Through the Lens of a Momentum Microscope: Viewing Light-Induced Quantum Phenomena in 2D Materials.

Van der Waals (vdW) materials at their 2D limit are diverse, flexible, and unique laboratories to study fundamental quantum phenomena and their future applications. Their novel properties rely on their pronounced Coulomb interactions, variety of crystal symmetries and spin-physics, and the ease of incorporation of different vdW materials to form sophisticated heterostructures. In particular, the excited state properties of many 2D semiconductors and semi-metals are relevant for their technological applications, particularly those that can be induced by light. In this paper, the recent advances made in studying out-of-equilibrium, light-induced, phenomena in these materials are reviewed using powerful, surface-sensitive, time-resolved photoemission-based techniques, with a particular emphasis on the emerging multi-dimensional photoemission spectroscopy technique of time-resolved momentum microscopy. The advances this technique has enabled in studying the nature and dynamics of occupied excited states in these materials are discussed. Then, the future research directions opened by these scientific and instrumental advancements are projected for studying the physics of 2D materials and the opportunities to engineer their band-structure and band-topology by laser fields.

Local nanoscale phase impurities are degradation sites in halide perovskites.

Understanding the nanoscopic chemical and structural changes that drive instabilities in emerging energy materials is essential for mitigating device degradation. The power conversion efficiency of halide perovskite photovoltaic devices has reached 25.7 per cent in single-junction and 29.8 per cent in tandem perovskite/silicon cells1,2, yet retaining such performance under continuous operation has remained elusive3. Here we develop a multimodal microscopy toolkit to reveal that in leading formamidinium-rich perovskite absorbers, nanoscale phase impurities, including hexagonal polytype and lead iodide inclusions, are not only traps for photoexcited carriers, which themselves reduce performance4,5, but also, through the same trapping process, are sites at which photochemical degradation of the absorber layer is seeded. We visualize illumination-induced structural changes at phase impurities associated with trap clusters, revealing that even trace amounts of these phases, otherwise undetected with bulk measurements, compromise device longevity. The type and distribution of these unwanted phase inclusions depends on the film composition and processing, with the presence of polytypes being most detrimental for film photo-stability. Importantly, we reveal that both performance losses and intrinsic degradation processes can be mitigated by modulating these defective phase impurities, and demonstrate that this requires careful tuning of local structural and chemical properties. This multimodal workflow to correlate the nanoscopic landscape of beam-sensitive energy materials will be applicable to a wide range of semiconductors for which a local picture of performance and operational stability has yet to be established.

Dominating Interlayer Resonant Energy Transfer in Type-II 2D Heterostructure.

Type-II heterostructures (HSs) are essential components of modern electronic and optoelectronic devices. Earlier studies have found that in type-II transition metal dichalcogenide (TMD) HSs, the dominating carrier relaxation pathway is the interlayer charge transfer (CT) mechanism. Here, this report shows that, in a type-II HS formed between monolayers of MoSe2 and ReS2, nonradiative energy transfer (ET) from higher to lower work function material (ReS2 to MoSe2) dominates over the traditional CT process with and without a charge-blocking interlayer. Without a charge-blocking interlayer, the HS area shows 3.6 times MoSe2 photoluminescence (PL) enhancement as compared to the MoSe2 area alone. In a completely encapsulated sample, the HS PL emission further increases by a factor of 6.4. After completely blocking the CT process, more than 1 order of magnitude higher MoSe2 PL emission was achieved from the HS area. This work reveals that the nature of this ET is truly a resonant effect by showing that in a similar type-II HS formed by ReS2 and WSe2, CT dominates over ET, resulting in a severely quenched WSe2 PL. This study not only provides significant insight into the competing interlayer processes but also shows an innovative way to increase the PL emission intensity of the desired TMD material using the ET process by carefully choosing the right material combination for HS.

Structure of the moiré exciton captured by imaging its electron and hole.

Interlayer excitons (ILXs) - electron-hole pairs bound across two atomically thin layered semiconductors - have emerged as attractive platforms to study exciton condensation1-4, single-photon emission and other quantum information applications5-7. Yet, despite extensive optical spectroscopic investigations8-12, critical information about their size, valley configuration and the influence of the moiré potential remains unknown. Here, in a WSe2/MoS2 heterostructure, we captured images of the time-resolved and momentum-resolved distribution of both of the particles that bind to form the ILX: the electron and the hole. We thereby obtain a direct measurement of both the ILX diameter of around 5.2 nm, comparable with the moiré-unit-cell length of 6.1 nm, and the localization of its centre of mass. Surprisingly, this large ILX is found pinned to a region of only 1.8 nm diameter within the moiré cell, smaller than the size of the exciton itself. This high degree of localization of the ILX is backed by Bethe-Salpeter equation calculations and demonstrates that the ILX can be localized within small moiré unit cells. Unlike large moiré cells, these are uniform over large regions, allowing the formation of extended arrays of localized excitations for quantum technology.

An On-Demand Drug Delivery System for Control of Epileptiform Seizures.

Drug delivery systems have the potential to deliver high concentrations of drug to target areas on demand, while elsewhere and at other times encapsulating the drug, to limit unwanted actions. Here we show proof of concept in vivo and ex vivo tests of a novel drug delivery system based on hollow-gold nanoparticles tethered to liposomes (HGN-liposomes), which become transiently permeable when activated by optical or acoustic stimulation. We show that laser or ultrasound simulation of HGN-liposomes loaded with the GABAA receptor agonist, muscimol, triggers rapid and repeatable release in a sufficient concentration to inhibit neurons and suppress seizure activity. In particular, laser-stimulated release of muscimol from previously injected HGN-liposomes caused subsecond hyperpolarizations of the membrane potential of hippocampal pyramidal neurons, measured by whole cell intracellular recordings with patch electrodes. In hippocampal slices and hippocampal-entorhinal cortical wedges, seizure activity was immediately suppressed by muscimol release from HGN-liposomes triggered by laser or ultrasound pulses. After intravenous injection of HGN-liposomes in whole anesthetized rats, ultrasound stimulation applied to the brain through the dura attenuated the seizure activity induced by pentylenetetrazol. Ultrasound alone, or HGN-liposomes without ultrasound stimulation, had no effect. Intracerebrally-injected HGN-liposomes containing kainic acid retained their contents for at least one week, without damage to surrounding tissue. Thus, we demonstrate the feasibility of precise temporal control over exposure of neurons to the drug, potentially enabling therapeutic effects without continuous exposure. For future application, studies on the pharmacokinetics, pharmacodynamics, and toxicity of HGN-liposomes and their constituents, together with improved methods of targeting, are needed, to determine the utility and safety of the technology in humans.

Nanoscale chemical heterogeneity dominates the optoelectronic response of alloyed perovskite solar cells.

Halide perovskites perform remarkably in optoelectronic devices. However, this exceptional performance is striking given that perovskites exhibit deep charge-carrier traps and spatial compositional and structural heterogeneity, all of which should be detrimental to performance. Here, we resolve this long-standing paradox by providing a global visualization of the nanoscale chemical, structural and optoelectronic landscape in halide perovskite devices, made possible through the development of a new suite of correlative, multimodal microscopy measurements combining quantitative optical spectroscopic techniques and synchrotron nanoprobe measurements. We show that compositional disorder dominates the optoelectronic response over a weaker influence of nanoscale strain variations even of large magnitude. Nanoscale compositional gradients drive carrier funnelling onto local regions associated with low electronic disorder, drawing carrier recombination away from trap clusters associated with electronic disorder and leading to high local photoluminescence quantum efficiency. These measurements reveal a global picture of the competitive nanoscale landscape, which endows enhanced defect tolerance in devices through spatial chemical disorder that outcompetes both electronic and structural disorder.

Ultrafast Frequency-Shift Dynamics at Temporal Boundary Induced by Structural-Dispersion Switching of Waveguides.

We experimentally demonstrate the observation of a frequency-shift dynamics at a temporal boundary in the terahertz (THz) region relying on a scheme that controls the structural dispersion of a metal-semiconductor waveguide. Ultrafast structural-dispersion switching is achieved within a subpicosecond timescale by illuminating a waveguide surface with an optical pump pulse during the propagation of a THz pulse in the waveguide. Owing to the relatively high conversion efficiency, up to 23%, under the condition that the frequency shift is sufficiently larger than the bandwidth of the incident pulse, the rapid variation of the THz frequency around the temporal boundary is directly observed in the time domain.

Experimental measurement of the intrinsic excitonic wave function.

An exciton, a two-body composite quasiparticle formed of an electron and hole, is a fundamental optical excitation in condensed matter systems. Since its discovery nearly a century ago, a measurement of the excitonic wave function has remained beyond experimental reach. Here, we directly image the excitonic wave function in reciprocal space by measuring the momentum distribution of electrons photoemitted from excitons in monolayer tungsten diselenide. By transforming to real space, we obtain a visual of the distribution of the electron around the hole in an exciton. Further, by also resolving the energy coordinate, we confirm the elusive theoretical prediction that the photoemitted electron exhibits an inverted energy-momentum dispersion relationship reflecting the valence band where the partner hole remains, rather than that of conduction band states of the electron.

Unraveling the varied nature and roles of defects in hybrid halide perovskites with time-resolved photoemission electron microscopy.

With rapidly growing photoconversion efficiencies, hybrid perovskite solar cells have emerged as promising contenders for next generation, low-cost photovoltaic technologies. Yet, the presence of nanoscale defect clusters, that form during the fabrication process, remains critical to overall device operation, including efficiency and long-term stability. To successfully deploy hybrid perovskites, we must understand the nature of the different types of defects, assess their potentially varied roles in device performance, and understand how they respond to passivation strategies. Here, by correlating photoemission and synchrotron-based scanning probe X-ray microscopies, we unveil three different types of defect clusters in state-of-the-art triple cation mixed halide perovskite thin films. Incorporating ultrafast time-resolution into our photoemission measurements, we show that defect clusters originating at grain boundaries are the most detrimental for photocarrier trapping, while lead iodide defect clusters are relatively benign. Hexagonal polytype defect clusters are only mildly detrimental individually, but can have a significant impact overall if abundant in occurrence. We also show that passivating defects with oxygen in the presence of light, a previously used approach to improve efficiency, has a varied impact on the different types of defects. Even with just mild oxygen treatment, the grain boundary defects are completely healed, while the lead iodide defects begin to show signs of chemical alteration. Our findings highlight the need for multi-pronged strategies tailored to selectively address the detrimental impact of the different defect types in hybrid perovskite solar cells.

Directly visualizing the momentum-forbidden dark excitons and their dynamics in atomically thin semiconductors.

Resolving momentum degrees of freedom of excitons, which are electron-hole pairs bound by the Coulomb attraction in a photoexcited semiconductor, has remained an elusive goal for decades. In atomically thin semiconductors, such a capability could probe the momentum-forbidden dark excitons, which critically affect proposed opto-electronic technologies but are not directly accessible using optical techniques. Here, we probed the momentum state of excitons in a tungsten diselenide monolayer by photoemitting their constituent electrons and resolving them in time, momentum, and energy. We obtained a direct visual of the momentum-forbidden dark excitons and studied their properties, including their near degeneracy with bright excitons and their formation pathways in the energy-momentum landscape. These dark excitons dominated the excited-state distribution, a surprising finding that highlights their importance in atomically thin semiconductors.

Strong Plasmon-Exciton Coupling in Ag Nanoparticle-Conjugated Polymer Core-Shell Hybrid Nanostructures.

Strong plasmon-exciton coupling between tightly-bound excitons in organic molecular semiconductors and surface plasmons in metal nanostructures has been studied extensively for a number of technical applications, including low-threshold lasing and room-temperature Bose-Einstein condensates. Typically, excitons with narrow resonances, such as J-aggregates, are employed to achieve strong plasmon-exciton coupling. However, J-aggregates have limited applications for optoelectronic devices compared with organic conjugated polymers. Here, using numerical and analytical calculations, we demonstrate that strong plasmon-exciton coupling can be achieved for Ag-conjugated polymer core-shell nanostructures, despite the broad spectral linewidth of conjugated polymers. We show that strong plasmon-exciton coupling can be achieved through the use of thick shells, large oscillator strengths, and multiple vibronic resonances characteristic of typical conjugated polymers, and that Rabi splitting energies of over 1000 meV can be obtained using realistic material dispersive relative permittivity parameters. The results presented herein give insight into the mechanisms of plasmon-exciton coupling when broadband excitonic materials featuring strong vibrational-electronic coupling are employed and are relevant to organic optoelectronic devices and hybrid metal-organic photonic nanostructures.

Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites.

Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices1,2. This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively3) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects4. Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance5, perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance6. The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions7 and with local strain8, both of which make devices less stable9. Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process10,11, we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices.

Ultrafast Control of the Dimensionality of Exciton-Exciton Annihilation in Atomically Thin Black Phosphorus.

Using microtransient absorption spectroscopy, we show that the dynamical form of exciton-exciton annihilation in atomically thin black phosphorous can be made to switch between time varying 1D scattering and time-independent 2D scattering. At low carrier densities, anisotropy drives the 1D behavior, but as the photoexcitation density approaches the exciton saturation limit, the 2D nature of exciton-exciton scattering takes over. Furthermore, lowering the temperature provides a handle on the ultrafast timescale at which the 1D to 2D transition occurs. We understand our results quantitatively using a diffusion based model of exciton-exciton scattering.

Improving Signal and Photobleaching Characteristics of Temporal Focusing Microscopy with the Increase in Pulse Repetition Rate.

Wide-field temporal focused (WF-TeFo) two-photon microscopy allows for the simultaneous imaging of a large planar area, with a potential order of magnitude enhancement in the speed of volumetric imaging. To date, low repetition rate laser sources with over half a millijoule per pulse have been required in order to provide the high peak power densities for effective two-photon excitation over the large area. However, this configuration suffers from reduced signal intensity due to the low repetition rate, saturation effects due to increased excitation fluences, as well as faster photobleaching of the fluorescence probe. In contrast, with the recent advent of high repetition rate, high pulse energy laser systems could potentially provide the advantages of high repetition rate systems that are seen in traditional two-photon microscopes, while minimizing the negatives of high fluences in WF-TeFo setups to date. Here, we use a 100 microjoule/high repetition rate (50-100 kHz) laser system to investigate the performance of a WF-TeFo two-photon microscope. While using micro-beads as a sample, we demonstrate a proportionate increase in signal intensity with repetition rate, at no added cost in photobleaching. By decreasing pulse intensity, via a corresponding increase in repetition rate to maintain fluorescence signal intensity, we find that the photobleaching rate is reduced by ~98.4%. We then image live C. elegans at a high repetition rate for 25 min. as a proof-of-principle. Lastly, we identify the steady state temperature increase as the limiting process in further increasing the repetition rate, and we estimate that repetition rate in the range between 0.5 and 5 MHz is ideal for live imaging with a simple theoretical model. With new generation low-cost fiber laser systems offering high pulse energy/high repetition rates in what is essentially a turn-key solution, we anticipate increased adoption of this microscopy technique by the neuroscience community.

Pulling apart photoexcited electrons by photoinducing an in-plane surface electric field.

The study and control of spatiotemporal dynamics of photocarriers at the interfaces of materials have led to transformative modern technologies, such as light-harvesting devices and photodetectors. At the heart of these technologies is the ability to separate oppositely charged electrons and holes. Going further, the ability to separate like charges and manipulate their distribution could provide a powerful new paradigm in opto-electronic control, more so when done on ultrafast time scales. However, this requires one to selectively address subpopulations of the photoexcited electrons within the distribution-a challenging task, particularly on ultrafast time scales. By exploiting the spatial intensity variations in an ultrafast light pulse, we generate local surface fields within the optical spot of a doped semiconductor and thereby pull apart the electrons into two separate distributions. Using time-resolved photoemission microscopy, we directly record a movie of this redistribution process lasting a few hundred picoseconds, which we control via the spatial profile and intensity of the photoexciting pulse. Our quantitative model explains the underlying charge transport phenomena, thus providing a roadmap to the more generalized ability to manipulate photocarrier distributions with high spatiotemporal resolution.

High-Temperature Terahertz Optical Diode Effect without Magnetic Order in Polar FeZnMo_{3}O_{8}.

We present a terahertz spectroscopic study of polar ferrimagnet FeZnMo_{3}O_{8}. Our main finding is a giant high-temperature optical diode effect, or nonreciprocal directional dichroism, where the transmitted light intensity in one direction is over 100 times lower than intensity transmitted in the opposite direction. The effect takes place in the paramagnetic phase with no long-range magnetic order in the crystal, which contrasts sharply with all existing reports of the terahertz optical diode effect in other magnetoelectric materials, where the long-range magnetic ordering is a necessary prerequisite. In FeZnMo_{3}O_{8}, the effect occurs resonantly with a strong magnetic dipole active transition centered at 1.27 THz and assigned as electron spin resonance between the eigenstates of the single-ion anisotropy Hamiltonian. We propose that the optical diode effect in paramagnetic FeZnMo_{3}O_{8} is driven by single-ion terms in magnetoelectric free energy.

Obtaining Cross-Sections of Paint Layers in Cultural Artifacts Using Femtosecond Pulsed Lasers.

Recently, ultrafast lasers exhibiting high peak powers and extremely short pulse durations have created a new paradigm in materials processing. The precision and minimal thermal damage provided by ultrafast lasers in the machining of metals and dielectrics also suggests a novel application in obtaining precise cross-sections of fragile, combustible paint layers in artwork and cultural heritage property. Cross-sections of paint and other decorative layers on artwork provide critical information into its history and authenticity. However, the current methodology which uses a scalpel to obtain a cross-section can cause further damage, including crumbling, delamination, and paint compression. Here, we demonstrate the ability to make controlled cross-sections of paint layers with a femtosecond pulsed laser, with minimal damage to the surrounding artwork. The femtosecond laser cutting overcomes challenges such as fragile paint disintegrating under scalpel pressure, or oxidation by the continuous-wave (CW) laser. Variations in laser power and translational speed of the laser while cutting exhibit different benefits for cross-section sampling. The use of femtosecond lasers in studying artwork also presents new possibilities in analyzing, sampling, and cleaning of artwork with minimal destructive effects.

Imaging the motion of electrons across semiconductor heterojunctions.

Technological progress since the late twentieth century has centred on semiconductor devices, such as transistors, diodes and solar cells. At the heart of these devices is the internal motion of electrons through semiconductor materials due to applied electric fields or by the excitation of photocarriers. Imaging the motion of these electrons would provide unprecedented insight into this important phenomenon, but requires high spatial and temporal resolution. Current studies of electron dynamics in semiconductors are generally limited by the spatial resolution of optical probes, or by the temporal resolution of electronic probes. Here, by combining femtosecond pump-probe techniques with spectroscopic photoemission electron microscopy, we imaged the motion of photoexcited electrons from high-energy to low-energy states in a type-II 2D InSe/GaAs heterostructure. At the instant of photoexcitation, energy-resolved photoelectron images revealed a highly non-equilibrium distribution of photocarriers in space and energy. Thereafter, in response to the out-of-equilibrium photocarriers, we observed the spatial redistribution of charges, thus forming internal electric fields, bending the semiconductor bands, and finally impeding further charge transfer. By assembling images taken at different time-delays, we produced a movie lasting a few trillionths of a second of the electron-transfer process in the photoexcited type-II heterostructure-a fundamental phenomenon in semiconductor devices such as solar cells. Quantitative analysis and theoretical modelling of spatial variations in the movie provide insight into future solar cells, 2D materials and other semiconductor devices.

Ultrafast Charge Transfer and Enhanced Absorption in MoS2-Organic van der Waals Heterojunctions Using Plasmonic Metasurfaces.

Hybrid organic-inorganic heterostructures are attracting tremendous attention for optoelectronic applications due to their low-cost processing and high performance in devices. In particular, van der Waals p-n heterojunctions formed between inorganic two-dimensional (2D) materials and organic semiconductors are of interest due to the quantum confinement effects of 2D materials and the synthetic control of the physical properties of organic semiconductors, enabling a high degree of tunable optoelectronic properties for the heterostructure. However, for photovoltaic applications, hybrid 2D-organic heterojunctions have demonstrated low power conversion efficiencies due to the limited absorption from constraints on the physical thickness of each layer. Here, we investigate the ultrafast charge transfer dynamics between an organic polymer:fullerene blend and 2D n-type MoS2 using transient pump-probe reflectometry. We employ plasmonic metasurfaces to enhance the absorption and charge photogeneration within the physically thin hybrid MoS2-organic heterojunction. For the hybrid MoS2-organic heterojunction in the presence of the plasmonic metasurface, the charge generation within the polymer is enhanced 6-fold, and the total active layer absorption bandwidth is increased by 90 nm relative to the polymer:fullerene blend alone. We demonstrate that MoS2-organic heterojunctions can serve as hybrid solar cells, and their efficiencies can be improved using plasmonic metasurfaces.

Interfacing with Neural Activity via Femtosecond Laser Stimulation of Drug-Encapsulating Liposomal Nanostructures.

External control over rapid and precise release of chemicals in the brain potentially provides a powerful interface with neural activity. Optical manipulation techniques, such as optogenetics and caged compounds, enable remote control of neural activity and behavior with fine spatiotemporal resolution. However, these methods are limited to chemicals that are naturally present in the brain or chemically suitable for caging. Here, we demonstrate the ability to interface with neural functioning via a wide range of neurochemicals released by stimulating loaded liposomal nanostructures with femtosecond lasers. Using a commercial two-photon microscope, we released inhibitory or excitatory neurochemicals to evoke subthreshold and suprathreshold changes in membrane potential in a live mouse brain slice. The responses were repeatable and could be controlled by adjusting laser stimulation characteristics. We also demonstrate the release of a wider range of chemicals-which previously were impossible to release by optogenetics or uncaging-including synthetic analogs of naturally occurring neurochemicals. In particular, we demonstrate the release of a synthetic receptor-specific agonist that exerts physiological effects on long-term synaptic plasticity. Further, we show that the loaded liposomal nanostructures remain functional for weeks in a live mouse. In conclusion, we demonstrate new techniques capable of interfacing with live neurons, and extendable to in vivo applications.