. The linear dichroic photodetection with a high photoresponsivity reported here demonstrates a route to exploit the intrinsic anisotropy of 2D materials and the possibility to open up new ways for the applications of 2D materials for light polarization detection.
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