Non-local dielectric effects in nanoscience.

The physical properties of charges and excitations in nanoscale materials are influenced both by the dielectric properties of the material itself and the surrounding environment. This non-local dielectric effect was first discussed in the context of molecules in solvents over a century ago. In this perspective, we discuss non-local dielectric effects in zero-dimensional, one-dimensional, and two-dimensional nanoscale systems.

Nanocrystal Quantum Dots: From Discovery to Modern Development.

This review traces nanocrystal quantum dot (QD) research from the early discoveries to the present day and into the future. We describe the extensive body of theoretical and experimental knowledge that comprises the modern science of QDs. Indeed, the spatial confinement of electrons, holes, and excitons in nanocrystals, coupled with the ability of modern chemical synthesis to make complex designed structures, is today enabling multiple applications of QD size-tunable electronic and optical properties.

Dynamic emission Stokes shift and liquid-like dielectric solvation of band edge carriers in lead-halide perovskites.

Lead-halide perovskites have emerged as promising materials for photovoltaic and optoelectronic applications. Their significantly anharmonic lattice motion, in contrast to conventional harmonic semiconductors, presents a conceptual challenge in understanding the genesis of their exceptional optoelectronic properties. Here we report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielectric response originating from the incipient anharmonicity of the LO phonon at about 20 meV (160 cm-1) in the lead-bromide framework. We reconcile this liquid-like model incorporating thermally-activated dielectric solvation with more standard solid-state theories of the emission Stokes shift in crystalline semiconductors.

Enhancement of Exciton-Phonon Scattering from Monolayer to Bilayer WS2.

Layered transition metal dichalcogenides exhibit the emergence of a direct bandgap at the monolayer limit along with pronounced excitonic effects. In these materials, interaction with phonons is the dominant mechanism that limits the exciton coherence lifetime. Exciton-phonon interaction also facilitates energy and momentum relaxation, and influences exciton diffusion under most experimental conditions. However, the fundamental changes in the exciton-phonon interaction are not well understood as the material undergoes the transition from a direct to an indirect bandgap semiconductor. Here, we address this question through optical spectroscopy and microscopic theory. In the experiment, we study room-temperature statistics of the exciton line width for a large number of mono- and bilayer WS2 samples. We observe a systematic increase in the room-temperature line width of the bilayer compared to the monolayer of 50 meV, corresponding to an additional scattering rate of ∼0.1 fs-1. We further address both phonon emission and absorption processes by examining the temperature dependence of the width of the exciton resonances. Using a theoretical approach based on many-body formalism, we are able to explain the experimental results and establish a microscopic framework for exciton-phonon interactions that can be applied to naturally occurring and artificially prepared multilayer structures.

Controlled Electrochemical Intercalation of Graphene/h-BN van der Waals Heterostructures.

Electrochemical intercalation is a powerful method for tuning the electronic properties of layered solids. In this work, we report an electrochemical strategy to controllably intercalate lithium ions into a series of van der Waals (vdW) heterostructures built by sandwiching graphene between hexagonal boron nitride (h-BN). We demonstrate that encapsulating graphene with h-BN eliminates parasitic surface side reactions while simultaneously creating a new heterointerface that permits intercalation between the atomically thin layers. To monitor the electrochemical process, we employ the Hall effect to precisely monitor the intercalation reaction. We also simultaneously probe the spectroscopic and electrical transport properties of the resulting intercalation compounds at different stages of intercalation. We achieve the highest carrier density >5 × 1013 cm2 with mobility >103 cm2/(V s) in the most heavily intercalated samples, where Shubnikov-de Haas quantum oscillations are observed at low temperatures. These results set the stage for further studies that employ intercalation in modifying properties of vdW heterostructures.

Coulomb engineering of the bandgap and excitons in two-dimensional materials.

The ability to control the size of the electronic bandgap is an integral part of solid-state technology. Atomically thin two-dimensional crystals offer a new approach for tuning the energies of the electronic states based on the unusual strength of the Coulomb interaction in these materials and its environmental sensitivity. Here, we show that by engineering the surrounding dielectric environment, one can tune the electronic bandgap and the exciton binding energy in monolayers of WS2 and WSe2 by hundreds of meV. We exploit this behaviour to present an in-plane dielectric heterostructure with a spatially dependent bandgap, as an initial step towards the creation of diverse lateral junctions with nanoscale resolution.

Local Polar Fluctuations in Lead Halide Perovskite Crystals.

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH_{3}NH_{3}PbBr_{3}) and all-inorganic (CsPbBr_{3}) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr_{3}.

Li Intercalation into Graphite: Direct Optical Imaging and Cahn-Hilliard Reaction Dynamics.

Lithium intercalation into graphite is a critical process in energy storage technology. Studies of Li intercalation kinetics have proved challenging due to structural and phase complexity, and sample heterogeneity. Here we report direct time- and space-resolved, all-optical measurement of Li intercalation. We use a single crystal graphite electrode with lithographically defined disc geometry. All-optical, Raman and reflectance measurements distinguish the intrinsic intercalation process from side reactions, and provide new insight into the microscopic intercalation process. The recently proposed Cahn-Hilliard reaction (CHR) theory quantitatively captures the observed phase front spatial patterns and dynamics, using a two-layer free-energy model with novel, generalized Butler-Volmer kinetics. This approach unites Cahn-Hilliard and electrochemical kinetics, using a thermodynamically consistent description of the Li injection reaction at the crystal edge that involves a cooperative opening of graphene planes. The excellent agreement between experiment and theory presented here, with single-crystal resolution, provides strong support for the CHR theory of solid-state reactions.

Energy Transfer from Quantum Dots to Graphene and MoS2: The Role of Absorption and Screening in Two-Dimensional Materials.

We report efficient nonradiative energy transfer (NRET) from core-shell, semiconducting quantum dots to adjacent two-dimensional sheets of graphene and MoS2 of single- and few-layer thickness. We observe quenching of the photoluminescence (PL) from individual quantum dots and enhanced PL decay rates in time-resolved PL, corresponding to energy transfer rates of 1-10 ns(-1). Our measurements reveal contrasting trends in the NRET rate from the quantum dot to the van der Waals material as a function of thickness. The rate increases significantly with increasing layer thickness of graphene, but decreases with increasing thickness of MoS2 layers. A classical electromagnetic theory accounts for both the trends and absolute rates observed for the NRET. The countervailing trends arise from the competition between screening and absorption of the electric field of the quantum dot dipole inside the acceptor layers. We extend our analysis to predict the type of NRET behavior for the near-field coupling of a chromophore to a range of semiconducting and metallic thin film materials.

Probing the Dynamics of the Metallic-to-Semiconducting Structural Phase Transformation in MoS2 Crystals.

We have investigated the phase transformation of bulk MoS2 crystals from the metastable metallic 1T/1T' phase to the thermodynamically stable semiconducting 2H phase. The metastable 1T/1T' material was prepared by Li intercalation and deintercalation. The thermally driven kinetics of the phase transformation were studied with in situ Raman and optical reflection spectroscopies and yield an activation energy of 400 ± 60 meV (38 ± 6 kJ/mol). We calculate the expected minimum energy pathways for these transformations using DFT methods. The experimental activation energy corresponds approximately to the theoretical barrier for a single formula unit, suggesting that nucleation of the phase transformation is quite local. We also report that femtosecond laser writing converts 1T/1T' to 2H in a single laser pass. The mechanisms for the phase transformation are discussed.

Observation of Excitonic Rydberg States in Monolayer MoS2 and WS2 by Photoluminescence Excitation Spectroscopy.

We have identified excited exciton states in monolayers of MoS2 and WS2 supported on fused silica by means of photoluminescence excitation spectroscopy. In monolayer WS2, the positions of the excited A exciton states imply an exciton binding energy of 0.32 eV. In monolayer MoS2, excited exciton transitions are observed at energies of 2.24 and 2.34 eV. Assigning these states to the B exciton Rydberg series yields an exciton binding energy of 0.44 eV.

Ferromagnetic ordering in superatomic solids.

In order to realize significant benefits from the assembly of solid-state materials from molecular cluster superatomic building blocks, several criteria must be met. Reproducible syntheses must reliably produce macroscopic amounts of pure material; the cluster-assembled solids must show properties that are more than simply averages of those of the constituent subunits; and rational changes to the chemical structures of the subunits must result in predictable changes in the collective properties of the solid. In this report we show that we can meet these requirements. Using a combination of magnetometry and muon spin relaxation measurements, we demonstrate that crystallographically defined superatomic solids assembled from molecular nickel telluride clusters and fullerenes undergo a ferromagnetic phase transition at low temperatures. Moreover, we show that when we modify the constituent superatoms, the cooperative magnetic properties change in predictable ways.

Physical adsorption and charge transfer of molecular Br2 on graphene.

We present a detailed study of gaseous Br2 adsorption and charge transfer on graphene, combining in situ Raman spectroscopy and density functional theory (DFT). When graphene is encapsulated by hexagonal boron nitride (h-BN) layers on both sides, in a h-BN/graphene/h-BN sandwich structure, it is protected from doping by strongly oxidizing Br2. Graphene supported on only one side by h-BN shows strong hole doping by adsorbed Br2. Using Raman spectroscopy, we determine the graphene charge density as a function of pressure. DFT calculations reveal the variation in charge transfer per adsorbed molecule as a function of coverage. The molecular adsorption isotherm (coverage versus pressure) is obtained by combining Raman spectra with DFT calculations. The Fowler-Guggenheim isotherm fits better than the Langmuir isotherm. The fitting yields the adsorption equilibrium constant (∼0.31 Torr(-1)) and repulsive lateral interaction (∼20 meV) between adsorbed Br2 molecules. The Br2 molecule binding energy is ∼0.35 eV. We estimate that at monolayer coverage each Br2 molecule accepts 0.09 e- from single-layer graphene. If graphene is supported on SiO2 instead of h-BN, a threshold pressure is observed for diffusion of Br2 along the (somewhat rough) SiO2/graphene interface. At high pressure, graphene supported on SiO2 is doped by adsorbed Br2 on both sides.

Nanoscale atoms in solid-state chemistry.

We describe a solid-state material formed from binary assembly of atomically precise molecular clusters. [Co6Se8(PEt3)6][C60]2 and [Cr6Te8(PEt3)6][C60]2 assembled into a superatomic relative of the cadmium iodide (CdI2) structure type. These solid-state materials showed activated electronic transport with activation energies of 100 to 150 millielectron volts. The more reducing cluster Ni9Te6(PEt3)8 transferred more charge to the fullerene and formed a rock-salt-related structure. In this material, the constituent clusters are able to interact electronically to produce a magnetically ordered phase at low temperature, akin to atoms in a solid-state compound.

Intrinsic line shape of the Raman 2D-mode in freestanding graphene monolayers.

We report a comprehensive study of the two-phonon intervalley (2D) Raman mode in graphene monolayers, motivated by recent reports of asymmetric 2D-mode line shapes in freestanding graphene. For photon energies in the range 1.53-2.71 eV, the 2D-mode Raman response of freestanding samples appears as bimodal, in stark contrast with the Lorentzian approximation that is commonly used for supported monolayers. The transition between the freestanding and supported cases is mimicked by electrostatically doping freestanding graphene at carrier densities above 2 × 10(11) cm(-2). This result quantitatively demonstrates that low levels of charging can obscure the intrinsically bimodal 2D-mode line shape of monolayer graphene. In pristine freestanding graphene, we observe a broadening of the 2D-mode feature with decreasing photon energy that cannot be rationalized using a simple one-dimensional model based on resonant inner and outer processes. This indicates that phonon wavevectors away from the high-symmetry lines of the Brillouin zone must contribute to the 2D-mode, so that a full two-dimensional calculation is required to properly describe multiphonon-resonant Raman processes.

Slow gold adatom diffusion on graphene: effect of silicon dioxide and hexagonal boron nitride substrates.

We examine the nucleation kinetics of Au clusters on graphene and explore the relationship with layer number and underlying supporting substrate of graphene. Using the mean field theory of diffusion-limited aggregation, morphology patterns are semiquantitatively analyzed to obtain Au adatom effective diffusion constants and activation energies. Under specified assumptions, the Au adatom diffusion constant for single-layer graphene supported on SiO2 is ∼50 times smaller than that for hexagonal boron nitride (h-BN)-supported graphene and on the order of 800 times smaller than that for multilayer graphite. Bilayer graphene on SiO2 shows a Au adatom diffusion constant similar to single-layer graphene on h-BN. Scanning probe data show that single-layer graphene is far flatter on h-BN than on SiO2. Two factors are proposed as contributing to the observed lower diffusion constants on single-layer graphene: local surface roughness and homogeneous loss of dispersion/van der Waals electronic stability in multilayers. Graphene Raman spectroscopy shows little charge transfer between Au nanoparticles and graphene.

Negligible environmental sensitivity of graphene in a hexagonal boron nitride/graphene/h-BN sandwich structure.

Using Raman spectroscopy, we study the environmental sensitivity of mechanically exfoliated and electrically floating single-layer graphene transferred onto a hexagonal boron nitride (h-BN) substrate, in comparison with graphene deposited on a SiO(2) substrate. In order to understand and isolate the substrate effect on graphene electrical properties, we model and correct for Raman optical interference in the substrates. As-deposited and unannealed graphene shows a large I(2D)/I(G) ratio on both substrates, indicating extremely high quality, close to that of graphene suspended in vacuum. Thermal annealing strongly activates subsequent environmental sensitivity on the SiO(2) substrate; such activation is reduced but not eliminated on the h-BN substrate. In contrast, in a h-BN/graphene/h-BN sandwich structure, with graphene protected on both sides, graphene remains pristine despite thermal processing. Raman data provide a deeper understanding of the previously observed improved graphene electrical conductivity on h-BN substrates. In the sandwich structure, the graphene 2D Raman feature has a higher frequency and narrower line width than in pristine suspended graphene, implying that the local h-BN environment modestly yet measurably changes graphene electron and phonon dispersions.

R6G on graphene: high Raman detection sensitivity, yet decreased Raman cross-section.

Several recent studies have demonstrated the use of single and few-layer graphene as a substrate for the enhancement of Raman scattering by adsorbed molecules in a method termed graphene-enhanced Raman spectroscopy (GERS). Here we determine the resonance Raman scattering cross-section for the dye molecule rhodamine 6G (R6G) adsorbed on bilayer graphene. For the 1650 cm(-1) R6G mode, we obtain a cross-section of 5.1 × 10(-24) cm(2)·molecule(-1), a greater than 3-fold reduction from the previously reported solution value. We show that the absorption spectrum of adsorbed R6G can be measured using micro-optical contrast spectroscopy, and we find that detuning of the molecular resonance explains the decreased Raman scattering cross-section. We find no evidence for a graphene Raman enhancement process. We also study the graphene thickness dependence of the adsorbed R6G Raman signal and show that a model incorporating electromagnetic interference effects can qualitatively explain the decrease in signal with increasing graphene thickness.

Strong charge-transfer doping of 1 to 10 layer graphene by NO2.

We use resonance Raman and optical reflection contrast methods to study charge transfer in 1-10 layer (1L-10L) thick graphene samples on which NO(2) has adsorbed. Electrons transfer from the graphene to NO(2), leaving the graphene layers doped with mobile delocalized holes. Doping follows a Langmuir-type isotherm as a function of NO(2) pressure. Raman and optical contrast spectra provide independent, self-consistent measures of the hole density and distribution as a function of the number of layers (N). At high doping, as the Fermi level shift E(F) reaches half the laser photon energy, a resonance in the graphene G mode Raman intensity is observed. We observe a decrease of graphene optical absorption in the near-IR that is due to hole-doping. Highly doped graphene is more optically transparent and much more electrically conductive than intrinsic graphene. In thicker samples, holes are effectively confined near the surface, and in these samples, a small band gap opens near the surface. We discuss the properties and versatility of these highly charge-transfer-doped, few-layer-thick graphene samples as a new class of electronic materials.

Raman spectroscopy of lithographically patterned graphene nanoribbons.

Nanometer-scale graphene objects are attracting much research interest because of newly emerging properties originating from quantum confinement effects. We present Raman spectroscopy studies of graphene nanoribbons (GNRs), which are known to have nonzero electronic bandgap. GNRs of width ranging from 15 to 100 nm have been prepared by e-beam lithographic patterning of mechanically exfoliated graphene followed by oxygen plasma etching. Raman spectra of narrow GNRs can be characterized by an upshifted G band and a prominent disorder-related D band originating from scattering at the ribbon edges. The D-to-G band intensity ratio generally increases with decreasing ribbon width. However, its decrease in width of <25 nm, partly attributed to amorphization at the edges, provides a valuable experimental estimate on D mode relaxation length of <5 nm. The upshift in the G band of the narrowest GNRs can be attributed to confinement effect or chemical doping by functional groups on the GNR edges. Notably, GNRs are much more susceptible to photothermal effects resulting in reversible hole doping caused by atmospheric oxygen than bulk graphene sheets. Finally we show that the 2D band is still a reliable marker in determining the number of layers of GNRs despite its significant broadening for very narrow GNRs.