Electronic Structure of Isolated Graphene Nanoribbons in Solution Revealed by Two-Dimensional Electronic Spectroscopy.

Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.

Lead Halide Perovskite Nanocrystals with Low Inhomogeneous Broadening and High Coherent Fraction through Dicationic Ligand Engineering.

Lead halide perovskite nanocrystals (LHP NCs) are an emerging materials system with broad potential applications, including as emitters of quantum light. We apply design principles aimed at the structural optimization of surface ligand species for CsPbBr3 NCs, leading us to the study of LHP NCs with dicationic quaternary ammonium bromide ligands. Through the selection of linking groups and aliphatic backbones guided by experiments and computational support, we demonstrate consistently narrow photoluminescence line shapes with a full-width-at-half-maximum below 70 meV. We observe bulk-like Stokes shifts throughout our range of particle sizes, from 7 to 16 nm. At cryogenic temperatures, we find sub-200 ps lifetimes, significant photon coherence, and the fraction of photons emitted into the coherent channel increasing markedly to 86%. A 4-fold reduction in inhomogeneous broadening from previous work paves the way for the integration of LHP NC emitters into nanophotonic architectures to enable advanced quantum optical investigation.

A Practical Review of NMR Lineshapes for Spin-1/2 and Quadrupolar Nuclei in Disordered Materials.

NMR is a powerful spectroscopic method that can provide information on the structural disorder in solids, complementing scattering and diffraction techniques. The structural disorder in solids can generate a dispersion of local magnetic and electric fields, resulting in a distribution of isotropic chemical shift δiso and quadrupolar coupling CQ. For spin-1/2 nuclei, the NMR linewidth and shape under high-resolution magic-angle spinning (MAS) reflects the distributions of isotropic chemical shift, providing a rich source of disorder information. For quadrupolar nuclei, the second-order quadrupolar broadening remains present even under MAS. In addition to isotropic chemical shift, structural disorder can impact the electric field gradient (EFG) and consequently the quadrupolar NMR parameters. The distributions of quadrupolar coupling and isotropic chemical shift are superimposed with the second-order quadrupolar broadening, but can be potentially characterized by MQMAS (multiple-quantum magic-angle spinning) spectroscopy. We review analyses of NMR lineshapes in 2D DQ-SQ (double-quantum single-quantum) and MQMAS spectroscopies, to provide a guide for more general lineshape analysis. In addition, methods to enhance the spectral resolution and sensitivity for quadrupolar nuclei are discussed, including NMR pulse techniques and the application of high magnetic fields. The role of magnetic field strength and its impact on the strategy of determining optimum NMR methods for disorder characterization are also discussed.

Probing of local polarity in poly(methyl methacrylate) with the charge transfer transition in Nile red.

The permittivity of polymers and its spatial distribution play a crucial role in the behavior of thin films, such as those used, e.g., as sensor coatings. In an attempt to develop a conclusive approach to determine these quantities, the polarity of the model polymer poly(methyl methacrylate) (PMMA) in 600 nm thin films on a glass support was probed by the energy of the charge transfer transition in the oxazine dye Nile red (NR) at 25 °C. The absorption and fluorescence spectra of NR were observed to shift to the red with increasing solvent polarity, because of the intramolecular charge transfer character of the optical transition. New types of solvatochromic plots of emission frequency against absorption frequency and vice versa afforded the Onsager radius-free estimation of the ground and excited states dipole moment ratio. With this approach the values of these dipole moments of 11.97 D and 18.30-19.16 D, respectively, were obtained for NR. An effective local dielectric constant of 5.9-8.3 for PMMA thin films was calculated from the solvatochromic plot and the fluorescence maximum of NR observed in the PMMA films. The fluorescence band of NR in the rigid PMMA films shifted to the red by 130 cm-1 with increasing excitation wavelength from 470 to 540 nm, while in a series of liquids the position of the emission maximum of NR remained constant within same range of the excitation wavelength. It is concluded that the fluorescence spectrum of NR in PMMA undergoes inhomogeneous broadening due to different surroundings of NR molecules in the ground state and slow sub-glass transition (T g) relaxations in PMMA.

Charge Carrier Hopping Dynamics in Homogeneously Broadened PbS Quantum Dot Solids.

Energetic disorder in quantum dot solids adversely impacts charge carrier transport in quantum dot solar cells and electronic devices. Here, we use ultrafast transient absorption spectroscopy to show that homogeneously broadened PbS quantum dot arrays (σhom2:σinh2 > 19:1, σinh/kBT < 0.4) can be realized if quantum dot batches are sufficiently monodisperse (δ ≲ 3.3%). The homogeneous line width is found to be an inverse function of quantum dot size, monotonically increasing from ∼25 meV for the largest quantum dots (5.8 nm diameter/0.92 eV energy) to ∼55 meV for the smallest (4.1 nm/1.3 eV energy). Furthermore, we show that intrinsic charge carrier hopping rates are faster for smaller quantum dots. This finding is the opposite of the mobility trend commonly observed in device measurements but is consistent with theoretical predictions. Fitting our data to a kinetic Monte Carlo model, we extract charge carrier hopping times ranging from 80 ps for the smallest quantum dots to over 1 ns for the largest, with the same ethanethiol ligand treatment. Additionally, we make the surprising observation that, in slightly polydisperse (δ ≲ 4%) quantum dot solids, structural disorder has a greater impact than energetic disorder in inhibiting charge carrier transport. These findings emphasize how small improvements in batch size dispersity can have a dramatic impact on intrinsic charge carrier hopping behavior and will stimulate further improvements in quantum dot device performance.

Ultraclean Single Photon Emission from a GaN Quantum Dot.

Wide bandgap III-nitride quantum dots (QDs) are promising materials for the realization of solid-state single-photon sources, especially operating at room temperature. However, so far a large degree of inhomogeneous broadening induced by spectral diffusion has compromised their use. Here, we demonstrate the ultraclean emission from single GaN QDs formed at macrostep edges in a GaN/AlGaN quantum well. As a likely consequence of the high growth temperature and hence a reduced defect density, spectral diffusion is heavily suppressed to levels at least 1 order of magnitude lower than conventional GaN QDs. A record narrow line width of as small as 87 µeV is obtained, while the low inhomogeneous broadening enables us to assess an upper limit of homogeneous broadening in the QDs (27 µeV). Furthermore, the uncontaminated emission facilitates the generation of ultraviolet single-photons with unprecedented purity (g(2)(0) = 0.02). The realization of high-quality GaN QDs will enable exploration of optoelectronic properties of III-nitrides, opening up the possibility of realizing single-photon quantum information systems operating at room temperature.

Dual-laser homo-FRET on the cell surface.

Inhomogeneous broadening and red-edge effects have been detected on a highly mobile system of fluorescently conjugated mAbs targeted to cell surface receptors. By exploiting site-selective spectroscopy and the characteristic loss of homo-FRET on increasing excitation and decreasing emission wavelengths, contributions of physical rotation and homo-FRET to the depolarization of fluorescence anisotropy have been separated. Absolute homo-FRET efficiency has been determined by ratioing two anisotropies: a homo-FRET-sensitive one, which is excited at the absorption main band and detected at the long wavelength region of emission, and a homo-FRET-insensitive one, which is excited at the long wavelength region of absorption and detected at the short wavelength region of emission. Because the anisotropies are simultaneously detected in a unified detection scheme of a dual T-format arrangement, the method is applicable for the real-time tracking of dynamical changes of physical rotations and proximities. The utility of the method is demonstrated in the context of the MHCII molecule and the heavy and light chains of the MHCI molecule, a system of three receptors with well-characterized close mutual proximities. Although the method is presented for a flow cytometer, it can also be realized in a fluorescence microscope capable for dual-laser excitation and dual-anisotropy detection.

Time-Resolved Emission Reveals Ensemble of Emissive States as the Origin of Multicolor Fluorescence in Carbon Dots.

The origin of photoluminescence in carbon dots has baffled scientists since its discovery. We show that the photoluminescence spectra of carbon dots are inhomogeneously broadened due to the slower relaxation of the solvent molecules around it. This gives rise to excitation-dependent fluorescence that violates the Kasha-Vavilov rule. The time-resolved experiment shows significant energy redistribution, relaxation among the emitting states, and spectral migration of fluorescence spectra in the nanosecond time scale. The excitation-dependent multicolor emission in time-integrated spectra is typically governed by the relative population of these emitting states.

Magnetization transfer from inhomogeneously broadened lines: A potential marker for myelin.

PURPOSE: To characterize a new approach to magnetization transfer (MT) imaging with improved specificity for myelinated tissues relative to conventional MT. METHODS: Magnetization transfer preparation sequences were implemented with all radiofrequency power centered on a single frequency and also with power evenly divided between positive and negative frequencies. Dual frequency saturation was achieved both with short, alternating frequency pulses and with sinusoidal modulation of continuous irradiation. Images following preparation were acquired with a single shot fast spin echo sequence. Single and dual frequency preparation should achieve similar saturation of molecules except for those with inhomogenously broadened lines. Inhomogenous MT (IHMT) images were generated by subtraction of dual from single frequency prepared images. IHMT imaging was performed with different power and frequency in the brains of normal volunteers. RESULTS: The IHMT method demonstrated a greater white/gray matter ratio than conventional MT and virtual elimination of signal in scalp and other unmyelinated tissues. IHMT exceeded 5% of the fully relaxed magnetization in white matter. A broad frequency spectrum and signs of axonal angular dependence at high frequency were observed that are consistent with dipolar broadening. CONCLUSION: IHMT shows promise for myelin-specific imaging. Further study of physical mechanisms and diagnostic sensitivity are merited.

The lineshape of the electronic spectrum of the green fluorescent protein chromophore, part II: solution phase.

The vibronic spectra of the green fluorescent protein chromophore analogues p-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) and 3,5-tert-butyl-HBDI (35Bu) are similar in the vacuum, but very different in water or ethanol. To understand this difference, we have computed the vibrationally resolved solution spectra of these chromophores, using the polarizable continuum model (PCM) to account for solvent effects on the (harmonic) potential energy surfaces (PES). In agreement with experiment, we found that the vibrational progression increases with the polarity of the solvent, but we could neither reproduce the broadening, nor the large difference between the absorption spectra of HBDI and 35Bu. To account for the inhomogeneous broadening of the solution spectra, we used two approaches. In the first, we estimated the polar broadening from the solvent reorganization energy upon photo-excitation, using the state-specific PCM implementation. In the second, we estimated the broadening from the variance of the vertical excitation energies in molecular dynamics trajectories. Although we found good agreement for the lineshape of 35Bu in ethanol, and to a lesser extent in water, we highly underestimated the broadening for HBDI. To resolve this discrepancy, we explored the PES of HBDI in water and found that in contrast to the PCM result, the ground-state geometry is not planar in explicit solvent. We furthermore found that nonplanar geometries enhance the intramolecular charge transfer upon excitation. Therefore, the solvent reorganization and broadening are much larger and we speculate that the much broader spectrum of HBDI in water is due to the population of nonplanar geometries.

Collective States in Molecular Monolayers on 2D Materials.

Collective excited states form in organic two-dimensional layers through Coulomb coupling of the molecular transition dipole moments. They manifest as characteristic strong and narrow peaks in the excitation and emission spectra that are shifted to lower energies compared with the monomer transition. We study experimentally and theoretically how robust the collective states are against homogeneous and inhomogeneous broadening, as well as spatial disorder that occurs in real molecular monolayers. Using a microscopic model for a two-dimensional dipole lattice in real space, we calculate the properties of collective states and their extinction spectra. We find that the collective states persist even for 1-10% random variation in the molecular position and in the transition frequency, with a peak position and integrated intensity similar to those for the perfectly ordered system. We measured the optical response of a monolayer of the perylene derivative MePTCDI on two-dimensional materials. On the wide-band-gap insulator hexagonal boron nitride, it shows strong emission from the collective state with a line width that is dominated by the inhomogeneous broadening of the molecular state. When the semimetal graphene is used as a substrate, however, the luminescence is completely quenched. By combining optical absorption, luminescence, and multiwavelength Raman scattering, we verify that the MePTCDI molecules form very similar collective monolayer states on hexagonal boron nitride and graphene substrates, but on graphene the line width is dominated by nonradiative excitation transfer from the molecules to the substrate. Our study highlights the transition from the localized molecular state of the monomer to a delocalized collective state in the two-dimensional molecular lattice that is entirely based on Coulomb coupling between optically active excitations of the electrons and molecular vibrations. The excellent properties of organic monolayers make them promising candidates for components of soft-matter optoelectronic devices.

Study and analysis of the optical absorption cross section and energy states broadenings in quantum dot lasers.

In this report, we measured experimentally the modal absorption spectra of the InP and InAsP quantum dot (QD) lasers using multi-section device technique. The optical absorption cross section ( σ 0 ) and inhomogeneous broadening for the ground state (GS) and excited state (ES) were analyzed and calculated theoretically from the absorption spectra. The results showed that the InP QD laser exhibited σ 0 to be 1.347 × 10 - 14  â€‹cm 2 . eV and 3.016 × 10 - 14  â€‹cm 2 eV for GS and ES respectively, whereas for the InAsP QD material it was found as 0.511 × 10 - 14 cm 2 eV and 3.099 × 10 - 14 cm 2 . eV for GS and ES respectively. Moreover, the inhomogeneous broadening in the GS increases from 35.6 eV to 63.6 eV when As was added to InP QD, similarly, the inhomogeneous broadening of ES increases from 46.9 eV to 103.8 eV. The alloying InP QDs with arsenic decreases the σ 0 of the ground state (lasing state) and increases both inhomogeneous and linewidth broadenings. This finding may help the grower to control the growth conditions and the molecule fractions of the crystal to improve the spectral properties of the optoelectronics devices.

Effect of Inhomogeneous Broadening in Ultraviolet III-Nitride Light-Emitting Diodes.

In the past years, light-emitting diodes (LED) made of GaN and its related ternary compounds with indium and aluminium have become an enabling technology in all areas of lighting. Visible LEDs have yet matured, but research on deep ultraviolet (UV) LEDs is still in progress. The polarisation in the anisotropic wurtzite lattice and the low free hole density in p-doped III-nitride compounds with high aluminium content make the design for high efficiency a critical step. The growth kinetics of the rather thin active quantum wells in III-nitride LEDs makes them prone to inhomogeneous broadening (IHB). Physical modelling of the active region of III-nitride LEDs supports the optimisation by revealing the opaque active region physics. In this work, we analyse the impact of the IHB on the luminescence and carrier transport III-nitride LEDs with multi-quantum well (MQW) active regions by numerical simulations comparing them to experimental results. The IHB is modelled with a statistical model that enables efficient and deterministic simulations. We analyse how the lumped electronic characteristics including the quantum efficiency and the diode ideality factor are related to the IHB and discuss how they can be used in the optimisation process.

Superradiant lasing in inhomogeneously broadened ensembles with spatially varying coupling.

Background: Theoretical studies of superradiant lasing on optical clock transitions predict a superb frequency accuracy and precision closely tied to the bare atomic linewidth. Such a superradiant laser is also robust against cavity fluctuations when the spectral width of the lasing mode is much larger than that of the atomic medium. Recent predictions suggest that this unique feature persists even for a hot and thus strongly broadened ensemble, provided the effective atom number is large enough. Methods: Here we use a second-order cumulant expansion approach to study the power, linewidth and lineshifts of such a superradiant laser as a function of the inhomogeneous width of the ensemble including variations of the spatial atom-field coupling within the resonator. Results: We present conditions on the atom numbers, the pump and coupling strengths required to reach the buildup of collective atomic coherence as well as scaling and limitations for the achievable laser linewidth. Conclusions: We show how sufficiently large numbers of atoms subject to strong optical pumping can induce synchronization of the atomic dipoles over a large bandwidth. This generates collective stimulated emission of light into the cavity mode leading to narrow-band laser emission at the average of the atomic frequency distribution. The linewidth is orders of magnitudes smaller than that of the cavity as well as the inhomogeneous gain broadening and exhibits reduced sensitivity to cavity frequency noise.

Spectroscopic Properties of Phase-Pure and Polytypic Colloidal Semiconductor Quantum Wires.

We report ensemble extinction and photoluminesence spectra for colloidal CdTe quantum wires (QWs) with nearly phase-pure, defect-free wurtzite (WZ) structure, having spectral line widths comparable to the best ensemble or single quantum-dot values, to the single polytypic (having WZ and zinc blende (ZB) alternations) QW values, and to those of two-dimensional quantum belts or platelets. The electronic structures determined from the multifeatured extinction spectra are in excellent agreement with the theoretical results of WZ QWs having the same crystallographic orientation. Optical properties of polytypic QWs of like diameter and diameter distribution are provided for comparison, which exhibit smaller bandgaps and broader spectral line widths. The nonperiodic WZ-ZB alternations are found to generate non-negligible shifts of the bandgap to intermediate energies between the quantum-confined WZ and ZB energies. The alternations and variations in the domain sizes result in inhomogeneous spectral line width broadening that may be more significant than that arising from the 12-13% diameter distributions within the QW ensembles.

Analytical approximations to inhomogeneously broadened, radiation damped free precession and echo signals.

The Dirac-Frenkel-Maclachlan (DFM) variation of parameters approach to approximately solving the time dependent Schrödinger equation is used to generate free precession and echo signals from the Bloch equations corrected for the effects of radiation damping and inhomogeneous broadening. Following a brief description of how the DFM method can be applied to the non-linear Bloch equations, two figures of merit designed to evaluate how a DFM optimized approximation compares with the exact solution is provided. This framework is used to optimize and evaluate the performance of six trial functions describing inhomogeneously broadened, radiation damped free precession and echo signals. The trial functions are then used to analyze the resolution enhancement and signal attenuation produced by pulse sequences that suppress radiation damping.