Designing highly conducting metal–organic frameworks (MOFs) is currently a subject of great interest for their potential applications in diverse areas encompassing energy storage and generation. Herein, a strategic design in which a metal–sulfur plane is integrated within a MOF to achieve high electrical conductivity, is successfully demonstrated. The MOF {[Cu
2
(6-Hmna)(6-mn)]·NH
4
}
n
(
1
, 6-Hmna = 6-mercaptonicotinic acid, 6-mn = 6-mercaptonicotinate), consisting of a two dimensional (–Cu–S–)
n
plane, is synthesized from the reaction of Cu(NO
3
)
2
, and 6,6′-dithiodinicotinic acid via the in situ cleavage of an S–S bond under hydrothermal conditions. A single crystal of the MOF is found to have a low activation energy (6 meV), small bandgap (1.34 eV) and a highest electrical conductivity (10.96 S cm
−1
) among MOFs for single crystal measurements. This approach provides an ideal roadmap for producing highly conductive MOFs with great potential for applications in batteries, thermoelectric, supercapacitors and related areas.
Upconversion nanoparticles on graphene based broadband photodetector showing unprecedented values of device parameters is demonstrated with response even for hand held domestic appliances.
We report on the observation of the substantial thickness (t)-dependent electrical conductivity (σ) at a wide thickness range for an MoSe₂ layer semiconductor. The conductivity increases for more than two orders of magnitude from 4.6 to 1500 Ω(-1) cm(-1) with a decrease in thickness from 2700 to 6 nm. The conductivity was found to follow a nearly linear relationship with the reciprocal thickness, i.e. σ ∝ 1/t. The temperature-dependent conductivity measurements also show that the MoSe₂ multilayers have much lower activation energies at 3.5-8.5 meV than those (36-38 meV) of their bulk counterparts, indicating the different origins of the majority carrier. These results imply the presence of higher surface conductivity or carrier surface accumulation in this layer crystal. The fabrication of ohmic contacts for the MoSe₂ layer nanocrystals using the focused-ion beam (FIB) technique was also demonstrated. This study provides a new understanding which is crucial for the development of flexible electronic devices and transparent conducting materials using ultrathin dichalcogenide layer materials.
The thickness-dependent surface states of MoS2 thin films grown by the chemical vapor deposition process on the SiO2-Si substrates are investigated by X-ray photoelectron spectroscopy. Raman and high-resolution transmission electron microscopy suggest the thicknesses of MoS2 films to be ranging from 3 to 10 layers. Both the core levels and valence band edges of MoS2 shift downward ∼0.2 eV as the film thickness increases, which can be ascribed to the Fermi level variations resulting from the surface states and bulk defects. Grainy features observed from the atomic force microscopy topographies, and sulfur-vacancy-induced defect states illustrated at the valence band spectra imply the generation of surface states that causes the downward band bending at the n-type MoS2 surface. Bulk defects in thick MoS2 may also influence the Fermi level oppositely compared to the surface states. When Au contacts with our MoS2 thin films, the Fermi level downshifts and the binding energy reduces due to the hole-doping characteristics of Au and easy charge transfer from the surface defect sites of MoS2. The shift of the onset potentials in hydrogen evolution reaction and the evolution of charge-transfer resistances extracted from the impedance measurement also indicate the Fermi level varies with MoS2 film thickness. The tunable Fermi level and the high chemical stability make our MoS2 a potential catalyst. The observed thickness-dependent properties can also be applied to other transition-metal dichalcogenides (TMDs), and facilitates the development in the low-dimensional electronic devices and catalysts.
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