Rhombohedral-stacked bilayer transition metal dichalcogenides for high-performance atomically thin CMOS devices.

Van der Waals coupling with different stacking configurations is emerging as a powerful method to tune the optical and electronic properties of atomically thin two-dimensional materials. Here, we investigate 3R-stacked transition-metal dichalcogenides as a possible option for high-performance atomically thin field-effect transistors (FETs). We report that the effective mobility of 3R bilayer WS2 (WSe2) is 65% (50%) higher than that of 2H WS2 (WSe2). The 3R bilayer WS2 n-type FET exhibits a high on-state current of 480 µA/µm at Vds = 1 V and an ultralow on-state resistance of 1 kilohm·µm. Our observations, together with multiscale simulations, reveal that these improvements originate from the strong interlayer coupling in the 3R stacking, which is reflected in a higher conductance compared to the 2H stacking. Our method provides a general and scalable route toward advanced channel materials in future electronic devices for ultimate scaling, especially for complementary metal oxide semiconductor applications.

Electrical properties of graphene-metal contacts.

The performance of devices and systems based on two-dimensional material systems depends critically on the quality of the contacts between 2D material and metal. A low contact resistance is an imperative requirement to consider graphene as a candidate material for electronic and optoelectronic devices. Unfortunately, measurements of contact resistance in the literature do not provide a consistent picture, due to limitations of current graphene technology, and to incomplete understanding of influencing factors. Here we show that the contact resistance is intrinsically dependent on graphene sheet resistance and on the chemistry of the graphene-metal interface. We present a physical model of the contacts based on ab-initio simulations and extensive experiments carried out on a large variety of samples with different graphene-metal contacts. Our model explains the spread in experimental results as due to uncontrolled graphene doping and suggests ways to engineer contact resistance. We also predict an achievable contact resistance of 30 Ω·µm for nickel electrodes, extremely promising for applications.

Semiempirical Hamiltonian for simulation of azobenzene photochemistry.

We present a semiempirical Hamiltonian that provides an accurate description of the first singlet and triplet potential energy surfaces of azobenzene for use in direct simulations of the excited-state dynamics. The parameterization made use of spectroscopic and thermochemical data and the best ab initio results available to date. Two-dimensional potential energy surfaces based on constrained geometry optimizations are presented for the states that are most relevant for the photochemistry of azobenzene, namely, S(0), S(1), and S(2). In order to run simulations of the photodynamics of azobenzene in hydrocarbons or hydroxylic solvents, we determined the interactions of methane and methanol with the azo group by ab initio calculations and fitted the interactions with a QM/MM interaction Hamiltonian.

Photodynamics and time-resolved fluorescence of azobenzene in solution: a mixed quantum-classical simulation.

We have simulated the photodynamics of azobenzene by means of the Surface Hopping method. We have considered both the trans → cis and the cis → trans processes, caused by excitation in the n → π* band (S(1) state). To bring out the solvent effects on the excited state dynamics, we have run simulations in four different environments: in vacuo, in n-hexane, in methanol, and in ethylene glycol. Our simulations reproduce very well the measured quantum yields and the time dependence of the intensity and anisotropy of the transient fluorescence. Both the photoisomerization and the S(1) → S(0) internal conversion require the torsion of the N═N double bond, but the N-C bond rotations and the NNC bending vibrations also play a role. In the trans → cis photoconversion the N═N torsional motion and the excited state decay are delayed by increasing the solvent viscosity, while the cis → trans processes are less affected. The analysis of the simulation results allows the experimental observations to be explained in detail, and in particular the counterintuitive increase of the trans → cis quantum yield with viscosity, as well as the relationship between the excited state dynamics and the solvent effects on the fluorescence lifetimes and depolarization.

Oscillator strength and polarization of the forbidden n-->pi* band of trans-azobenzene: a computational study.

The trans-azobenzene molecule is thought to prefer a planar C2h geometry, in gas phase as well as in solution, according to the most recent computational studies. As a consequence, the weak n-->pi* absorption band is forbidden by symmetry at the equilibrium geometry, and its intensity depends on the effect of the vibrational motions on the electronic structure. In this computational study, we determine the contribution of the vibrational modes to the oscillator strength, taking into account the anharmonicity, the thermal distributions, and the solvent effects. The good agreement of our results with the measured absorption spectrum confirms the C2h equilibrium structure of trans-azobenzene, with a relatively easy torsion of the phenyl groups around the N--C bonds. We also address the question of the polarization of this transition, which is a preliminary step to interpret the time-resolved fluorescence anisotropy measurements [C.-W. Chang et al., J. Am. Chem. Soc., 126, 10109 (2004)], a very sensitive probe of solvent effects on the excited state dynamics.