Approaching the intrinsic exciton physics limit in two-dimensional semiconductor diodes.

Two-dimensional (2D) semiconductors have attracted intense interest for their unique photophysical properties, including large exciton binding energies and strong gate tunability, which arise from their reduced dimensionality1-5. Despite considerable efforts, a disconnect persists between the fundamental photophysics in pristine 2D semiconductors and the practical device performances, which are often plagued by many extrinsic factors, including chemical disorder at the semiconductor-contact interface. Here, by using van der Waals contacts with minimal interfacial disorder, we suppress contact-induced Shockley-Read-Hall recombination and realize nearly intrinsic photophysics-dictated device performance in 2D semiconductor diodes. Using an electrostatic field in a split-gate geometry to independently modulate electron and hole doping in tungsten diselenide diodes, we discover an unusual peak in the short-circuit photocurrent at low charge densities. Time-resolved photoluminescence reveals a substantial decrease of the exciton lifetime from around 800 picoseconds in the charge-neutral regime to around 50 picoseconds at high doping densities owing to increased exciton-charge Auger recombination. Taken together, we show that an exciton-diffusion-limited model well explains the charge-density-dependent short-circuit photocurrent, a result further confirmed by scanning photocurrent microscopy. We thus demonstrate the fundamental role of exciton diffusion and two-body exciton-charge Auger recombination in 2D devices and highlight that the intrinsic photophysics of 2D semiconductors can be used to create more efficient optoelectronic devices.

De novo design of proteins housing excitonically coupled chlorophyll special pairs.

Natural photosystems couple light harvesting to charge separation using a 'special pair' of chlorophyll molecules that accepts excitation energy from the antenna and initiates an electron-transfer cascade. To investigate the photophysics of special pairs independently of the complexities of native photosynthetic proteins, and as a first step toward creating synthetic photosystems for new energy conversion technologies, we designed C2-symmetric proteins that hold two chlorophyll molecules in closely juxtaposed arrangements. X-ray crystallography confirmed that one designed protein binds two chlorophylls in the same orientation as native special pairs, whereas a second designed protein positions them in a previously unseen geometry. Spectroscopy revealed that the chlorophylls are excitonically coupled, and fluorescence lifetime imaging demonstrated energy transfer. The cryo-electron microscopy structure of a designed 24-chlorophyll octahedral nanocage with a special pair on each edge closely matched the design model. The results suggest that the de novo design of artificial photosynthetic systems is within reach of current computational methods.

Measuring the total photon economy of molecular species through fluorescent optical cycling.

The total photon economy of a chromophore molecular species represents a study of how absorbed photons partition among various electronic states and ultimately dissipate their excited energy into the environment. A complete accounting of these rates and pathways would allow one to optimize chromophores and their environments for applications. We describe a technique, fluorescent optical cycling (FOC), which allows for simultaneous observation of prompt and delayed emission during and after multiple pulsed excitation, ultimately granting access to multi-state photophysical rates. We exercise control over the excitation pulse train, which allows us to "optically shelve" long-lived intermediate states without the use of diode or flashlamp excitation. By recording all photon arrival times in the visible and shortwave infrared, we can simultaneously resolve fluorescence, phosphorescence, and singlet oxygen sensitization in a single experiment. We use FOC to examine the photophysics of dual emitting bis(di-R-phosphino)alkanethiophene-pyridine-platinum ([Pt(thpy)(dppm)]+) under different solvation conditions, revealing changes in intersystem crossing and phosphorescent rates induced by the external heavy atom effect. Coupling FOC with decay associated Fourier spectroscopy (DAFS), we demonstrate simultaneous correlated spectral and lifetime data in this dual emitting complex. Finally, FOC combined with superconducting nanowire single photon detectors (SNSPDs) allows us to observe the shortwave infrared region (SWIR) phosphorescence of singlet oxygen sensitized by Rose Bengal. Overall, FOC provides a powerful tool to simultaneously study multiple photophysics across timescales, even in weakly populated electronic states.

No more gap-shifting: Stochastic many-body-theory based TDHF for accurate theory of polymethine cyanine dyes.

We introduce an individually fitted screened-exchange interaction for the time-dependent Hartree-Fock (TDHF) method and show that it resolves the missing binding energies in polymethine organic dye molecules compared to time-dependent density functional theory (TDDFT). The interaction kernel, which can be thought of as a dielectric function, is generated by stochastic fitting to the screened-Coulomb interaction of many-body perturbation theory (MBPT), specific to each system. We test our method on the flavylium and indocyanine green dye families with a modifiable length of the polymethine bridge, leading to excitations ranging from visible to short-wave infrared. Our approach validates earlier observations on the importance of inclusion of medium range exchange for the exciton binding energy. Our resulting method, TDHF@vW, also achieves a mean absolute error on a par with MBPT at a computational cost on a par with local-functional TDDFT.

On the inadequacy of Stern-Volmer and FRET in describing quenching in binary donor-acceptor solutions.

Quantitative fluorescence quenching is a common analytical approach to studying the mechanism of chemical reactions. The Stern-Volmer (S-V) equation is the most common expression used to analyze the quenching behavior and can be used to extract kinetics in complex environments. However, the approximations underlying the S-V equation are incompatible with Förster Resonance Energy Transfer (FRET) acting as the primary quenching mechanism. The nonlinear distance dependence of FRET leads to significant departures from "standard" S-V quenching curves, both by modulating the interaction range of donor species and by increasing the effect of component diffusion. We demonstrate this inadequacy by probing the fluorescence quenching of long-lifetime lead sulfide quantum dots mixed with plasmonic covellite copper sulfide nanodisks (NDs), which serve as perfect fluorescent quenchers. By applying kinetic Monte Carlo methods, which consider particle distributions and diffusion, we are able to quantitatively reproduce experimental data, which show significant quenching at very small concentrations of NDs. The distribution of interparticle distances and diffusion are concluded to play important roles in fluorescence quenching, particularly in the shortwave infrared, where photoluminescent lifetimes are often long relative to diffusion time scales.

Participation in a High-Structure General Chemistry Course Increases Student Sense of Belonging and Persistence to Organic Chemistry.

A parallel series of general chemistry courses for Life Science Majors was created in an effort to support students and improve general chemistry outcomes. We created a two-quarter enhanced general chemistry course series that is not remedial, but instead implements several evidence-based teaching practices including Process Oriented Guided Inquiry Learning (POGIL), Peer-Led Team Learning (PLTL), and the Learning Assistant (LA) model. We found that students who took enhanced general chemistry had higher persistence to the subsequent first organic chemistry course, and performed equally well in the organic course compared to their peers who took standard general chemistry. Students in the first enhanced general chemistry course also reported significantly higher belonging, although we were unable to determine if increased belonging was associated with the increased persistence to organic chemistry. Rather we found that the positive association between taking the enhanced general chemistry course and persistence to organic chemistry was mediated by higher grades received in the enhanced general chemistry course. Our findings highlight the responsibility we have as educators to carefully consider the pedagogical practices we use, in addition to how we assign student grades.

Bethe-Salpeter equation spectra for very large systems.

We present a highly efficient method for the extraction of optical properties of very large molecules via the Bethe-Salpeter equation. The crutch of this approach is the calculation of the action of the effective Coulombic interaction, W, through a stochastic time-dependent Hartree propagation, which uses only ten stochastic orbitals rather than propagating the full sea of occupied states. This leads to a scaling that is at most cubic in system size with trivial parallelization of the calculation. We apply this new method to calculate the spectra and electronic density of the dominant excitons of a carbon-nanohoop bound fullerene system with 520 electrons using less than 4000 core hours.

Large-Area Synthesis and Patterning of All-Inorganic Lead Halide Perovskite Thin Films and Heterostructures.

All-inorganic lead halide perovskites have attracted tremendous interest for their excellent stability when compared with hybrid perovskites. Here we report a large-area growth of monocrystalline all-inorganic perovskite thin films and further patterning them into heterostructure arrays. We show that highly oriented CsPbBr3 microcrystal domains can be readily grown on muscovite mica substrates with a well-defined epitaxial relationship, which can further expand and eventually merge into large-area monocrystalline CsPbBr3 thin films with an excellent optical quality. Taking a step further, we show the large-area CsPbBr3 thin film can be further patterned and selectively transformed into CsPbI3 using a selective anion-exchange process to produce CsPbBr3-CsPbI3 lateral heterostructure arrays with spatially modulated photoluminescence emission and an apparent current rectification behavior. The capability to grow large-area CsPbBr3 monocrystalline thin films and heterostructure arrays defines a robust material platform for both the fundamental investigations and potential applications in optoelectronics.

Bright Chromenylium Polymethine Dyes Enable Fast, Four-Color In Vivo Imaging with Shortwave Infrared Detection.

Optical imaging within the shortwave infrared (SWIR, 1000-2000 nm) region of the electromagnetic spectrum has enabled high-resolution and high-contrast imaging in mice, non-invasively. Polymethine dyes, with their narrow absorption spectra and high absorption coefficients, are optimal probes for fast and multiplexed SWIR imaging. Here, we expand upon the multiplexing capabilities in SWIR imaging by obtaining brighter polymethine dyes with varied excitation wavelengths spaced throughout the near-infrared (700-1000 nm) region. Building on the flavylium polymethine dye scaffold, we explored derivatives with functional group substitution at the 2-position, deemed chromenylium polymethine dyes. The reported dyes have reduced nonradiative rates and enhanced emissive properties, enabling non-invasive imaging in mice in a single color at 300 fps and in three colors at 100 fps. Combined with polymethine dyes containing a red-shifted julolidine flavylium heterocycle and indocyanine green, distinct channels with well-separated excitation wavelengths provide non-invasive video-rate in vivo imaging in four colors.

Franck-Condon Tuning of Optical Cycling Centers by Organic Functionalization.

Laser induced electronic excitations that spontaneously emit photons and decay directly to the initial ground state ("optical cycling transitions") are used in quantum information and precision measurement for state initialization and readout. To extend this primarily atomic technique to large, organic compounds, we theoretically investigate optical cycling of alkaline earth phenoxides and their functionalized derivatives. We find that optical cycle leakage due to wave function mismatch is low in these species, and can be further suppressed by using chemical substitution to boost the electron-withdrawing strength of the aromatic molecular ligand through resonance and induction effects. This provides a straightforward way to use chemical functional groups to construct optical cycling moieties for laser cooling, state preparation, and quantum measurement.

Surface chemical trapping of optical cycling centers.

Quantum information processors based on trapped atoms utilize laser-induced optical cycling transitions for state preparation and measurement. These transitions consist of an electronic excitation from the ground to an excited state and a decay back to the initial ground state, associated with a photon emission. While this technique has been used primarily with atoms, it has also recently been shown to work for some divalent metal hydroxides (e.g. SrOH) and alkoxides (e.g. SrOCH3). This extension to molecules is possible because these molecules feature nearly isolated, atomic-like ground and first-excited electronic states centered on the radical metal atom. We theoretically investigate the extension of this idea to a larger scale by growing the alkyl group, R, beyond the initial methyl group, CH3, while preserving the isolated and highly vertical character of the electronic excitation on the radical metal atom, M. Theory suggests that in the limit as the size of the ligand carbon chain increases, it can be considered a functionalized diamond (or cubic boron nitride) surface. Several requirements must be observed for the cycling centers to function when bound to the surface. First, the surface must have a significant band gap that fully encapsulates both the ground and excited states of the cycling center. Second, while the surface lattice imposes strict limits on the achievable spacing between the SrO- groups, at high coverage, SrO- centers can interact, and show geometric changes and/or electronic state mixing. We show that the coverage of the diamond surface with SrO- cycling centers needs to be significantly sub-monolayer for the functionality of the cycling center to be preserved. Having the lattice-imposed spatial control of SrO- placements will allow nanometer-scale proximity between qubits and will eliminate the need for atom traps for localized cycling emitters. Our results also imply that a functionalization could be done on a scanning microscope tip for local quantum sensing or on photonic structures for optically-mediated quantum information processing.

Shortwave infrared fluorescence imaging with the clinically approved near-infrared dye indocyanine green.

Fluorescence imaging is a method of real-time molecular tracking in vivo that has enabled many clinical technologies. Imaging in the shortwave IR (SWIR; 1,000-2,000 nm) promises higher contrast, sensitivity, and penetration depths compared with conventional visible and near-IR (NIR) fluorescence imaging. However, adoption of SWIR imaging in clinical settings has been limited, partially due to the absence of US Food and Drug Administration (FDA)-approved fluorophores with peak emission in the SWIR. Here, we show that commercially available NIR dyes, including the FDA-approved contrast agent indocyanine green (ICG), exhibit optical properties suitable for in vivo SWIR fluorescence imaging. Even though their emission spectra peak in the NIR, these dyes outperform commercial SWIR fluorophores and can be imaged in the SWIR, even beyond 1,500 nm. We show real-time fluorescence imaging using ICG at clinically relevant doses, including intravital microscopy, noninvasive imaging in blood and lymph vessels, and imaging of hepatobiliary clearance, and show increased contrast compared with NIR fluorescence imaging. Furthermore, we show tumor-targeted SWIR imaging with IRDye 800CW-labeled trastuzumab, an NIR dye being tested in multiple clinical trials. Our findings suggest that high-contrast SWIR fluorescence imaging can be implemented alongside existing imaging modalities by switching the detection of conventional NIR fluorescence systems from silicon-based NIR cameras to emerging indium gallium arsenide-based SWIR cameras. Using ICG in particular opens the possibility of translating SWIR fluorescence imaging to human clinical applications. Indeed, our findings suggest that emerging SWIR-fluorescent in vivo contrast agents should be benchmarked against the SWIR emission of ICG in blood.

Stochastically Realized Observables for Excitonic Molecular Aggregates.

We show that a stochastic approach enables calculations of the optical properties of large 2-dimensional and nanotubular excitonic molecular aggregates. Previous studies of such systems relied on numerically diagonalizing the dense and disordered Frenkel Hamiltonian, which scales approximately as O(N3) for N dye molecules. Our approach scales much more efficiently as O(Nlog(N)), enabling quick study of systems with a million of coupled molecules on the micrometer size scale. We calculate several important experimental observables, including the optical absorption spectrum and density of states, and develop a stochastic formalism for the participation ratio. Quantitative agreement with traditional matrix diagonalization methods is demonstrated for both small- and intermediate-size systems. The stochastic methodology enables the study of the effects of spatial-correlation in site energies on the optical signatures of large 2D aggregates. Our results demonstrate that stochastic methods present a path forward for screening structural parameters and validating experiments and theoretical predictions in large excitonic aggregates.

Decay-Associated Fourier Spectroscopy: Visible to Shortwave Infrared Time-Resolved Photoluminescence Spectra.

We describe and implement an interferometric approach to decay-associated photoluminescence spectroscopy, which we term decay-associated Fourier spectroscopy (DAFS). In DAFS, the emitted photon stream from a substrate passes through a variable path length Mach-Zehnder interferometer prior to detection and timing. The interferometer encodes spectral information in the intensity measured at each detector enabling simultaneous spectral and temporal resolution. We detail several advantages of DAFS, including wavelength-range insensitivity, drift-noise cancellation, and optical mode retention. DAFS allows us to direct the photon stream into an optical fiber, enabling the implementation of superconducting nanowire single photon detectors for energy-resolved spectroscopy in the shortwave infrared spectral window (λ = 1-2 µm). We demonstrate the broad applicability of DAFS, in both the visible and shortwave infrared, using two Förster resonance energy transfer pairs: a pair operating with conventional visible wavelengths and a pair showing concurrent acquisition in the visible and the shortwave infrared regime.

Multiexciton Lifetimes Reveal Triexciton Emission Pathway in CdSe Nanocrystals.

Multiexcitons in emerging semiconducting nanomaterials play a critical role in potential optoelectronic and quantum computational devices. We describe photon resolved single molecule methods to directly probe the dynamics of biexcitons and triexcitons in colloidal CdSe quantum dots. We confirm that biexcitons emit from a spin-correlated state, consistent with statistical scaling. Contrary to current understanding, we find that triexciton emission is dominated by band-edge 1Se1S3/2 recombination rather than the higher energy 1Pe1P3/2 recombination.

Understanding the influence of disorder on the exciton dynamics and energy transfer in Zn-phthalocyanine H-aggregates.

The photophysics of 9(19),16(17),23(24)-tri-tert-butyl-2-[ethynyl-(4-carboxymethyl)phenyl]phthalocyaninatozinc(ii) and its H-aggregates is studied in different solvents by means of ultrafast non-linear optical spectroscopy and computational modeling. In non-coordinating solvents, both stationary and time-resolved spectroscopies highlight the formation of extended molecular aggregates, whose dimension and spectral properties depends on the concentration. In all the explored experimental conditions, time-resolved transient absorption experiments show multi exponential decay of the signals. Additional insights into the excited state relaxation mechanisms of the system is obtained with 2D electronic spectroscopy, which is employed to compare the deactivation channels in the absence or presence of aggregates. In ethanol and diethylether, where only monomers are present, an ultrafast relaxation process among the two non-degenerate Q-states of the molecule is evidenced by the appearance of a cross peak in the 2D-maps. In chloroform or CCl4, where disordered H-aggregates are formed, an energy transfer channel among aggregates with different composition and size is observed, leading to the non-radiative decay towards the lower energy dark state of the aggregates. Efficient coupling between less and more aggregated species is highlighted in two-dimensional electronic spectra by the appearance of a cross peak. The kinetics and intensity of the latter depend on the concentration of the solution. Finally, the linear spectroscopic properties of the aggregate are reproduced using a simplified structural model of an extended aggregate, based on Frenkel Hamiltonian Calculations and on an estimate of the electronic couplings between each dimer composing the aggregate computed at DFT level.

Near-Infrared Quantum Dot Emission Enhanced by Stabilized Self-Assembled J-Aggregate Antennas.

Enhancing photoluminescent emission (PL) in the near-infrared-infrared (NIR-IR) spectral region has broad applications from solar energy conversion to biological imaging. We show that self-assembled molecular dye J-aggregates (light-harvesting nanotubes, LHNs) can increase the PL emission of NIR PbS quantum dots (QDs) in both liquid and solid media more than 8-fold, promoted primarily by a long-range antenna effect and efficient Förster resonance energy transfer (FRET) from donor to acceptor. To create this composite material and preserve the optical properties of the nanocrystals, we performed an in situ ligand substitution followed by a functionalization reaction using click-chemistry. This resulted in PbS QDs soluble in an aqueous environment compatible with the molecular J-aggregates (LHNs). Theoretical and experimental results demonstrate that long-range diffusive exciton transport in LHNs enables efficient energy transfer to low concentrations of QDs despite there being no direct binding between molecular donors and QD acceptors. This suggests a broad application space for mixed light harvesting and photophysically active nanocomposite materials based on self-assembling molecular aggregates.

Room-Temperature Micron-Scale Exciton Migration in a Stabilized Emissive Molecular Aggregate.

We report 1.6 ± 1 µm exciton transport in self-assembled supramolecular light-harvesting nanotubes (LHNs) assembled from amphiphillic cyanine dyes. We stabilize LHNs in a sucrose glass matrix, greatly reducing light and oxidative damage and allowing the observation of exciton-exciton annihilation signatures under weak excitation flux. Fitting to a one-dimensional diffusion model, we find an average exciton diffusion constant of 55 ± 20 cm2/s, among the highest measured for an organic system. We develop a simple model that uses cryogenic measurements of static and dynamic energetic disorder to estimate a diffusion constant of 32 cm2/s, in agreement with experiment. We ascribe large exciton diffusion lengths to low static and dynamic energetic disorder in LHNs. We argue that matrix-stabilized LHNS represent an excellent model system to study coherent excitonic transport.

PbS Nanocrystal Emission Is Governed by Multiple Emissive States.

Lead chalcogenide colloidal nanocrystals (NCs) are promising materials for solution processable optoelectronics. However, there is little agreement on the identity and character of PbS NC emission for different degrees of quantum confinement-a critical parameter for realizing applications for these nanocrystals. In this work, we combine ensemble and single NC spectroscopies to interrogate preparations of lead sulfide NCs. We use solution photon correlation Fourier spectroscopy (S-PCFS) to measure the average single NC linewidth of near-infrared-emitting PbS quantum dots and find it to be dominated by homogeneous broadening. We further characterize PbS NCs using temperature-dependent linear and time-resolved emission spectroscopy which demonstrate that a kinetically accessed defect state dominates room temperature emission of highly confined emitting NCs. These experiments, taken together, demonstrate that the linewidth and Stokes shift of PbS NCs are the result of emission from two states: a thermally accessed defect-with an energetically pinned charge carrier-and an inhomogeneously broadened band-edge state.

Flavylium Polymethine Fluorophores for Near- and Shortwave Infrared Imaging.

Bright fluorophores in the near-infrared and shortwave infrared (SWIR) regions of the electromagnetic spectrum are essential for optical imaging in vivo. In this work, we utilized a 7-dimethylamino flavylium heterocycle to construct a panel of novel red-shifted polymethine dyes, with emission wavelengths from 680 to 1045 nm. Photophysical characterization revealed that the 1- and 3-methine dyes display enhanced photostability and the 5- and 7-methine dyes exhibit exceptional brightness for their respective spectral regions. A micelle formulation of the 7-methine facilitated SWIR imaging in mice. This report presents the first polymethine dye designed and synthesized for SWIR in vivo imaging.