Samantha Bruzzone

Ab-Initio Simulations of Deformation Potentials and Electron Mobility in Chemically Modified Graphene and two-dimensional hexagonal Boron-Nitride

We present an ab-initio study of electron mobility and electron-phonon coupling in chemically modified graphene, considering fluorinated and hydrogenated graphene at different percentage coverage. Hexagonal boron carbon nitrogen is also investigated due the increased interest shown by the research community towards this material. In particular, the deformation potentials are computed by means of density functional theory, while the carrier mobility is obtained according to the Takagi model (S. Takagi, A. Toriumi, and H. Tango, IEEE Trans. Electron Devices 41, 2363 (1994)). We will show that graphene with a reduced degree of hydrogenation can compete, in terms of mobility, with silicon technology.

Lateral graphene-hBCN heterostructures as a platform for fully two-dimensional transistors.

We propose that lateral heterostructures of single-atomic-layer graphene and hexagonal boron-carbon-nitrogen (hBCN) domains, can represent a powerful platform for the fabrication and the technological exploration of real two-dimensional field-effect transistors. Indeed, hBCN domains have an energy bandgap between 1 and 5 eV, and are lattice-matched with graphene; therefore they can be used in the channel of a FET to effectively inhibit charge transport when the transistor needs to be switched off. We show through ab initio and atomistic simulations that a FET with a graphene-hBCN-graphene heterostructure in the channel can exceed the requirements of the International Technology Roadmap for Semiconductors for logic transistors at the 10 and 7 nm technology nodes. Considering the main figures of merit for digital electronics, a FET with gate length of 7 nm at a supply voltage of 0.6 V exhibits I(on)/I(off) ratio larger than 10(4), intrinsic delay time of about 0.1 ps, and a power-delay-product close to 0.1 nJ/m. More complex graphene-hBCN heterostructures can allow the realization of different multifunctional devices, translating on a truly two-dimensional structure some of the device principles proposed during the first wave of nanoelectronics based on III-V heterostructures, as for example the resonant tunneling FET.

Very Large Current Modulation in Vertical Heterostructure Graphene/hBN Transistors

In this paper, we investigate the electrical behavior of transistors based on a vertical graphene-hexagonal boron nitride (hBN) heterostructure, using atomistic multiphysics simulations based on density-functional theory and non-equilibrium Greens function formalism. We show that the hBN current-blocking layer is effective and allows modulation of the current by five orders of magnitude, confirming experimental results. We also highlight - through accurate numerical calculations and simplified analytical modeling - some intrinsic limitations of vertical heterostructure transistors. We show that the overlap between gate contacts and source/drain leads screens the electric field induced by the gates and is responsible for the excessive degradation of the sub-threshold swing, the ION/IOFF ratio, and the cut-off frequency.

Ab initio study of ionic liquids by KS-DFT/3D-RISM-KH theory.

Properties of molecules solvated in ionic liquids (ILs) are strongly affected by solvent environment. For this reason, to give reliable results, ab initio calculations on solutes in ILs, including ions constituting ionic liquid itself, have to self-consistently account for the change of both electronic and classical solvation structure in ILs. Here, we study the electronic structure of the methyl-methylimidazolium ion in the bulk liquid of [mmim][Cl] by using the self-consistent field coupling of Kohn-Sham density functional theory and three-dimensional molecular theory of solvation (aka 3D-RISM) with the closure approximation of Kovalenko and Hirata. The KS-DFT/3D-RISM-KH method yields the 3D distribution of the IL solvent species around the [mmim] solute, underlying the most important peculiarities of this kind of systems such as the stacking interaction between neighboring cations, and reproduces the enhancement of the dipole moment resulting from the polarization of the cation by the solvent in a very good agreement with the results of an ab initio MD calculation. The KS-DFT/3D-RISM-KH method offers an accurate and computationally efficient procedure to perform ab initio calculations on species solvated in ionic liquids.

Solvation thermodynamics of alkali and halide ions in ionic liquids through integral equations

In this work, we study the solvation thermodynamics and other solvation properties of small ions in two room-temperature ionic liquids, dimethyl imidazolium hexafluorophosphate [mmim] [pf6] and dimethyl imidazolium chloride [mmim][cl] with the reference interaction site model (RISM). The nature of the charge affects several aspects of solvation, from electrostriction to the mutual disposition of cations around the solute; nevertheless, the long-range screening behavior of the liquid appears to be insensitive to both charge and dimensions of the solute. The ion solvation is energy driven, as expected for the nature of the solvent, and displays a marked asymmetry between cation and anion solvation chemical potential. Such asymmetry is dependent, even qualitatively, on the ionic liquid chosen as solvent. Partial molar volumes of ions in solution are found to follow the nature of ion-solvent interaction.

An Open-Source Multiscale Framework for the Simulation of Nanoscale Devices

We present a general simulation framework for assessing the performance of nanoscale devices that combines several powerful and widely used open-source codes, and based on minimal but chemically accurate tight-binding Hamiltonians obtained from density-functional theory calculations and using maximally localized Wannier functions to represent the electronic state. Transport properties are then computed within the nonequilibrium Greens function formalism. We illustrate the capabilities of this framework applying it to a transistor with generic gate geometries, i.e., a double-gate nanoscale field-effect transistor where the channel is formed by graphene nanoribbons terminated with hydrogen, fluorine, and OH groups.

Experimental and TDDFT Characterization of the Light-Induced Cluster-to-Iron Charge Transfer in the (Ferrocenylethynyl)-Substituted Trinuclear Platinum Derivative [Pt3(μ-PBut2)3(CO)2(C≡C−Fc)]+

The reaction between Pt(3)(mu-PBu(t)(2))(3)(CO)(2)Cl (2) and ethynylferrocene, in the presence of catalytic amounts of CuI, gives Pt(3)(mu-PBu(t)(2))(3)(CO)(2)C[triple bond]CFc (1), characterized by X-ray crystallography and representing a rare example of the sigma-coordination of an alkynyl moiety to a cluster unit. In a dichloromethane (CH(2)Cl(2)) solution, compound 1 undergoes three consecutive one-electron oxidations, the first of which is assigned to the ferrocene-centered Fe(II)/Fe(III) redox couple. Spectroelectrochemistry, carried out on a solution of 1, shows the presence of a broad band in the near-IR region, growing after the electrochemical oxidation, preliminarily associated with a metal-to-metal charge transfer toward the Fe(III) ion of the ferrocenium unit. Density functional theory (DFT) has been employed to analyze the ground- and excited-state properties of 1 and 1(+), both in the gas phase and in a CH(2)Cl(2) solution. Vertical excitation energies have been computed by the B3LYP hybrid functional in the framework of the time-dependent DFT approach, and the polarizable continuum model has been used to assess the solvent effect. Our results show that taking into account the medium effects together with the choice of an appropriate molecular model is crucial to correctly reproducing the excitation spectra of such compounds. Indeed, the nature of the substituents on P atoms has been revealed to have a key role in the quality of the calculated spectra.

Some spectroscopic properties of gold nanorods according to a schematic quantum model founded on the dielectric behavior of the electron-gas confined in a box. I

Abstract The long-standing confined-electron-gas approach employed for simulating in a simple way the size-dependent “free electron” dielectric behavior of isotropic nanoparticles has been extended to the investigation of some spectroscopic properties of gold nanorods. The model adopted takes also into accounts size-independent interband effects estimated in a semiempirical way from bulk dielectric data. Predictions relative to the optical absorption and photoluminescence behavior, associated with the coherent, collective excitation of the electron gas, are derived on the basis of a fairly simple formalism, whose implementation allows to deal with a number of conduction electrons of the order of ca. 10 4 , at a tolerable computational cost. The predictions of the model agree reasonably well with the few available experimental data. The nature of some approximations introduced suggests also the opportunity of a further analysis of specific points.

Vertical transport in graphene-hexagonal boron nitride heterostructure devices

Research in graphene-based electronics is recently focusing on devices based on vertical heterostructures of two-dimensional materials. Here we use density functional theory and multiscale simulations to investigate the tunneling properties of single- and double-barrier structures with graphene and few-layer hexagonal boron nitride (h-BN) or hexagonal boron carbon nitride (h-BC2N). We find that tunneling through a single barrier exhibit a weak dependence on energy. We also show that in double barriers separated by a graphene layer we do not observe resonant tunneling, but a significant increase of the tunneling probability with respect to a single barrier of thickness equal to the sum of the two barriers. This is due to the fact that the graphene layer acts as an effective phase randomizer, suppressing resonant tunneling and effectively letting a double-barrier structure behave as two single-barriers in series. Finally, we use multiscale simulations to reproduce a current-voltage characteristics resembling that of a resonant tunneling diode, that has been experimentally observed in single barrier structure. The peak current is obtained when there is perfect matching between the densities of states of the cathode and anode graphene regions.

Nanodevices in Flatland: Two-dimensional graphene-based transistors with high I on /I off ratio

We present a multi-scale investigation of graphene-based transistors with a hexagonal boron-carbon-nitride (h-BCN) barrier in the channel. Our approach exploits ab-initio calculations for an accurate extraction of energy bands and tight-binding simulations in order to compute charge transport. We show that the h-BCN barrier inhibits the ambipolar behavior of graphene transistors, leading to a large Ion/Ioff ratio, within the ITRS roadmap specifications for future semiconductor technology nodes.