One-Dimensional Magnetic Conduction Channels across Zigzag Graphene Nanoribbon/Hexagonal Boron Nitride Heterojunctions.

We examine the electronic structure of recently fabricated in-plane heterojunctions of zigzag graphene nanoribbons embedded in hexagonal boron nitride. We focus on hitherto unexplored interface configurations in which both edges of the nanoribbon are bonded to the same chemical species, either boron or nitrogen atoms. Using ab initio and mean-field Hubbard model calculations, we reveal the emergence of one-dimensional magnetic conducting channels at these interfaces. These channels originate from the energy shift of the magnetic interface states that is induced by charge transfer between the nanoribbon and hexagonal boron nitride. We further address the response of these heterojunctions to external electric and magnetic fields, demonstrating the tunability of energy and spin splittings in the electronic structure. Our findings establish that zigzag graphene nanoribbon/hexagonal boron nitride heterojunctions are a suitable platform for exploring and engineering spin transport in the atomically thin limit, with potential applications in integrated spintronic devices.

Trap-Mediated Sensitization Governs Near-Infrared Emission from Yb3+-Doped Mixed-Halide CsPbClxBr3-x Perovskite Nanocrystals.

Understanding the photosensitization mechanisms in Yb3+-doped perovskite nanocrystals is crucial for developing their anticipated photonic applications. Here, we address this question by investigating near-infrared photoluminescence of Yb3+-doped mixed-halide CsPbClxBr3-x nanocrystals as a function of temperature and revealing its strong dependence on the stoichiometry of the host perovskite matrix. To explain the observed experimental trends, we developed a theoretical model in which energy transfer from the perovskite matrix to Yb3+ ions occurs through intermediate trap states situated beneath the conduction band of the host. The developed model provides an excellent agreement with experimental results and is further validated through the measurements of emission saturation at high excitation powers and near-infrared photoluminescence quantum yield as a function of the anion composition. Our findings establish trap-mediated energy transfer as a dominant photosensitization mechanism in Yb3+-doped CsPbClxBr3-x nanocrystals and open up new ways of engineering their optical properties for light-emitting and light-harvesting applications.

Dirac Half-Semimetallicity and Antiferromagnetism in Graphene Nanoribbon/Hexagonal Boron Nitride Heterojunctions.

Half-metals have been envisioned as active components in spintronic devices by virtue of their completely spin-polarized electrical currents. Actual materials hosting half-metallic phases, however, remain scarce. Here, we predict that recently fabricated heterojunctions of zigzag nanoribbons embedded in two-dimensional hexagonal boron nitride are half-semimetallic, featuring fully spin-polarized Dirac points at the Fermi level. The half-semimetallicity originates from the transfer of charges from hexagonal boron nitride to the embedded graphene nanoribbon. These charges give rise to opposite energy shifts of the states residing at the two edges, while preserving their intrinsic antiferromagnetic exchange coupling. Upon doping, an antiferromagnetic-to-ferrimagnetic phase transition occurs in these heterojunctions, with the sign of the excess charge controlling the spatial localization of the net magnetic moments. Our findings demonstrate that such heterojunctions realize tunable one-dimensional conducting channels of spin-polarized Dirac fermions seamlessly integrated into a two-dimensional insulator, thus holding promise for the development of carbon-based spintronics.

Unveiling and Manipulating Hidden Symmetries in Graphene Nanoribbons.

Armchair graphene nanoribbons are a highly promising class of semiconductors for all-carbon nanocircuitry. Here, we present a new perspective on their electronic structure from simple model Hamiltonians and ab initio calculations. We focus on a specific set of nanoribbons of width n=3p+2, where n is the number of carbon atoms across the nanoribbon axis and p is a positive integer. We demonstrate that the energy-gap opening in these nanoribbons originates from the breaking of a previously unidentified hidden symmetry by long-ranged hopping of π electrons and structural distortions occurring at the edges. This hidden symmetry can be restored or manipulated through the application of in-plane lattice strain, which enables continuous energy-gap tuning, the emergence of Dirac points at the Fermi level, and topological quantum phase transitions. Our work establishes an original interpretation of the semiconducting character of armchair graphene nanoribbons and offers guidelines for rationally designing their electronic structure.

Crystal Field Effect and Electric Field Screening in Multilayer Graphene with and without Twist.

We address the intrinsic polarization and screening of an external electric field in a broad range of ordered and twisted configurations of multilayer graphene, using an ab initio approach combining density functional theory and the Wannier function formalism. We show that multilayer graphene is intrinsically polarized due to the crystal field effect, an effect that is often neglected in tight-binding models of twisted bilayer graphene and similar systems. This intrinsic polarization of the order of up to a few tens of millielectronvolts has different out-of-plane alignments in ordered and twisted graphene multilayers, while the in-plane potential modulation is found to be much stronger in twisted systems. We further investigate the dielectric permittivity ε in same multilayer graphene configurations at different electric field strengths. Our findings establish a deep insight into intrinsic and extrinsic polarization in graphene multilayers and provide parameters necessary for building accurate models of these systems.

Electrically Induced Dirac Fermions in Graphene Nanoribbons.

Graphene nanoribbons are widely regarded as promising building blocks for next-generation carbon-based devices. A critical issue to their prospective applications is whether their electronic structure can be externally controlled. Here, we combine simple model Hamiltonians with extensive first-principles calculations to investigate the response of armchair graphene nanoribbons to transverse electric fields. Such fields can be achieved either upon laterally gating the nanoribbon or incorporating ambipolar chemical codopants along the edges. We reveal that the field induces a semiconductor-to-semimetal transition with the semimetallic phase featuring zero-energy Dirac fermions that propagate along the armchair edges. The transition occurs at critical fields that scale inversely with the width of the nanoribbons. These findings are universal to group-IV honeycomb lattices, including silicene and germanene nanoribbons, irrespective of the type of edge termination. Overall, our results create new opportunities to electrically engineer Dirac semimetallic phases in otherwise semiconducting graphene-like nanoribbons.

Electric-field-enhanced circular dichroism of helical semiconductor nanoribbons.

In this Letter, we analyze circular dichroism (CD) enhancement of a helical semiconductor nanoribbon exposed to a weak homogenous electric field. By creating a periodic superlattice for the confined electrons, the electric field splits the electronic sub-bands into minibands and gives rise to critical points in the electronic density of states. We show that the modification of the electronic energy spectrum results in the appearance of new optically active transitions in the CD and absorption spectra, and that the CD signal of the nanoribbon is significantly enhanced at the critical points. The ability to dynamically control the chiroptical response of semiconductor nanoribbons by an external electric field makes them promising for the next-generation nanophotonic devices.

Excitonic phenomena in perovskite quantum-dot supercrystals.

Quantum confinement and collective excitations in perovskite quantum-dot (QD) supercrystals offer multiple benefits to the light emitting and solar energy harvesting devices of modern photovoltaics. Recent advances in the fabrication technology of low dimensional perovskites has made the production of such supercrystals a reality and created a high demand for the modelling of excitonic phenomena inside them. Here we present a rigorous theory of Frenkel excitons in lead halide perovskite QD supercrystals with a square Bravais lattice. The theory shows that such supercrystals support three bright exciton modes whose dispersion and polarization properties are controlled by the symmetry of the perovskite lattice and the orientations of QDs. The effective masses of excitons are found to scale with the ratio of the superlattice period and the number of QDs along the supercrystal edge, allowing one to fine-tune the electro-optical response of the supercrystals as desired for applications. We also calculate the conductivity of perovskite QD supercrystals and analyze how it is affected by the optical generation of the three types of excitons. This paper provides a solid theoretical basis for the modelling of two- and three-dimensional supercrystals made of perovskite QDs and the engineering of photovoltaic devices with superior optoelectronic properties.

Analytical theory of real-argument Laguerre-Gaussian beams beyond the paraxial approximation.

We study the propagation of real-argument Laguerre-Gaussian beams beyond the paraxial approximation using the perturbation corrections to the complex-argument Laguerre-Gaussian beams derived earlier by Takenaka et al. [J. Opt. Soc. Am. A2, 826 (1985)JOAOD60740-323210.1364/JOSAA.2.000826]. Each higher-order correction to the amplitude of the real-argument beam (l, m) is represented as a superposition of the same-order corrections to the amplitudes of the complex-argument beams (l, q) with q=0,1,2,…,m. We derive explicit expressions for the electric and magnetic fields of transversely and longitudinally polarized real-argument beams and calculate the chirality densities of these beams up to the fourth order of the smallness parameter. For the first time to the best of our knowledge, we show that essentially achiral Gaussian beams (corresponding to l=m=0) possess nonzero chirality density due to the wavefront curvature. The obtained corrections to the paraxial beams may prove useful for precise laser beam shaping and in studies of optomechanical forces.

Intraband optical activity of semiconductor nanocrystals.

Here we review our three recently developed analytical models describing the intraband optical activity of semiconductor nanocrystals, which is induced by screw dislocations, ionic impurities, or irregularities of the nanocrystal surface. The models predict that semiconductor nanocrystals can exhibit strong optical activity upon intraband transitions and have large dissymmetry of magnetic-dipole absorption. The developed models can be used to interpret experimental circular dichroism spectra of nanocrystals and to advance the existing techniques of enantioseparation, biosensing, and chiral chemistry.

Quantum theory of electroabsorption in semiconductor nanocrystals.

We develop a simple quantum-mechanical theory of interband absorption by semiconductor nanocrystals exposed to a dc electric field. The theory is based on the model of noninteracting electrons and holes in an infinitely deep quantum well and describes all the major features of electroabsorption, including the Stark effect, the Franz-Keldysh effect, and the field-induced spectral broadening. It is applicable to nanocrystals of different shapes and dimensions (quantum dots, nanorods, and nanoplatelets), and will prove useful in modeling and design of electrooptical devices based on ensembles of semiconductor nanocrystals.

Shape-induced optical activity of chiral nanocrystals.

We present a general approach to analyzing the optical activity of semiconductor nanocrystals of chiral shapes. By using a coordinate transformation that turns a chiral nanocrystal into a nanocuboid, we calculate the rotatory strengths, dissymmetry factors, and peak values of the circular dichroism (CD) signal upon intraband transitions inside the nanocrystal. It is shown that the atomic roughness of the nanocrystal surface can result in rotatory strengths as high as 10-36 erg×cm3 and in peak CD signals of about 0.1 cm-1 for typical nanocrystal densities of 1016 cm-3. The developed approach may prove useful for other nanocrystal shapes whereas the derived expressions apply directly for the modeling and interpretation of experimental CD spectra of quantum dots, nanorods, and nanoplatelets.

Chiral Optical Properties of Möbius Graphene Nanostrips.

The advancement of optical technology demands the development of chiral nanostructures with a strong dissymmetry of optical response. Here, we comprehensively analyze the chiral optical properties of circular twisted graphene nanostrips, with a particular emphasis on the case of a Möbius graphene nanostrip. We use the method of coordinate transformation to analytically model the electronic structure and optical spectra of the nanostrips, while employing the cyclic boundary conditions to account for their topology. It is found that the dissymmetry factors of twisted graphene nanostrips can reach 0.01, exceeding the typical dissymmetry factors of small chiral molecules by 1-2 orders of magnitude. The results of this work thus demonstrate that twisted graphene nanostrips of Möbius and similar geometries are highly promising nanostructures for chiral optical applications.

Exciton g-factors in monolayer and bilayer WSe2 from experiment and theory.

The optical properties of monolayer and bilayer transition metal dichalcogenide semiconductors are governed by excitons in different spin and valley configurations, providing versatile aspects for van der Waals heterostructures and devices. Here, we present experimental and theoretical studies of exciton energy splittings in external magnetic field in neutral and charged WSe2 monolayer and bilayer crystals embedded in a field effect device for active doping control. We develop theoretical methods to calculate the exciton g-factors from first principles for all possible spin-valley configurations of excitons in monolayer and bilayer WSe2 including valley-indirect excitons. Our theoretical and experimental findings shed light on some of the characteristic photoluminescence peaks observed for monolayer and bilayer WSe2. In more general terms, the theoretical aspects of our work provide additional means for the characterization of single and few-layer transition metal dichalcogenides, as well as their heterostructures, in the presence of external magnetic fields.

Toward Bright Red-Emissive Carbon Dots through Controlling Interaction among Surface Emission Centers.

Relatively weak red photoluminescence of carbon dots (CDots) is a major challenge on the way to their successful implementation in biological and optoelectronic devices. We present a theoretical analysis of the interaction among the surface emission centers of CDots, showing that it may determine efficiency of the red photoluminescence of CDots. Based on the previous experimental studies, it is assumed that the optical response of the CDots is determined by the molecule-like subunits of polycyclic aromatic hydrocarbons (PAHs) attached to the CDots' surface. Three characteristic types of coupling of these PAH subunits are considered: non-interacting monomers, noncovalently bound dimers, and covalently bound dimers with two, three, or four carbon linkers. We demonstrate that the CDots' photoluminescence broadens, redshifts, and weakens by 2 orders of magnitude when the free monomers are substituted by the covalently bridged centers. These and other results of our study show that the realization of CDots with many weakly interacting surface emission centers may constitute an efficient way to achieve their efficient red photoluminescence, which is highly desirable for biological and optoelectronic applications.

Amino Functionalization of Carbon Dots Leads to Red Emission Enhancement.

The availability of carbon dots (CDots) with bright red photoluminescence (PL) would significantly broaden the range of their biological and optoelectronic applications. We present a theoretical model that predicts that amino functionalization of CDots not only shifts their PL to longer wavelengths but also preserves large oscillator strengths of the fundamental radiative transitions of CDots. The model considers the optical response of amino-functionalized CDots determined by molecule-like subunits of polycyclic aromatic hydrocarbons with one, two, or three -NH2 groups at the CDots' surface; the excited state of those subunits is characterized by strong charge separation between the amino groups and CDots' carbon core. Such a separation determines the Stokes shift of the CDots' emission, which increases with the growing amount of the amino functional groups at the CDot surface. Our model explains the experimentally observed dependence of the PL spectra of CDots on the excitation wavelength, the phenomenon well documented in the literature for nitrogen-containing CDots.

sp2-sp3-Hybridized Atomic Domains Determine Optical Features of Carbon Dots.

Carbon dots (CDots) are a promising biocompatible nanoscale source of light, yet the origin of their emission remains under debate. Here, we show that all the distinctive optical properties of CDots, including the giant Stokes shift of photoluminescence and the strong dependence of emission color on excitation wavelength, can be explained by the linear optical response of the partially sp2-hybridized carbon domains located on the surface of the CDots' sp3-hybridized amorphous cores. Using a simple quantum chemical approach, we show that the domain hybridization factor determines the localization of electrons and the electronic bandgap inside the domains and analyze how the distribution of this factor affects the emission properties of CDots. Our calculation data fully agree with the experimental optical properties of CDots, confirming the overall theoretical picture underlying the model. It is also demonstrated that fabrication of CDots with large hybridization factors of carbon domains shifts their emission to the red side of the visible spectrum, without a need to modify the size or shape of the CDots. Our theoretical model provides a useful tool for experimentalists and may lead to extending the applications of CDots in biophysics, optoelectronics, and photovoltaics.

Optical Activity of Semiconductor Gammadions beyond Planar Chirality.

We present rigorous analysis of optical activity of chiral semiconductor gammadions whose chirality in three dimensions is caused by the nonuniformity of thickness in the transverse plane. It is shown that such gammadions not only distinguish between the two circular polarizations upon scattering and reflection of light, like all two-dimensional semiconductor nanostructures with planar chirality do, but also exhibit circular dichroism and circularly polarized luminescence. Chiral semiconductor gammadions whose charge carriers are mostly confined to the arms are found to feature both high dissymmetry of optical response and a constant-sign circular dichroism signal over a wide frequency range. It is also shown that the strength of the gammadion's chiroptical response is determined solely by two geometric factors: the variation range of the gammadion's thickness and the arms' curvature. Our seminal theoretical study is intended to lay the foundation for future applications of semiconductor gammadions in chiral nanophotonics and nanotechnology.

Induction of Chirality in Two-Dimensional Nanomaterials: Chiral 2D MoS2 Nanostructures.

Two-dimensional (2D) nanomaterials have been intensively investigated due to their interesting properties and range of potential applications. Although most research has focused on graphene, atomic layered transition metal dichalcogenides (TMDs) and particularly MoS2 have gathered much deserved attention recently. Here, we report the induction of chirality into 2D chiral nanomaterials by carrying out liquid exfoliation of MoS2 in the presence of chiral ligands (cysteine and penicillamine) in water. This processing resulted in exfoliated chiral 2D MoS2 nanosheets showing strong circular dichroism signals, which were far past the onset of the original chiral ligand signals. Using theoretical modeling, we demonstrated that the chiral nature of MoS2 nanosheets is related to the presence of chiral ligands causing preferential folding of the MoS2 sheets. There was an excellent match between the theoretically calculated and experimental spectra. We believe that, due to their high aspect ratio planar morphology, chiral 2D nanomaterials could offer great opportunities for the development of chiroptical sensors, materials, and devices for valleytronics and other potential applications. In addition, chirality plays a key role in many chemical and biological systems, with chiral molecules and materials critical for the further development of biopharmaceuticals and fine chemicals, and this research therefore should have a strong impact on relevant areas of science and technology such as nanobiotechnology, nanomedicine, and nanotoxicology.

Erratum: Mixing of quantum states: A new route to creating optical activity.

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