Publications

We present super-resolved coherent anti-Stokes Raman scattering (CARS) microscopy by implementing phase-resolved image scanning microscopy, achieving up to two-fold resolution increase as compared with a conventional CARS microscope. Phase-sensitivity is required for the standard pixel-reassignment procedure since the scattered field is coherent, thus the point-spread function is well-defined only for the field amplitude. We resolve the complex field by a simple add-on to the CARS setup enabling inline interferometry. Phase-sensitivity offers additional contrast which informs the spatial distribution of both resonant and nonresonant scatterers. As compared with alternative super-resolution schemes in coherent nonlinear microscopy, the proposed method is simple, requires only low-intensity excitation, and is compatible with any conventional forward-detected CARS imaging setup.

Modern imaging technologies are widely based on classical principles of light or electromagnetic wave propagation. They can be remarkably sophisticated, with recent successes ranging from single-molecule microscopy to imaging far-distant galaxies. However, new imaging technologies based on quantum principles are gradually emerging. They can either surpass classical approaches or provide novel imaging capabilities that would not otherwise be possible. Here we provide an overview of the most recently developed quantum imaging systems, highlighting the nonclassical properties of sources, such as bright squeezed light, entangled photons and single-photon emitters that enable their functionality. We outline potential upcoming trends and the associated challenges, all driven by a central enquiry, which is to understand whether quantum light can make visible the invisible.

Advanced optical microscopy techniques, such as fluorescence and vibrational imaging, play a key role in science and technology. Both the sensitivity and the chemical selectivity are important for applications of these methods in biomedical research. However, there are few bioimaging techniques that could offer vibrational sensitivity and selectivity simultaneously. Here, we demonstrate electronic-resonance coherent anti-Stokes Raman scattering (ER-CARS) spectroscopy and microscopy with high sensitivity and high selectivity by using lock-in detection. With this ER-CARS strategy, we observed the low-wavenumber Raman spectra of various infrared dyes in solution at ultralow vibrational frequencies (from ∼20 to 330 cm^-1) using a sharp edge filter and impulsive CARS excitation at low input power. We demonstrate low-frequency ER-CARS imaging of cells stained with infrared dyes using only 200 mW of input power, fundamentally mitigating photobleaching issues. We also show the application of ER-CARS in the detection of nonfluorescent molecules. Finally, we demonstrate the chemically selective capabilities of ER-CARS microscopy by imaging tissues stained with two different infrared dyes. These ER-CARS spectroscopy and microscopy results pave the way toward ultrasensitive Raman imaging of biological systems and present a pathway toward highly multiplexed selective imaging.

Super-resolution imaging is a powerful tool in modern biological research, allowing for the optical observation of subcellular structures with great detail. In this paper, we present a deep learning approach for image fusion of intensity and super-resolution optical fluctuation imaging (SOFI) microscopy images. We construct a network that can successfully combine the advantages of these two imaging methods, producing a fused image with a resolution comparable to that of SOFI and an SNR comparable to that of the intensity image. We also demonstrate the effectiveness of our approach experimentally, specifically on cell samples where microtubules were stained with ATTO647N and imaged using a confocal microscope with a single photon fiber bundle camera, allowing for the simultaneous acquisition of an image scanning microscopy (ISM) image and a SOFISM (ISM and SOFI) image. Our network is designed as a self-supervised network and shows the ability to train on a single pair of images and to generalize to other image pairs without the need for additional training. Our approach offers a flexible and efficient way to combine the strengths of correlation based imaging techniques along with traditional intensity based microscopy, and can be readily applied to other fluctuation based imaging modalities.

Self-healing (SH) of (opto)electronic material damage can have a huge impact on resource sustainability. The rising interest in halide perovskite (HaP) compounds over the past decade is due to their excellent semiconducting properties for crystals and films, even if made by low-temperature solution-based processing. Direct proof of self-healing in Pb-based HaPs is demonstrated through photoluminescence recovery from photodamage, fracture healing and their use as high-energy radiation and particle detectors. Here, the question of how to find additional semiconducting materials exhibiting SH, in particular lead-free ones is addressed. Applying a data-mining approach to identify semiconductors with favorable mechanical and thermal properties, for which Pb HaPs are clear outliers, it is found that the Cs₂Au^IAu^IIIX₆, (X = I, Br, Cl) family, which is synthesized and tested for SH. This is the first demonstration of self-healing of Pb-free inorganic HaP thin films, by photoluminescence recovery.

Photoisomerization of azobenzenes from their stable E isomer to the metastable Z state is the basis of numerous applications of these molecules. However, this reaction typically requires ultraviolet light, which limits applicability. In this study, we introduce disequilibration by sensitization under confinement (DESC), a supramolecular approach to induce the E-to-Z isomerization by using light of a desired color, including red. DESC relies on a combination of a macrocyclic host and a photosensitizer, which act together to selectively bind and sensitize E-azobenzenes for isomerization. The Z isomer lacks strong affinity for and is expelled from the host, which can then convert additional E-azobenzenes to the Z state. In this way, the host-photosensitizer complex converts photon energy into chemical energy in the form of out-of-equilibrium photostationary states, including ones that cannot be accessed through direct photoexcitation.

Quantum dots are engineered to use dopant states to achieve substantially enhanced impact ionization, which is potentially useful for light-harvesting applications.

Semiconductor nanocrystal emission polarization is a crucial probe of nanocrystal physics and an essential factor for nanocrystal-based technologies. While the transition dipole moment for the lowest excited state to ground state transition is well characterized, the dipole moment of higher multiexcitonic transitions is inaccessible via most spectroscopy techniques. Here, we realize direct characterization of the doubly excited-state relaxation transition dipole by heralded defocused imaging. Defocused imaging maps the dipole emission pattern onto a fast single-photon avalanche diode detector array, allowing the postselection of photon pairs emitted from the biexciton-exciton emission cascade and resolving the differences in transition dipole moments. Type-I¹/₂ seeded nanorods exhibit higher anisotropy of the biexciton-to-exciton transition compared to the exciton-to-ground state transition. In contrast, type-II seeded nanorods display a reduction of biexciton emission anisotropy. These findings are rationalized in terms of an interplay between the transient dynamics of the refractive index and the excitonic fine structure.

In terms of sustainable use, halide perovskite (HaP) semiconductors have a strong advantage over most other classes of materials for (opto)electronics, as they can self-heal (SH) from photodamage. While there is considerable literature on SH in devices, where it may not be clear exactly where damage and SH occur, there is much less on the HaP material itself. Here we perform \u201cfluorescence recovery after photobleaching\u201d (FRAP) measurements to study SH on polycrystalline thin films for which encapsulation is critical to achieving complete and fast self-healing. We compare SH in three photoactive APbI₃ perovskite films by varying the A-site cation ranging from (relatively) small inorganic Cs through medium-sized MA to large FA (the last two are organic cations). While the A cation is often considered electronically relatively inactive, it significantly affects both SH kinetics and the threshold for photodamage. The SH kinetics are markedly faster for γ-CsPbI₃ and α-FAPbI₃ than for MAPbI₃. Furthermore, γ-CsPbI₃ exhibits an intricate interplay between photoinduced darkening and brightening. We suggest possible explanations for the observed differences in SH behavior. This studys results are essential for identifying absorber materials that can regain intrinsic, insolation-induced photodamage-linked efficiency loss during its rest cycles, thus enabling applications such as autonomously sustainable electronics.

While most single-nanocrystal spectroscopy experiments rely on fluorescent emission, recent years have seen an increasing number of experiments based on absorption and scattering, enabling to correlate those with fluorescence intermittency. Herein, it is shown that nonlinear scattering by second-harmonic generation can also be measured from single CdSe/CdS core/shell nanoplatelets (NPLs) alongside fluorescence despite the weak scattering signal. It is shown that even under resonant two-photon conditions the second-harmonic scattering signal is uncorrelated with fluorescence intermittency and follows Poisson statistics.

Semiconductor nanocrystals feature multiply-excited states that display intriguing physics and significantly impact nanocrystal-based technologies. Fluorescence supplies a natural probe to investigate these states. Still, direct observation of multiexciton fluorescence has proved elusive to existing spectroscopy techniques. Heralded Spectroscopy is a new tool based on a breakthrough single-particle, single-photon, sub-nanosecond spectrometer that utilizes temporal photon correlations to isolate multiexciton emission. This proceedings paper introduces Heralded Spectroscopy and reviews some of the novel insights it uncovered into excitonexciton interactions within single nanocrystals. These include weak excitonexciton interactions and their correlation with quantum confinement, biexciton spectral diffusion, multiple biexciton species and biexciton emission polarization.

Measurements of photon temporal correlations have been the mainstay of experiments in quantum optics. Over the past several decades, advancements in detector technologies have supported further extending photon correlation techniques to give rise to novel spectroscopy and imaging methods. This Perspective reviews the evolution of these techniques from temporal autocorrelations through multidimensional photon correlations to photon correlation imaging. State-of-the-art single-photon detector technologies are discussed, highlighting the main challenges and the unique current perspective of photon correlations to usher in a new generation of spectroscopy and imaging modalities.

We show that metal-organic frameworks, based on tetrahedral pyridyl ligands, can be used as a morphological and structural template to form a series of isostructural crystals having different metal ions and properties. An iterative crystal-to-crystal conversion has been demonstrated by consecutive cation exchanges. The primary manganese-based crystals are characterized by an uncommon space group ( P622 ). The packing includes chiral channels that can mediate the cation exchange, as indicated by energy-dispersive X-ray spectroscopy on microtome-sectioned crystals. The observed cation exchange is in excellent agreement with the Irving-Williams series (Mn Zn) associated with the relative stability of the resulting coordination nodes. Furthermore, we demonstrate how the metal cation controls the optical and magnetic properties. The crystals maintain their morphology, allowing a quantitative comparison of their properties at both the ensemble and single-crystal level.

Atomically-thin crystals remain an epicenter of today's ongoing efforts of materials exploration for both fundamental knowledge and technological applications. We show that key modifications in the nucleation and growth steps lead to a controlled self-seeded growth of the monolayer transition metal dichalcogenide (TMDC) crystals and their lateral heterostructures via an halide chemical vapor deposition (HCVD) process which is a proven industrial scale and carbon-free synthesis technique for various material types. We present a general growth model with the limiting conditions on the nucleation density and crystal size of the 2D TMDCs grown in HCVD process. Furthermore, upon reduction of the self-seeded growth by a suitable surface pre-treatment, and by the modification of the nucleation step, epitaxial growth of monolayer TMDCs is also demonstrated using HCVD approach. The steady-state and time-resolved photoluminescence spectroscopic studies revealed the high optical and electronic quality of the as-grown 2D TMDCs semiconducting crystals. Field-effect transistor device characteristics of HCVD grown monolayer MoS2 using SiO2 gate dielectric shows an average mobility of 26 ± 7 cm2.V−1.s−1 and on-off ratio of ∼107, promising for large-scale device applications.

Impulsive spectroscopy provides a time-domain perspective of the active Raman modes of the specimen. As such, it serves as a complementary tool for the more common narrowband stimulated Raman techniques. In this chapter, we introduce the reader to the time-domain picture of vibrational excitation and detection, and discuss the advantages and disadvantages as compared to the narrowband variant of Raman scattering. We then proceed with mentioning recent advances in the experimental apparatus, aiming both at increasing the SNR and at increasing the delay scanning rate which constitutes a critical element in such time-domain techniques. We end up discussing preresonant impulsive Raman microspectroscopy and 2D impulsive Raman spectroscopy.

Understanding exciton-exciton interaction in multiply-excited nanocrystals is crucial to their utilization as functional materials. Yet, for lead halide perovskite nanocrystals, which are promising candidates for nanocrystal-based technologies, numerous contradicting values have been reported for the strength and sign of their exciton-exciton interaction. In this work we unambiguously determine the biexciton binding energy in single cesium lead halide perovskite nanocrystals at room temperature. This is enabled by the recently introduced SPAD array spectrometer, capable of temporally isolating biexciton-exciton emission cascades while retaining spectral resolution. We demonstrate that CsPbBr$_3$ nanocrystals feature an attractive exciton-exciton interaction, with a mean biexciton binding energy of 10 meV. For CsPbI$_3$ nanocrystals we observe a mean biexciton binding energy that is close to zero, and individual nanocrystals show either weakly attractive or weakly repulsive exciton-exciton interaction. We further show that within ensembles of both materials, single-nanocrystal biexciton binding energies are correlated with the degree of charge-carrier confinement.

Metal halide perovskites (MHPs) have unique characteristics and hold great potential for next-generation optoelectronic technologies. Recently, the importance of lattice strain in MHPs has been gaining recognition as a significant optimization parameter for device performance. While the effect of strain on the fundamental properties of MHPs has been at the center of interest, its combined effect with an external electric field has been largely overlooked. Here we perform an electric-field-dependent photoluminescence study on heteroepitaxially strained surface-guided CsPbBr₃ nanowires. We reveal an unexpected strong linear dependence of the photoluminescence intensity on the alternating field amplitude, stemming from an induced internal dipole. Using low-frequency polarized-Raman spectroscopy, we reveal structural modifications in the nanowires under an external field, associated with the observed polarity. These results reflect the important interplay between strain and an external field in MHPs and offer opportunities for the design of MHP-based optoelectronic nanodevices.

Upconverting semiconductor quantum dots (QDs) combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Here, we present upconverting type-II/type-I colloidal double QDs that enable enhancement of the performance of near-infrared to visible photon upconversion in QDs and broadening the range of relevant materials used. The resulting ZnTe/CdSe@CdS@CdSe/ZnSe type-II/type-I double QDs possess a very high photoluminescence quantum yield, monoexponential decay dynamics, and a narrow line width, approaching those of state-of-the-art upconverting QDs. We quantitatively characterize the upconversion cross section by direct comparison with two-photon absorption when varying the pump frequency across the absorption edge. Finally, we show that these upconversion QDs maintain their optical performance in a much more demanding geometry of a dense solid film and can thus be incorporated in devices as upconversion films. Our design provides guidance for fabricating highly efficient upconverting QDs with potential applications such as security coding and bioimaging.

Image scanning microscopy (ISM), an upgraded successor of the ubiquitous confocal microscope, facilitates up to two-fold improvement in lateral resolution, and has become an indispensable element in the toolbox of the bio-imaging community. Recently, super-resolution optical fluctuation image scanning microscopy (SOFISM) integrated the analysis of intensity-fluctuations information into the basic ISM architecture, to enhance its resolving power. Both of these techniques typically rely on pixel-reassignment as a fundamental processing step, in which the parallax of different detector elements to the sample is compensated by laterally shifting the point spread function (PSF). Here, we propose an alternative analysis approach, based on the recent high-performing sparsity-based super-resolution correlation microscopy (SPARCOM) method. Through measurements of DNA origami nano-rulers and fixed cells labeled with organic dye, we experimentally show that confocal SPARCOM (cSPARCOM), which circumvents pixel-reassignment altogether, provides enhanced resolution compared to pixel-reassigned based analysis. Thus, cSPARCOM further promotes the effectiveness of ISM, and particularly that of correlation based ISM implementations such as SOFISM, where the PSF deviates significantly from spatial invariance.

The rediscovery of the halide perovskite class of compounds and, in particular, the organic and inorganic lead halide perovskite (LHP) materials and lead-free derivatives has reached remarkable landmarks in numerous applications. First among these is the field of photovoltaics, which is at the core of todays environmental sustainability efforts. Indeed, these efforts have born fruit, reaching to date a remarkable power conversion efficiency of 25.2% for a double-cation Cs, FA lead halide thin film device. Other applications include light and particle detectors as well as lighting. However, chemical and thermal degradation issues prevent perovskite-based devices and particularly photovoltaic modules from reaching the market. The soft ionic nature of LHPs makes these materials susceptible to delicate changes in the chemical environment. Therefore, control over their interface properties plays a critical role in maintaining their stability. Here we focus on LHP nanocrystals, where surface termination by ligands determines not only the stability of the material but also the crystallographic phase and crystal habit. A surface analysis of nanocrystal interfaces revealed the involvement of Brønsted type acidbase equilibrium in the modification of the ligand moieties present, which in turn can invoke dissolution and recrystallization into the more favorable phase in terms of minimization of the surface energy. A large library of surface ligands has already been developed showing both good chemical stability and good electronic surface passivation, resulting in near-unity emission quantum yields for some materials, particularly CsPbBr3. However, most of those ligands have a large organic tail hampering charge carrier transport and extraction in nanocrystal-based solid films.

Metalorganic chemical vapor deposition (MOCVD) is one of the main methodologies used for thin-film fabrication in the semiconductor industry today and is considered one of the most promising routes to achieve large-scale and high-quality 2D transition metal dichalcogenides (TMDCs). However, if special measures are not taken, MOCVD suffers from some serious drawbacks, such as small domain size and carbon contamination, resulting in poor optical and crystal quality, which may inhibit its implementation for the large-scale fabrication of atomic-thin semiconductors. Here we present a growth-etch MOCVD (GE-MOCVD) methodology, in which a small amount of water vapor is introduced during the growth, while the precursors are delivered in pulses. The evolution of the growth as a function of the amount of water vapor, the number and type of cycles, and the gas composition is described. We show a significant domain size increase is achieved relative to our conventional process. The improved crystal quality of WS2 (and WSe2) domains wasis demonstrated by means of Raman spectroscopy, photoluminescence (PL) spectroscopy, and HRTEM studies. Moreover, time-resolved PL studies show very long exciton lifetimes, comparable to those observed in mechanically exfoliated flakes. Thus, the GE-MOCVD approach presented here may facilitate their integration into a wide range of applications.

In this work, we extend low frequency impulsive stimulated Raman microspectroscopy to the pre-electronic resonance regime, using a broadband two-color collinear pump probe scheme which can be readily extended to imaging. We discuss the difficulties unique to this type of measurements in the form of competing resonant two-photon absorption processes and the means to overcome them, and successfully reduce the noise which arises due to those competing processes by eliminating the detected spectral components which do not contribute to the vibrational signature of the sample yet introduce most of the noise. Finally, we demonstrate low frequency spectroscopy of crystalline samples under near-resonant pumping showing both enhancement and spectral modification due to coupling with the electronic degree of freedom.

We reintroduce the concept of SOFISM and discuss its practical aspects. We demonstrate that supplying a confocal microscope with a SPAD array detector enables super-resolution imaging relying on fluorophore blinking within reasonable dwell times.

Excitons in colloidal semiconductor nanoplatelets (NPLs) are weakly confined in the lateral dimensions. This results in significantly smaller Auger rates and, consequently, larger biexciton quantum yields, when compared to spherical quantum dots (QDs). Here we report a study of the temperature dependence of the biexciton Auger rate in individual CdSe/CdS core-shell NPLs, through the measurement of time-gated second-order photon correlations in the photoluminescence. We also utilize this method to directly estimate the single-exciton radiative rate. We find that whereas the radiative lifetime of NPLs increases with temperature, the Auger lifetime is almost temperature-independent. Our findings suggest that Auger recombination in NPLs is qualitatively similar to that of semiconductor quantum wells. Time-gated photon correlation measurements offer the unique ability to study multiphoton emission events, while excluding effects of competing fast processes, and can provide significant insight into the photophysics of a variety of nanocrystal multiphoton emitters.

In the past decade, optical imaging methods have significantly improved our understanding of the information processing principles in the brain. Although many promising tools have been designed, sensors of membrane potential are lagging behind the rest. Semiconductor nanoparticles are an attractive alternative to classical voltage indicators, such as voltage-sensitive dyes and proteins. Such nanoparticles exhibit high sensitivity to external electric fields via the quantum-confined Stark effect. Here we report the development of semiconductor voltage-sensitive nanorods (vsNRs) that self-insert into the neuronal membrane. To facilitate interaction of the nanorods with the membrane, we functionalized their surface with the lipid mixture derived from brain extract. We describe a workflow to detect and process the photoluminescent signal of vsNRs after wide-field time-lapse recordings. We also present data indicating that vsNRs are feasible for sensing membrane potential in neurons at a single-particle level. This shows the potential of vsNRs for the detection of neuronal activity with unprecedentedly high spatial and temporal resolution.

Ligand-induced chirality in semiconducting nanocrystals has been the subject of extensive study in the past few years and shows potential applications in optics and biology. Yet, the origin of the chiroptical effect in semiconductor nanoparticles is still not fully understood. Here, we examine the effect of the interaction with amino acids on both the fluorescence and the optical activity of chiral semiconductor quantum dots (QDs). A significant fluorescence enhancement is observed for L/D-Cys-CdTe QDs upon interaction with all the tested amino acids, indicating suppression of non-radiative pathways as well as the passivation of surface trap sites brought via the interaction of the amino group with the CdTe QDs' surface. Hetero-chiral amino acids are shown to weaken the Circular Dichroism (CD) signal, which may be attributed to a different binding configuration of cysteine molecules on the QDs surface. Furthermore, a red shift of both CD and fluorescence signals in L/D-Cys-CdTe QDs is only observed upon adding cysteine, while other tested amino acids do not exhibit such an effect. We speculate that the thiol group induces orbital hybridization of the highest occupied molecular orbital (HOMOs) of cysteine and the valance band of CdTe QDs, leading to the decrease of the energy band-gap and a concomitant red shift of CD and fluorescence spectra. This is further verified by density functional theory (DFT) calculations. Both the experimental and theoretical findings indicate that the addition of ligands which do not "directly" interact with the VB of the QD (non-cysteine moieties) changes the QD photophysical properties as it probably modifies the way cysteine is bound to the surface. Hence, we conclude that it is not only the chemistry of the amino acid ligand which affects both CD and PL, rather, it is also the exact geometry of binding which modifies these properties. Understanding the relationship between QD's surface and chiral amino acid thus provides an additional perspective on the fundamental origin of induced chiroptical effects in semiconductor nanoparticles, potentially enabling us to optimize the design of chiral semiconductor QDs for chiroptic applications.

Spherulites are birefringent structures with spherical symmetry, typically observed in crystallized polymers. We compute the band structure of opals made of close-packed assemblies of highly birefringent spherulites. We demonstrate that spherulitic birefringence of constituent spheres does not affect the symmetries of an opal, yet significantly affects the dispersion of eigenmodes, leading to new pseudogaps in sections of the band structure and, consequently, enhanced reflectivity. 

Formation of a p-n junction-like with a large built-in field is demonstrated at the nanoscale, using two types of semiconducting nanoparticles, CsPbBr₃ nanocrystals and CdSe nanoplatelets, capped with molecular linkers. By exploiting chemical recognition of the capping molecules, the two types of nanoparticles are brought into mutual contact, thus initiating spontaneous charge transfer and the formation of a strong junction field. Depending on the choice of capping molecules, the magnitude of the latter field is shown to vary in a broad range, corresponding to an interface potential step as large as ∼1 eV. The band diagram of the system as well as the emergence of photoinduced charge transfer processes across the interface is studied here by means of optical and photoelectron based spectroscopies. Our results propose an interesting template for generating and harnessing internal built-in fields in heterogeneous nanocrystal solids.

Temporal photon correlation measurement, instrumental to probing the quantum properties of light, typically requires multiple single photon detectors. Progress in single photon avalanche diode (SPAD) array technology highlights their potential as high-performance detector arrays for quantum imaging and photon number-resolving (PNR) experiments. Here, we demonstrate this potential by incorporating a novel on-chip SPAD array with 42% peak photon detection efficiency, low dark count rate and crosstalk probability of 0.14% per detection in a contbcal microscope. This enables reliable measurements of second and third order photon correlations from a single quantum dot emitter. Our analysis overcomes the inter-detector optical crosstalk background even though it is over an order of magnitude larger than our faint signal. To showcase the vast application space of such an approach, we implement a recently introduced super-resolution imaging method, quantum image scanning microscopy (Q-ISM). (C) 2019 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

Organic photovoltaics enable cost-efficient, tunable, and flexible platforms for solar energy conversion, yet their performance and stability are still far from optimal. Here, we present a study of photoinduced charge transfer processes between electron donor and acceptor organic nanocrystals as part of a pathfinding effort to develop robust and efficient organic nanocrystalline materials for photovoltaic applications. For this purpose, we utilized nanocrystals of perylenediimides as the electron acceptors and nanocrystalline copper phthalocyanine as the electron donor. Three different configurations of donor-acceptor heterojunctions were prepared. Charge transfer in the heterojunctions was studied with Kelvin probe force microscopy under laser or white light excitation. Moreover, detailed morphology characterizations and time-resolved photoluminescence measurements were conducted to understand the differences in the photovoltaic processes of these organic nanocrystals. Our work demonstrates that excitonic properties can be tuned by controlling the crystal and interface structures in the nanocrystalline heterojunctions, leading to a minimization of photovoltaic losses.

We demonstrate an approach for super-resolution imaging by combining flu-orophore fluctuations analysis with a confocal detector array setup. This combination facilitates obtaining high resolution images without a complex experimental setup and prohibitively long data acquisition.

Coherent anti-Stokes Raman scattering (CARS) has found wide applications in biomedical research. Compared with alternatives, single-beam CARS is especially attractive at low frequencies. Yet, currently existing schemes necessitate a relatively complicated setup to perform high-resolution spectroscopy. Here we show that the spectral sharp edge formed by an ultra-steep long-pass filter is sufficient for performing CARS spectroscopy, simplifying the system significantly. We compare the sensitivity of the presented methodology with available counterparts both theoretically and experimentally. Importantly, we show that this method, to the best of our knowledge, is the simplest and most suitable for vibrational imaging and spectroscopy in the very low-frequency regime (

Low-temperature paintable carbon-electrode-based perovskite solar cells (LC-PSCs) are developed predominantly due to several significant advantages of carbon electrodes: they do not require a hole transport layer (HTL) and are low-cost, easy to fabricate on a large scale, and possess high ambient stability. The most critical hindrance to the photovoltaic performance of LC-PSCs is the inferior contact between the perovskite and carbon layers. Herein, carbon quantum dots (CQDs) as interface modifiers between the perovskite layer and carbon electrode are applied, which can facilitate hole injection into the carbon electrode, thus improving the photovoltaic performance of LC-PSCs. Meanwhile, the crystalline properties and hole mobility of the perovskite layer are improved significantly, and defect states in the perovskite layer are passivated following the embedding of CQDs. Finally, a champion efficiency of 13.3% in LC-PSCs based on perovskite-CQDs hybrid films without HTL is achieved for an active area of 1 cm(2), which represents a 24.3% improvement over the pristine device. Furthermore, LC-PSC devices maintain more than 95% of their initial efficiency under demanding conditions (humidity >40%, 1000 h). This work opens up a promising pathway to improve the photovoltaic performance of LC-PSCs and potentially also of other thin-film solar cells.

Solution-processed core/multishell semiconductor quantum dots (QDs) could be tailored to facilitate the carrier separation, promotion, and recombination mechanisms necessary to implement photon upconversion. In contrast to other upconversion schemes, upconverting QDs combine the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. Nevertheless, their upconversion quantum yield (UCQY) is fairly low. Here, design rules are uncovered that enable to significantly enhance the performance of double QD upconversion systems, and these findings are leveraged to fabricate upconverting QDs with increased photon upconversion efficiency and reduced saturation intensities under pulsed excitation. The role of the intra-QD band alignment is exemplified by comparing the upconversion process in PbS/CdS/ZnSe QDs with that of PbS/CdS/CdSe ones with variable CdSe shell thicknesses. It is shown that electron delocalization into the shell leads to a longer-lived intermediate state in the QDs, facilitating further absorption of photons, and enhancing the upconversion process. The performance of these upconversion QDs under pulsed excitation versus continuous pumping is also compared; the reasons for the significant differences between these two regimes are discussed. The results show how one can overcome some of the limitations of previous upconverting QDs, with potential applications in biophotonics and infrared detection.

The mechanisms of exciton generation and recombination in semiconductor nanocrystals are crucial to the understanding of their photophysics and for their application in nearly all fields. While many studies have been focused on type-I heterojunction nanocrystals, the photophysics of type-II nanorods, where the hole is located in the core and the electron is located in the shell of the nanorod, remain largely unexplored. In this work, by scanning single nanorods through the focal spot of radially and azimuthally polarized laser beams and by comparing the measured excitation patterns with a theoretical model, we determine the dimensionality of the excitation transition dipole of single type-II nanorods. Additionally, by recording defocused patterns of the emission of the same particles, we measure their emission transition dipoles. The combination of these techniques allows us to unambiguously deduce the dimensionality and orientation of both excitation and emission transition dipoles of single type-II semiconductor nanorods. The results show that in contrast to previously studied quantum emitters, the particles possess a 3D degenerate excitation and a fixed linear emission transition dipole.

A key challenge in attosecond science is the temporal characterization of attosecond pulses that are essential for understanding the evolution of electronic wavefunctions in atoms, molecules and solids(1-7). Current characterization methods, based on nonlinear light-matter interactions, are limited in terms of stability and waveform complexity. Here, we experimentally demonstrate a conceptually new linear and all-optical pulse characterization method, inspired by double-blind holography. Holography is realized by measuring the extreme ultraviolet (XUV) spectra of two unknown attosecond signals and their interference. Assuming a finite pulse duration constraint, we reconstruct the missing spectral phases and characterize the unknown signals in both isolated pulse and double pulse scenarios. This method can be implemented in a wide range of experimental realizations, enabling the study of complex electron dynamics via a single-shot and linear measurement.

Nanomaterials that possess the ability to upconvert two low-energy photons into a single high-energy photon are of great potential to be useful in a variety of applications. Recent attempts to realize upconversion (UC) in semiconducting quantum dot (QD) systems focused mainly on fabrication of heterostructured colloidal double QDs, or by using colloidal QDs as sensitizers for triplet-triplet annihilation in organic molecules. Here we propose a simplified approach, in which colloidal QDs are coupled to organic thiol ligands and UC is achieved via a charge-transfer state at the molecule-dot interface. We synthesized core/shell CdSe/CdS QDs and replaced their native ligands with thiophenol molecules. The alignment of the molecular HOMO with respect to the QD conduction band resulted in the formation of a new charge-transfer transition from which UC can be promoted. We performed a series of pump-probe experiments and proved the non-linear emission exhibited by these QDs is the result of UC by sequential photon absorption, and further characterized the QD-ligand energy landscape by transient absorption. Finally, we demonstrate that this scheme can also be applied in a QD solid.

Vision mechanisms in animals, especially those living in water, are diverse. Many eyes have reflective elements that consist of multilayers of nanometer-sized crystalline plates, composed of organic molecules. The crystal multilayer assemblies owe their enhanced reflectivity to the high refractive indices of the crystals in preferred crystallographic directions. The high refractive indices are due to the molecular arrangements in their crystal structures. Herein, data regarding these difficult-to-characterize crystals are reviewed. This is followed by a discussion on the function of these crystalline assemblies, especially in visual systems whose anatomy has been well characterized under close to in vivo conditions. Three test cases are presented, and then the relations between the reflecting crystalline components and their functions, including the relations between molecular structure, crystal structure, and reflecting properties are discussed. Some of the underlying mechanisms are also discussed, and finally open questions in the field are identified.

In this study, a facile and effective approach to synthesize high-quality perovskite-quantum dots (QDs) hybrid film is demonstrated, which dramatically improves the photovoltaic performance of a perovskite solar cell (PSC). Adding PbS QDs into CH3NH3PbI3 (MAPbI(3)) precursor to form a QD-in-perovskite structure is found to be beneficial for the crystallization of perovskite, revealed by enlarged grain size, reduced fragmentized grains, enhanced characteristic peak intensity, and large percentage of (220) plane in X-ray diffraction patterns. The hybrid film also shows higher carrier mobility, as evidenced by Hall Effect measurement. By taking all these advantages, the PSC based on MAPbI(3)-PbS hybrid film leads to an improvement in power conversion efficiency by 14% compared to that based on pure perovskite, primarily ascribed to higher current density and fill factor (FF). Ultimately, an efficiency reaching up to 18.6% and a FF of over approximate to 0.77 are achieved based on the PSC with hybrid film. Such a simple hybridizing technique opens up a promising method to improve the performance of PSCs, and has strong potential to be applied to prepare other hybrid composite materials.

In recent years, wavefront shaping has been utilized to control and correct distorted light for enhancing a bright spot, generation of a Bessel beam or darkening a complete area at the output of a scattering system. All these outcomes can be thought of as enhancing a particular mode of the output field. In this letter, we study the relation between the attainable enhancement factor, corresponding to the efficiency of mode conversion, and the field distribution of the target mode. Working in the limit of a thin diffuser enables not only a comparison between experimental and simulated results, but also allows for derivation of an analytic formula. These results shed light on the ability to use a scattering medium as a mode converter and on the relationship between the desired shape and the efficiency. (C) 2018 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

Induced chirality in colloidal semiconductor nanoparticles has raised significant attention in the past few years as an extremely sensitive spectroscopic tool and due to the promising applications of chiral quantum dots in sensing, quantum optics, and spintronics. Yet, the origin of the induced chiroptical effects in semiconductor nanoparticles is still not fully understood, partly because almost all the theoretical and experimental studies to date are based on the simple model system of a spherical nanocrystal. Here, the realization of induced chirality in atomically flat 2D colloidal quantum wells is shown. A strong circular dichroism (CD) response as well as an absorptive-like CD line shape is observed in chiral CdSe nanoplatelets (NPLs), significantly differing from that previously observed in spherical dots. Furthermore, this intense CD signal almost completely disappears after coating with a very thin CdS shell. In contrast, CdSe-CdS core-crown NPLs exhibit a spectral response which seems to originate independently from the core and the crown regions of the NPL. This work on the one hand further advances the understanding of the fundamental origin of induced chiroptical effects in semiconductor nanoparticles, and on the other opens a pathway toward applications using chiroptical materials.

In recent decades, optogenetics has been transforming neuroscience research, enabling neuroscientists to drive and read neural circuits. The recent development in illumination approaches combined with two-photon (2P) excitation, either sequential or parallel, has opened the route for brain circuit manipulation with single-cell resolution and millisecond temporal precision. Yet, the high excitation power required for multi-target photostimulation, especially under 2P illumination, raises questions about the induced local heating inside samples. Here, we present and experimentally validate a theoretical model that makes it possible to simulate 3D light propagation and heat diffusion in optically scattering samples at high spatial and temporal resolution under the illumination configurations most commonly used to perform 2P optogenetics: single-and multi-spot holographic illumination and spiral laser scanning. By investigating the effects of photostimulation repetition rate, spot spacing, and illumination dependence of heat diffusion, we found conditions that make it possible to design a multi-target 2P optogenetics experiment with minimal sample heating.

Creating sub-micron hotspots for applications such as heat-assisted magnetic recording (HAMR) is a challenging task. The most common approach relies on a surface-plasmon resonator (SPR), whose design dictates the size of the hotspot to always be larger than its critical dimension. Here, we present an approach which circumvents known geometrical restrictions by resorting to electric field confinement via excitation of a gap-mode (GM) between a comparatively large Gold (Au) nano-sphere (radius of 100 nm) and the magnetic medium in a grazing-incidence configuration. Operating a lambda = 785 nm laser, sub-200 nm hot spots have been generated and successfully used for GM-assisted magnetic switching on commercial CoCrPt perpendicular magnetic recording media at laser powers and pulse durations comparable to SPR-based HAMR. Lumerical electric field modelling confirmed that operating in the near-infrared regime presents a suitable working point where most of the light's energy is deposited in the magnetic layer, rather than in the nano-particle. Further, modelling is used for predicting the limits of our method which, in theory, can yield sub-30 nm hotspots for Au nano-sphere radii of 25-50 nm for efficient heating of FePt recording media with a gap of 5 nm. Published by AIP Publishing.

Self-healing, where a modification in some parameter is reversed with time without any external intervention, is one of the particularly interesting properties of halide perovskites. While there are a number of studies showing such self-healing in perovskites, they all are carried out on thin films, where the interface between the perovskite and another phase (including the ambient) is often a dominating and interfering factor in the process. Here, self-healing in perovskite (methylammonium, formamidinium, and cesium lead bromide (MAPbBr3, FAPbBr3, and CsPbBr3)) single crystals is reported, using two-photon microscopy to create damage (photobleaching) ≈110 µm inside the crystals and to monitor the recovery of photoluminescence after the damage. Self-healing occurs in all three perovskites with FAPbBr3 the fastest (≈1 h) and CsPbBr3 the slowest (tens of hours) to recover. This behavior, different from surface-dominated stability trends, is typical of the bulk and is strongly dependent on the localization of degradation products not far from the site of the damage. The mechanism of self-healing is discussed with the possible participation of polybromide species. It provides a closed chemical cycle and does not necessarily involve defect or ion migration phenomena that are often proposed to explain reversible phenomena in halide perovskites.

Ficus trees are adapted to diverse environments and have some of the highest rates of photosynthesis among trees. Ficus leaves can deposit one or more of the three major mineral types found in leaves: amorphous calcium carbonate cystoliths, calcium oxalates, and silica phytoliths. In order to better understand the functions of these minerals and the control that the leaf exerts over mineral deposition, we investigated leaves from 10 Ficus species from vastly different environments (Rehovot, Israel; Bologna, Italy; Issa Valley, Tanzania; and Ngogo, Uganda). We identified the mineral locations in the soft tissues, the relative distributions of the minerals, and mineral volume contents using microcomputed tomography. Each Ficus species is characterized by a unique 3D mineral distribution that is preserved in different environments. The mineral distribution patterns are generally different on the adaxial and abaxial sides of the leaf. All species examined have abundant calcium oxalate deposits around the veins. We used micromodulated fluorimetry to examine the effect of cystoliths on photosynthetic efficiency in two species having cystoliths abaxially and adaxially (Ficus microcarpa) or only abaxially (Ficus carica). In F. microcarpa, both adaxial and abaxial cystoliths efficiently contributed to light redistribution inside the leaf and, hence, increased photosynthetic efficiency, whereas in F. carica, the abaxial cystoliths did not increase photosynthetic efficiency.

Halide perovskite (HaP) semiconductors are revolutionizing photovoltaic (PV) solar energy conversion by showing remarkable performance of solar cells made with HaPs, especially tetragonal methylammonium lead triiodide (MAPbI₃). In particular, the low voltage loss of these cells implies a remarkably low recombination rate of photogenerated carriers. It was suggested that low recombination can be due to the spatial separation of electrons and holes, a possibility if MAPbI₃ is a semiconducting ferroelectric, which, however, requires clear experimental evidence. As a first step, we show that, in operando, MAPbI₃ (unlike MAPbBr₃) is pyroelectric, which implies it can be ferroelectric. The next step, proving it is (not) ferroelectric, is challenging, because of the material's relatively high electrical conductance (a consequence of an optical band gap suitable for PV conversion) and low stability under high applied bias voltage. This excludes normal measurements of a ferroelectric hysteresis loop, to prove ferroelectricity's hallmark switchable polarization. By adopting an approach suitable for electrically leaky materials as MAPbI₃, we show here ferroelectric hysteresis from well-characterized single crystals at low temperature (still within the tetragonal phase, which is stable at room temperature). By chemical etching, we also can image the structural fingerprint for ferroelectricity, polar domains, periodically stacked along the polar axis of the crystal, which, as predicted by theory, scale with the overall crystal size. We also succeeded in detecting clear second harmonic generation, direct evidence for the material's noncentrosymmetry. We note that thematerial's ferroelectric nature, can, but need not be important in a PV cell at room temperature.

Colloidal CdSe nanoplatelets (NPLs) deposited on TiO₂ and overcoated by ZnS were explored as light absorbers in semiconductor-sensitized solar cells (SSSCs). Significant red shifts of both absorption and steady-state photoluminescence (PL) along with rapid PL quenching suggest a type II band alignment at the interface of the CdSe NPL and the ZnS barrier layer grown on the NPL layer, as confirmed by energy band measurements. The considerable red shift leads to enhanced spectral absorption coverage. Cell characterization shows an increased open-circuit voltage of 664 mV using a polysulfide electrolyte, which can be attributed to a photoinduced dipole effect created by the spatial charge separation across the nanoplatelet sensitizers. The observed short-circuit current density of 11.14 mA cm^-2 approaches the maximal theoretical current density for this choice of absorber, yielding an internal quantum efficiency of close to 100%, a clear signature of excellent charge transport and collection yields. With their steep absorption onset and negligible inhomogeneous broadening, NPL-based SSSCs are intriguing candidates for future high-voltage sensitized cells.

We present a method that utilizes quantum correlation measurements for multi-emitter sub-diffraction localization in a time-dependent scene. This is demonstrated using a newly developed imaging configuration based on fiber bundle coupled single-photon avalanche detectors.

The recovery of a signal from the magnitude of its Fourier transform, also known as phase retrieval, is of fundamental importance in many scientific fields. It is well known that due to the loss of Fourier phase the problem in one-dimensional (1D) is ill-posed. Without further constraints, there is no unique solution to the problem. In contrast, uniqueness up to trivial ambiguities very often exists in higher dimensions, with mild constraints on the input. In this paper, we focus on the 2D phase retrieval problem and provide insight into this uniqueness property by exploring the connection between the 2D and 1D formulations. In particular, we show that 2D phase retrieval can be cast as a 1D problem with additional constraints, which limit the solution space. We then prove that only one additional constraint is sufficient to reduce the many feasible solutions in the 1D setting to a unique solution for almost all signals. These results allow to obtain an analytical approach (with combinatorial complexity) to solve the 2D phase retrieval problem when it is unique.

Multicore fiber bundles are widely used in endoscopy due to their miniature size and their direct imaging capabilities. They have recently been used, in combination with spatial light modulators, in various realizations of endoscopy with little or no optics at the distal end. These schemes require characterization of the relative phase offsets between the different cores, typically done using off-axis holography, thus requiring both an interferometric setup and, typically, access to the distal tip. Here we explore the possibility of employing phase retrieval to extract the necessary phase information. We show that in the noise-free case, disordered fiber bundles are superior for phase retrieval over their periodic counterparts, and demonstrate experimentally accurate retrieval of phase information for up to 10 simultaneously illuminated cores. Thus, phase retrieval is presented as a viable alternative for real-timemonitoring of phase distortions in multicore fiber bundles. (C) 2017 Optical Society of America

Heat-assisted magnetic recording (HAMR) is often considered the next major step in the storage industry: it is predicted to increase the storage capacity, the read/write speed and the data lifetime of future hard disk drives. However, despite more than a decade of development work, the reliability is still a prime concern. Featuring an inherently fragile surface-plasmon resonator as a highly localized heat source, as part of a near-field transducer (NFT), the current industry concepts still fail to deliver drives with sufficient lifetime. This study presents a method to aid conventional NFT-designs by additional grazing-incidence laser illumination, which may open an alternative route to high-durability HAMR. Magnetic switching is demonstrated on consumer-grade CoCrPt perpendicular magnetic recording media using a green and a near-infrared diode laser. Sub-500 nm magnetic features are written in the absence of a NFT in a moderate bias field of only μ₀H = 0.3 T with individual laser pulses of 40 mW power and 50 ns duration with a laser spot size of 3 μm (short axis) at the sample surface - six times larger than the magnetic features. Herein, the presence of a nanoscopic object, i.e., the tip of an atomic force microscope in the focus of the laser at the sample surface, has no impact on the recorded magnetic features - thus suggesting full compatibility with NFT-HAMR.

We investigated the effect of cation exchange on the anionic framework of lightly doped CdSe:Te/CdS nanorods. In contrast with previously studied core/shell systems, the Te dopant, located in the center of the CdSe core, provides an extremely sensitive indicator for any structural changes of the anionic framework that may occur as a result of the cation exchange process. We first optimized the cation exchange procedure in order to retain the fluorescence properties of the CdSe:Te/CdS nanorods after exchange of Cd2+ for Cu+ and back to Cd2+. Next, using multiexciton spectroscopy, we were able to probe the magnitude of the exciton exciton repulsion interaction and use that to assess the degree of crystal structure conservation. Our findings provide a much stronger proof that the anion framework is indeed rigid, showing no evidence of significant migration of the anionic dopant.

The synthesis of hybrid nanostructures that have specific properties has become a significant topic for construction of "smart" nanomaterials for various applications. Formation of hybrid nanostructures, particularly those combining metals and semiconductors, often introduces new chemical, optical, and electronic properties. Here, we show a simple solution phase synthesis of multicomponent heterostructures based on the growth of metal and semiconductor onto the tips of semiconductor nanorods, leading to the formation of a hybrid semiconductor/semiconductor/metal structure. The synthesis involves the reduction of Pt-acetylacetonate to achieve selective growth of a Pt metal tip onto one side of the CdS rod, followed by the thermal decomposition of Pb-bis(diethyldithiocarbamate) to grow a PbS nanocrystal onto the other tip of the nanorod. The band alignment between the two semiconductor components as well as the alignment with the Fermi level of the metal could support intraparticle charge transfer, which is often sought after for photocatalysis applications. Yet, we show, using femtosecond transient differential absorption spectroscopy (TDA), that carrier dynamics in such a hybrid system can be more complex than that predicted simply by bulk band alignment considerations. This highlights the importance of the design of band alignment and interface passivation and its role in affecting carrier dynamics within hybrid nanostructures.

Cadmium chalcogenide nanoplatelet (NPL) synthesis has recently witnessed a significant advance in the production of more elaborate structures such as core/shell and core/crown NPLs. However, controlled doping in these structures has proved difficult because of the restrictive synthetic conditions required for 2D anisotropic growth. Here, we explore the incorporation of tellurium (Te) within CdSe NPLs with Te concentrations ranging from doping to alloying. For Te concentrations higher than similar to 30%, the CdSexTe(1-x) NPLs show emission properties characteristic of an alloyed material with a bowing of the band gap for increased concentrations of Te. This behavior is in line with observations in bulk samples and can be put in the context of the transition from a pure material to an alloy. In the dilute doping regime, CdSe: Te NPLs, in comparison to CdSe NPLs, show a distinct photoluminescence (PL) red shift and prolonged emission lifetimes (LTs) associated with Te hole traps which are much deeper than in bulk samples. Furthermore, single particle spectroscopy reveals dramatic modifications in PL properties. In particular, doped NPLs exhibit photon antibunching and emission dynamics significantly modified compared to undoped or alloyed NPLs.

Light-induced tunable photonic systems are rare in nature, and generally beyond the state-of-the-art in artificial systems. Sapphirinid male copepods produce some of the most spectacular colors in nature. The male coloration, used for communication purposes, is structural and is produced from ordered layers of guanine crystals separated by cytoplasm. It is generally accepted that the colors of the males are related to their location in the epipelagic zone. By combining correlative reflectance and cryoelectron microscopy image analyses, together with optical time lapse recording and transfer matrix modeling, it is shown that male sapphirinids have the remarkable ability to change their reflectance spectrum in response to changes in the light conditions. It is also shown that this color change is achieved by a change in the thickness of the cytoplasm layers that separate the guanine crystals. This change is reversible, and is both intensity and wavelength dependent. This capability provides the male with the ability to efficiently reflect light under certain conditions, while remaining transparent and hence camouflaged under other conditions. These copepods can thus provide inspiration for producing synthetic tunable photonic arrays.

In the hybrid structure employing CdS/N719 QD/dye co-sensitized photoelectrode, it is revealed by consistent results from the steady-state and time-resolved photoluminescence (PL) that the QD regeneration was realized by the effective charge transfer from the dye sensitizer, resulting in a significant PL quenching. This is helpful for retarding the recombination in the device. Furthermore, by varying the thickness of the TiO₂ film, the light harvesting efficiency and the charge collection efficiency were balanced, leading to an optimal TiO₂ thickness of 22 μm and a power conversion efficiency (PCE) of about 6.5%. Compared with the dye N719 only sensitized system with the same dye loading(with an efficiency of 5.09%), the co-sensitization of dye N719 and CdS (with an efficiency of 6.44%) enhanced the overall PCE significantly by 26.5% Notably, this is one of the best reported efficiencies for the QD-dye co-sensitized solar cells.

Upconversion is a nonlinear process in which two, or more, long wavelength photons are converted to a shorter wavelength photon. It holds great promise for bioimaging, enabling spatially resolved imaging in a scattering specimen and for photovoltaic devices as a means to surpass the Shockley-Queisser efficiency limit. Here, we present dual near-infrared and visible emitting PbSe/CdSe/CdS nanocrystals able to upconvert a broad range of NIR wavelengths to visible emission at room temperature. The synthesis is a three-step process, which enables versatility and tunability of both the visible emission color and the NIR absorption edge. Using this method, one can achieve a range of desired upconverted emission peak positions with a suitable NIR band gap.

Nonlinear optical processes can be dramatically enhanced via the use of localized surface plasmon modes in metal nanoparticles. Here we show how more elaborate structures, based on shape-controlled Au/Cu₂O core/shell nanostructures, enable further enhancement of the nanoparticle third-harmonic scattering cross-section. The semiconducting component takes a twofold role in this structure, both providing a knob to tune the resonant frequency of the gold plasmon and providing resonant enhancement by virtue of its excitonic states. The advantages and deficiencies of using such core/shell metal/semiconductor structures are discussed.

The fresh water fish neon tetra has the ability to change the structural color of its lateral stripe in response to a change in the light conditions, from blue-green in the light-adapted state to indigo in the dark-adapted state. The colors are produced by constructive interference of light reflected from stacks of intracellular guanine crystals, forming tunable photonic crystal arrays. We have used micro X-ray diffraction to track in time distinct diffraction spots corresponding to individual crystal arrays within a single cell during the color change. We demonstrate that reversible variations in crystal tilt within individual arrays are responsible for the light-induced color variations. These results settle a long-standing debate between the two proposed models, the "Venetian blinds" model and the "accordion" model. The insight gained from this biogenic light-induced photonic tunable system may provide inspiration for the design of artificial optical tunable systems.

According to quantum electrodynamics, the exchange of virtual photons in a system of identical quantum emitters causes a shift of its energy levels. Such shifts, known as cooperative Lamb shifts, have been studied mostly in the near-field regime. However, the resonant electromagnetic interaction persists also at large distances, providing coherent coupling between distant atoms. Here, we report a direct spectroscopic observation of the cooperative Lamb shift of an optical electric-dipole transition in an array of Sr+ ions suspended in a Paul trap at inter-ion separations much larger than the resonance wavelength. By controlling the precise positions of the ions, we studied the far-field resonant coupling in chains of up to eight ions, extending to a length of 40 mu m. This method provides a novel tool for experimental exploration of cooperative emission phenomena in extended mesoscopic atomic arrays.

Phase measurement is a long-standing challenge in a wide range of applications, from X-ray imaging to astrophysics and spectroscopy. While in some scenarios the phase is resolved by an interferometric measurement, in others it is reconstructed via numerical optimization, based on some a-priori knowledge about the signal. The latter commonly use iterative algorithms, and thus have to deal with their convergence, stagnation, and robustness to noise. Here we combine these two approaches and present a new scheme, termed double blind Fourier holography, providing an efficient solution to the phase problem in two dimensions, by solving a system of linear equations. We present and experimentally demonstrate our approach for the case of lens-less imaging.

The organic-inorganic interfacial chemical composition and interaction have a critical influence on the performance of corresponding hybrid photovoltaic devices. Such interfaces have been shown to be controlled by using surfactants to promote contact between the organic electron-donating conjugated polymer species and the inorganic electron-accepting metal oxides. However, the location of the surfactant at the organic-inorganic interface often hinders donor-acceptor charge transfer and limits the device performance. In this study we have replaced the conventional surfactant with an optically and electronically active amphiphilic polythiophene that both compatibilizes the conjugated polymer and metal oxide, and plays an active role in the charge generation process. Specifically, a polythiophene with hydrophilic urethane side-groups allows the formation of a fine continuous ZnO network in P3HT with an organic-inorganic interfacial chemical interaction and a high surface area. A combination of FTIR, absorption and photoluminescence life-time spectroscopies yields insights into the composition and nano-scale interaction of the components, while high-resolution electron microscopy reveals the morphology of the films. The control over morphology and electronic coupling at the hybrid interface is manifested in photovoltaic devices with improved performances.

The optical and electronic properties of suspensions of inorganic fullerene-like nanoparticles of MoS₂ are studied through light absorption and zeta-potential measurements and compared to those of the corresponding microscopic platelets. The total extinction measurements show that, in addition to excitonic peaks and the indirect band gap transition, a new peak is observed at 700-800 nm. This spectral peak has not been reported previously for MoS₂. Comparison of the total extinction and decoupled absorption spectrum indicates that this peak largely originates from scattering. Furthermore, the dependence of this peak on nanoparticle size, shape, and surface charge, as well as solvent refractive index, suggests that this transition arises from a plasmon resonance.

Super-resolution microscopy, the imaging of features below the Abbe diffraction limit, has been achieved by a number of methods in recent years. Each of these methods relies on breaking one of the assumptions made in the derivation of the diffraction limit. While uniform spatial illumination, linearity and time independence have been the most common cornerstones of the Abbe limit broken in super-resolution modalities, breaking the 'classicality of light' assumption as a pathway to achieve super-resolution has not been shown. Here we demonstrate a method that utilizes the antibunching characteristic of light emitted by Quantum Dots (QDs), a purely quantum feature of light, to obtain imaging beyond the diffraction limit. Measuring such high order correlations in the emission of a single QD necessitates stability at saturation conditions while avoiding damage and enhanced blinking. This ability was facilitated through new understandings that arisen from exploring the QD 'blinking' phenomena. We summarize here two studies that contributed to our current understanding of QD stability.

The optical diffraction limit imposes a bound on imaging resolution in classical optics. Over the last twenty years, many theoretical schemes have been presented for overcoming the diffraction barrier in optical imaging using quantum properties of light. Here, we demonstrate a quantum superresolution imaging method taking advantage of nonclassical light naturally produced in fluorescence microscopy due to photon antibunching, a fundamentally quantum phenomenon inhibiting simultaneous emission of multiple photons. Using a photon counting digital camera, we detect antibunching-induced second and third order intensity correlations and perform subdiffraction limited quantum imaging in a standard wide-field fluorescence microscope.

Luminescence upconversion nanocrystals capable of converting two low-energy photons into a single photon at a higher energy are sought-after for a variety of applications, including bioimaging and photovoltaic light harvesting. Currently available systems, based on rare-earth-doped dielectrics, are limited in both tunability and absorption cross-section. Here we present colloidal double quantum dots as an alternative nanocrystalline upconversion system, combining the stability of an inorganic crystalline structure with the spectral tunability afforded by quantum confinement. By tailoring its composition and morphology, we form a semiconducting nanostructure in which excited electrons are delocalized over the entire structure, but a double potential well is formed for holes. Upconversion occurs by excitation of an electron in the lower energy transition, followed by intraband absorption of the hole, allowing it to cross the barrier to a higher energy state. An overall conversion efficiency of 0.1% per double excitation event is achieved.

An all-inorganic compound colloidal quantum dot incorporating a highly emissive CdSe core, which is linked by a CdS tunneling barrier to an engineered charge carrier trap composed of PbS, is designed, and its optical properties are studied in detail at the single-particle level. Study of this structure enables a deeper understanding of the link between photoinduced charging and surface trapping of charge carriers and the phenomenon of quantum dot blinking. In the presence of the hole trap, a "gray" emissive state appears, associated with charging of the core. Rapid switching is observed between the "on" and the "gray" state, although the switching dynamics in and out of the dark "off" state remain unaffected. This result completes the links in the causality chain connecting charge carrier trapping, charging of QDs, and the appearance of a "gray" emission state.

Stochastic distortion of light beams in scattering samples makes in-depth photoexcitation in brain tissue a major challenge. A common solution for overcoming scattering involves adaptive pre-compensation of the unknown distortion^1-3. However, this requires long iterative searches for sample-specific optimized corrections, which is a problem when applied to optical neurostimulation where typical timescales in the system are in the millisecond range. Thus, photoexcitation in scattering media that is independent of the properties of a specific sample would be an ideal solution. Here, we show that temporally focused two-photon excitation⁴with generalized phase contrast⁵ enables photoexcitation of arbitrary spatial patterns within turbid tissues with remarkable robustness to scattering. We demonstrate three-dimensional confinement of tailored photoexcitation patterns >200 μm in depth, both in numerical simulations and through brain slices combined with patch-clamp recording of photoactivated channelrhodopsin-2.

We experimentally observe and measure the spectral phase shift of a pulse subjected to spectral focusing. We find a phase shift of π/2, reaffirming the Gouy phase shift as a general consequence of wave confinement whether in space/momentum or frequency/time coordinates.

Plasmonic antennas are key elements to control the luminescence of quantum emitters. However, the antenna's influence is often hidden by quenching losses. Here, the luminescence of a quantum dot coupled to a gold dimer antenna is investigated. Detailed analysis of the multiply excited states quantifies the antenna's influence on the excitation intensity and the luminescence quantum yield separately.

Although colloidal quantum dots (QDs) exhibit excellent photostability under mild excitation, intense illumination makes their emission increasingly intermittent, eventually leading to photobleaching. We study fluorescence of two commonly used types of QDs under pulsed excitation with varying power and repetition rate. The photostability of QDs is found to improve dramatically at low repetition rates, allowing for prolonged optical saturation of QDs without apparent photodamage. This observation suggests that QD blinking is facilitated by absorption of light in a transient state with a microsecond decay time. Enhanced photostability of generic quantum dots under intense illumination opens up new prospects for fluorescence microscopy and spectroscopy.

A highly efficient quantum dot (QD)/inorganic layer/dye molecule sandwich structure was designed and applied in electrochemical QD-sensitized solar cells. The key component TiO ₂/CdS/ZnS/N719 hybrid photoanode with ZnS insertion between the two types of sensitizers was demonstrated not only to efficiently extend the light absorption but also to suppress the charge recombination from either TiO ₂ or CdS QDs to electrolyte redox species, yielding a photocurrent density of 11.04 mA cm ^-2, an open-circuit voltage of 713 mV, a fill factor of 0.559, and an impressive overall energy conversion efficiency of 4.4%. More importantly, the cell exhibited enhanced photostability with the help of the synergistic stabilizing effect of both the organic and the inorganic passivation layers in the presence of a corrosive electrolyte.

Intraband hole relaxation of colloidal Te-doped CdSe quantum dots is studied using state-selective transient absorption spectroscopy. The dots are excited at the band edge, and the defect band bleach caused by state filling of the hole is probed. Close to the defect energy, the hole relaxation is substantially slowed down, indicating a gap separating the defect state from the CdSe band edge. A clear dependence of the relaxation time with the QDs size is presented, implying that the hole relaxation is mediated by longitudinal optical (LO) phonon modes of the CdSe host. In addition, we find that overcoating the quantum dots by two monolayers of a ZnS shell extends the hole relaxation time by a factor of 2, suggesting a combined effect of LO phonons and surface effects governing intraband hole relaxation.

Breaking the diffraction limit in microscopy by utilizing the quantum properties of light has been the goal of intense research in recent years. We propose a super-resolution technique based on nonclassical emission statistics of fluorescent markers, routinely used as contrast labels for bioimaging. The technique can be readily implemented with current technology.

The use of optogenetics, the technology that combines genetic and optical methods to monitor and control the activity of specific cell populations, is now widely adopted in neuroscience. The development of optogenetic tools, such as natural photosensitive ion channels and pumps or calcium- and voltage-sensitive proteins, has been growing tremendously during the past 10 years, thanks to the improvement of their performances in terms of facilitating light stimulation. To this aim, efficient illumination methods are also needed. The most common way to photostimulate optogenetic tools has been, so far, widefield illumination with visible light. However, the necessity of addressing the complexity of brain architecture has recently imposed switching to the use of two-photon excitation, which provides a better spatial specificity and deeper penetration in scattering tissue. Two-photon excitation is still challenging, due to intrinsic characteristics of optogenetic tools (e.g., the low conductivity of light-sensitive channels), and efficient illumination methods are therefore essential for advancing in this domain. Here, we present a review on the existing two-photon optical approaches for photoactivation of optogenetic tools, and future perspectives for the widespread implementation of these techniques.

The use of Forster resonant energy transfer (FRET) has recently shown promise for significant improvement in various aspects of photoelectrochemical cells. Considering the particular case of semiconductor quantum dot donors, we show that they can enable broadening of the spectral response and increased optical density of the cell, thus increasing the current while potentially decreasing the electrode thickness. Moreover, the use of FRET and the separation of optical and electrical function within the cell provide flexibility in the choice of materials for both the antenna and sensitizer, opening new paths for performance optimization and achievement of long-term cell stability.

Understanding how quantum dot (QD)-sensitized solar cells operate requires accurate determination of the offset between the lowest-unoccupied molecular orbital (LUMO) of the sensitizer quantum dot and the conduction band of the metal oxide electrode. We present detailed optical spectroscopy, low-energy photoelectron spectroscopy, and two-photon photoemission studies of the energetics of size-selected CdSe colloidal QDs deposited on TiO₂ electrodes. Our experimental findings show that in contrast to the prediction of simplified models based on bulk band offsets and effective mass considerations, band alignment in this system is strongly modified by the interaction between the QDs and the electrode. In particular, we find relatively small conduction band- LUMO offsets, and near "pinning" of the QD LUMO relative to the conduction band of the TiO₂ electrode, which is explained by the strongQD-electrode interaction. That interaction is the origin for the highly efficientQDto electrode charge transfer, and it also bears on the possibility of hot carrier injection in these types of cells.

Detection of the second harmonic generation from single CdTe quantum dots of similar to 11.5 nm diameter enables us to obtain an absolute value for the nonlinear susceptibility chi((2)) of these nanoparticles as well as their dispersion properties. These measurements, complemented by ensemble hyper-Rayleigh scattering characterization, elucidate the role of quantum confinement in the second harmonic generation process. We show that, under similar excitation conditions, the chi((2)) of quantum dots can significantly exceed that of the corresponding bulk material. The results indicate that by careful choice of excitation wavelength and material; kilo-counts per second rates of second harmonic generation photons can be obtained from quantum dots with

We study second-harmonic generation from single CdTe/CdS core/shell rod-on-dot nanocrystals with different geometrical parameters, which allow to fine tune the nonlinear properties of the nanostructure. These hybrid semiconductor-semiconductor nanoparticles exhibit extremely strong and stable second-harmonic emission, although the size of CdTe core is still within the strong quantum confinement regime. The orientation sensitive polarization response is analyzed by means of a pointwise additive model of the third-order tensors associated to the nanoparticle components. These findings prove that engineering of semiconducting complex heterostructures at the single nanoparticle scale can lead to extremely bright nanometric nonlinear light sources.

The energetics and dynamics of multiply excited states in single material colloidal quantum dots have already been shown to exhibit universal trends. Here we attempt to identify similar trends in exciton-exciton interactions within compound colloidal quantum dots. For this end, we thoroughly review previously available data and also present experimental data on several newly synthesized systems, focusing on core/shell nanocrystals with a type-II band alignment. A universal condition for the transition from binding to repulsion of the biexciton (type-I-type-II transition) is established in terms of the change in the exciton radiative lifetime. A scaling rule is also presented for the magnitude of exciton-exciton repulsion. In contrast, we do not identify a clear universal scaling of the non-radiative Auger recombination lifetime of the biexciton state. Finally, a perspective on future applications of engineered multiexcitonic states is presented.

Ultrafast science is inherently, due to the lack of fast enough detectors and electronics, based on nonlinear interactions. Typically, however, nonlinear measurements require significant powers and often operate in a limited spectral range. Here we overcome the difficulties of ultraweak ultrafast measurements by precision time-domain localization of spectral components. We utilize this for linear self-referenced characterization of pulse trains having ∼ 1 photon per pulse, a regime in which nonlinear techniques are impractical, at a temporal resolution of ∼ 10 fs. This technique does not only set a new scale of sensitivity in ultrashort pulse characterization, but is also applicable in any spectral range from the near-infrared to the deep UV.

Optical antennas are essential devices to interface light to nanoscale volumes and locally enhance the electromagnetic intensity. Various experimental methods can be used to quantify the antenna amplification on the emission process, yet characterizing the antenna amplification at the excitation frequency solely is a challenging task. Such experimental characterization is highly needed to fully understand and optimize the antenna response. Here, we describe a novel experimental tool to directly measure the antenna amplification on the excitation field independently of the emission process. We monitor the transient emission dynamics of colloidal quantum dots and show that the ratio of doubly to singly excited state photoluminescence decay amplitudes is an accurate tool to quantify the local excitation intensity amplification. This effect is demonstrated on optical antennas made of polystyrene microspheres and gold nanoapertures, and supported by numerical computations. The increased doubly excited state formation on nanoantennas realizes a new demonstration of enhanced light-matter interaction at the nanoscale.

The observed intermittent light emission from colloidal semiconductor nanocrystals has long been associated with Auger recombination assisted quenching. We test this view by observing transient emission dynamics of CdSe/CdS/ZnS semiconductor nanocrystals using time-resolved photon counting. The size and intensity dependence of the observed decay dynamics seem inconsistent with those expected from Auger processes. Rather, the data suggest that in the "off" state the quantum dot cycles in a three-step process: photoexcitation, rapid trapping, and subsequent slow nonradiative decay.

Nanoscale engineering of functional materials is reviving quadratic nonlinear optics in conjunction with new quantitative multiphoton imaging techniques allowing phase and polarization resolution. It permits full tensor characterization of individual nanoparticles as well as mapping of artificial and bio environments.

Biological photonic systems composed of anhydrous guanine crystals evolved separately in several taxonomie groups. Here, two such systems found in fish and spiders, both of which make use of anhydrous guanine crystal plates to produce structural colors, are examined. Measurements of the photoniccrystal structures using cryo-SEM show that the crystal plates in both fish skin and spider integument are ∼20-nm thick. The reflective unit in the fish comprises stacks of single plates alternating with ∼ 230-nm-thick cytoplasm layers. In the spiders the plates are formed as doublet crystals, cemented by 30-nm layers of amorphous guanine, and are stacked with ∼200nm of cytoplasm between crystal doublets. They achieve light reflective properties through the control of crystal morphology and stack dimensions, reaching similar efficiencies of light reflectivity in both fish skin and spider integument. The structure of guanine plates in spiders are compared with the more common situation in which guanine occurs in the form of relatively unorganized prismatic crystals, yielding a matt white coloration.

Blinking in colloidal nanocrystals is studied through photon counting from single nanocrystals. Size independent 'off' state dynamics are observed in contrast to predictions by prevailing models which attribute 'dark' states to Auger recombination assisted quenching.

Nanoparticles emitting two-photon luminescence are broadly used as photostable emitters for nonlinear microscopy. Second-harmonic generation (SHG) as another two-photon mechanism offers complementary optical properties but the reported sizes of nanoparticles are still large, of a few tens of nanometers. Herein, coherent SHG from single core/shell CdTe/CdS nanocrystals with a diameter of 10 to 15nm is reported. The nanocrystal excitation spectrum reveals resonances in the nonlinear efficiency with an overall maximum at about 970 nm. Polarization analysis of the second-harmonic emission confirms the expected zinc blende symmetry, and allows extraction of the three-dimensional nanocrystal orientation. The small size of these nonlinearly active quantum dots, together with the intrinsic coherence and orientation sensitivity of the SHG process, are well adapted for ultrafast probing of optical near-fields with high resolution as well as for orientation tracking for bioimaging applications.

Assemblies of CdSe nanoparticles (NPs) on a dithiol-coated Au electrode were created, and their electronic energetics were quantified. This report describes the energy level alignment of the filled and unfilled electronic states of CdSe nanoparticles with respect to the Au Fermi level. Using cyclic voltammetry, it was possible to measure the energy of the filled states of the CdSe NPs with respect to the Au substrate relative to a Ag/AgNO₃ electrode, and by using photoemission spectroscopy, it was possible to independently measure both the filled state energies (via single photon photoemission) and those of the unfilled states (via two photon photoemission) with respect to the vacuum level. Comparison of these two different measures shows good agreement with the IUPAC-accepted value of the absolute electrode potential. In contrast to the common model of energy level alignment, the experimental findings show that the CdSe filled states become 'pinned' to the Fermi level of the Au electrode, even for moderately small NP sizes.

We discuss theoretically and demonstrate experimentally the robustness of the adiabatic sum frequency conversion method. This technique, borrowed from an analogous scheme of robust population transfer in atomic physics and nuclear magnetic resonance, enables the achievement of nearly full frequency conversion in a sum frequency generation process for a bandwidth up to two orders of magnitude wider than in conventional conversion schemes. We show that this scheme is robust to variations in the parameters of both the nonlinear crystal and of the incoming light. These include the crystal temperature, the frequency of the incoming field, the pump intensity, the crystal length and the angle of incidence. Also, we show that this extremely broad bandwidth can be tuned to higher or lower central wavelengths by changing either the pump frequency or the crystal temperature. The detailed study of the properties of this converter is done using the Landau-Zener theory dealing with the adiabatic transitions in two level systems.

Temporal focusing of ultrashort pulses has been shown to enable wide-field depth-resolved two-photon fluorescence microscopy. In this process, an entire plane in the sample is selectively excited by introduction of geometrical dispersion to an ultrashort pulse. Many applications, such as multiphoton lithography, uncaging or region-of-interest imaging, require, however, illumination patterns which significantly differ from homogeneous excitation of an entire plane in the sample. Here we consider the effects of such spatial modulation of a temporally focused excitation pattern on both the generated excitation pattern and on its axial confinement. The transition in the axial response between line illumination and wide-field illumination is characterized both theoretically and experimentally. For 2D patterning, we show that in the case of amplitude-only modulation the axial response is generally similar to that of wide-field illumination, while for phase-and-amplitude modulation the axial response slightly deteriorates when the phase variation is rapid, a regime which is shown to be relevant to excitation by beams shaped using spatial light modulators. Finally, general guidelines for the use of spatially modulated temporally focused excitation are presented.

We observed second harmonic generation from semiconducting CdTe/CdS nanocrystals with a diameter below 15 nm. Their submicron size, high nonlinearity and orientation sensitive SHG response are adapted for ultrafast, high resolution probing of optical near-fields.

Our understanding of processes involved in two-photon photoemission (2PPE) from surfaces can be tested when we try to exercise control over the electron emission. In the past, coherently controlled 2PPE has been demonstrated using very short pulses and single crystal surfaces. Here we show that by applying polarization pulse shaping on surfaces, it is possible to vary both the angular distribution of the emitted photoelectrons and the total photoemission yield. The presented 2PPE experimental setup introduces pulse shaping in the visible range, which is a unique property that allows control of polarization. We relate the ability to use polarization as a means of control to the surface corrugation.

Depth resolved multiphoton microscopy is performed by collecting the fluorescent emission of two-exciton states in colloidal quantum dots. This process involves two consecutive resonant absorption events, thus requiring unprecedented low excitation energy and peak power.

Depth resolved multiphoton microscopy is performed by collecting the fluorescent emission of two-exciton states in colloidal quantum dots. The biexciton is formed via two sequential resonant absorption events. Due to the large absorption cross-section and the long lifetime of the intermediate (singly excited) state, unprecedented low excitation energy and peak powers (down to 105W/cm2) are required to generate this nonlinear response.Depending on the quantum dot parameters, the effective two-photon cross section can be as large as 1010 GM,orders of magnitude higher than for nonresonant excitation. The biexciton emission can be differentiated from that of the singly excited state by utilizing its different transient dynamics. Alternate methods for discrimination are also discussed. This system is ideal for performing three-dimensional microscopy using low excitation power. Moreover, it enables to perform multiphoton imaging even with near-infrared emitting quantum dots, which are highly compatible with imaging deep into a scattering tissue. The depth resolution of our microscope is shown to be equivalent to a standard two-photon microscope. The system also shows slow saturation due to the contribution of higher (triply and above) excited states to the emitted signal.

Multiphoton excitation by temporally focused pulses can be combined with spatial Fourier-transform pulse shaping techniques to enhance spatial control of the excitation volume. Here we propose and demonstrate an optical system for the generation of such spatiotemporally engineered light pulses using a combination of spatial control by a two-dimensional reconfigurable light modulator, with a dispersive optical setup for temporal focusing. We show that although the properties of a holographic beam significantly differ from those of plane-wave illumination used in previous temporal focusing realizations, this leads only to a slightly reduced axial resolution. We show that the system can provide scanning-less, arbitrarily shaped, depth resolved excitation patterns that offer new perspectives for multiphoton photoactivation and optical lithography applications.

Optical sectioning is performed by collecting the fluorescent emission of two-exciton states in colloidal quantum dots. The two-exciton state is created by two consecutive resonant absorption events, thus requiring unprecedented low excitation energy and peak powers as low as 10⁶ W/cm². The depth resolution is shown to be equivalent to that of standard multiphoton microscopy, and it was found to deteriorate only slowly as saturation of the two-exciton state is approached, owing to signal contribution from higher excitonic states.

Carrier (exciton) multiplication in colloidal InAs/CdSe/ZnSe core-shell quantum dots (QDs) is investigated using terahertz time-domain spectroscopy, time-resolved transient absorption, and quasi-continuous wave excitation spectroscopy. For excitation by high-energy photons (∼2.7 times the band gap energy), highly efficient carrier multiplication (CM) results in the appearance of multi-excitons, amounting to ∼ 1.6 excitons per absorbed photon. Multi-exciton recombination occurs within tens of picoseconds via Auger-type processes. Photodoping (i.e., photoinjection of an exciton) of the QDs prior to excitation results in a reduction of the CM efficiency to ~1.3. This exciton-induced reduction of CM efficiency can be explained by the twofold degeneracy of the lowest conduction band energy level. We discuss the implications of our findings for the potential application of InAs QDs as light absorbers in solar cells.

The effect of a self-assembled organized organic monolayer on the two-photon photoemission from semiconductor substrates was investigated. It has been found that the monolayer affects the relative yield of photoelectrons emitted by p -polarized versus s -polarized light. In addition, the monolayer affects the angular distribution of the ejected electrons. The effect on the photoelectron yield is attributed to the monolayer "smoothing" the electronic potential on the surface by eliminating surface states and dangling bonds. The effect on the angular distribution is attributed to a post-ejection interaction between the photoelectrons and the adsorbed molecules.

The transition probability of a two-photon absorption (TPA) process in atomic Cesium, excited by phase-controlled temporally focused ultrashort pulses is shown to be spatially modulated in a controlled manner. In particular, we demonstrate the generation of a dark nonlinear focus. By controlling the excitation pulse shape along the propagation coordinate we create a region in space where the TPA rate vanishes which is flanked by bright regions.

The properties of harmonic generation with temporally focused ultrashort pulses are explored both theoretically and experimentally. Analyzing the phase-matching conditions for harmonic generation we find a correspondence between temporal focusing and spatial focusing along one dimension. In particular, temporally focused pulses experience a π phase shift in passing through the temporal focus, similar to the Guoy phase shift experienced by spatially focused beams. This correspondence is confirmed by measurements of third-harmonic generation induced by temporally focused pulses.

Using a single shaped femtosecond pulse, a molecular wavepacket is both tailored and monitored. Several toluene vibrational levels are excited in a controlled manner, both in amplitude and phase, through a quantum coherently controlled non-resonant Raman process. The entire coherent anti-Stokes Raman spectroscopy (CARS) process, that includes excitation and probing of the Raman-induced wavepacket, is enabled by polarization and phase shaping. We achieve a wavepacket detection sensitive to the modes relative phase and further extend the capabilities of the single-pulse CARS technique.

The ability to perform optical sectioning is one of the great advantages of laser-scanning microscopy. This introduces, however, a number of difficulties due to the scanning process, such as lower frame rates due to the serial acquisition process. Here we show that by introducing spatiotemporal pulse shaping techniques to multiphoton microscopy it is possible to obtain full-frame depth resolved imaging completely without scanning. Our method relies on temporal focusing of the illumination pulse. The pulsed excitation field is compressed as it propagates through the sample, reaching its shortest duration at the focal plane, before stretching again beyond it. This method is applied to obtain depth-resolved two-photon excitation fluorescence (TPEF) images of drosophila egg-chambers with nearly 10⁵ effective pixels using a standard Ti:Sapphire laser oscillator.

All-optical processing of the entire vibrational spectrum was investigated by using a more complex and carefully designed probe pulse. The probe pulse was constructed containing contributions from several narrow spectral bands with controllable intensities and phases. Strong interference effcts were observed in the coherent anti-Stokes Raman spectroscopy (CARS) which resulted from the presence of several spectrally separated probe frequencies. A scheme for nonlinear spectroscopy was also suggested, where the information from the entire spectrum could be collected into a single coherent entity through coherent control of the nonlinear process.

We demonstrate a new scanning femtosecond pulse-shaping technique that allows pulse shapes to be modulated at kilohertz rates. This technique is particularly useful for lock-in measurements in which the signal is synchronized with the alternating pulse shapes. The pulse-shape lock-in technique is demonstrated in resonant coherent anti-Stokes Raman scattering, where it is shown to significantly improve the ratio of the resonant signal to both the nonresonant background and to noise.

The three-dimensional (3D) turbulent mixing zone (TMZ) evolution under Rayleigh-Taylor and Richtmyer-Meshkov conditions was studied using two approaches. First, an extensive numerical study was made, investigating the growth of a random 3D perturbation in a wide range of density ratios. Following that, a new 3D statistical model was developed, similar to the previously developed two-dimensional (2D) statistical model, assuming binary interactions between bubbles that are growing at a 3D asymptotic velocity. Confirmation of the theoretical model was gained by detailed comparison of the bubble size distribution to the numerical simulations, enabled by a new analysis scheme that was applied to the 3D simulations. In addition, the results for the growth rate of the 3D bubble front obtained from the theoretical model show very good agreement with both the experimental and the 3D simulation results. A simple 3D drag-buoyancy model is also presented and compared with the results of the simulations and the experiments with good agreement. Its extension to the spike-front evolution, made by assuming the spikes' motion is governed by the single-mode evolution determined by the dominant bubbles, is in good agreement with the experiments and the 3D simulations. The good agreement between the 3D theoretical models, the 3D numerical simulations, and the experimental results, together with the clear differences between the 2D and the 3D results, suggest that the discrepancies between the experiments and the previously developed models are due to geometrical effects.

The late-time growth rate of the Richtmyer-Meshkov instability was experimentally studied at different Atwood numbers with two-dimensional (2D) and three-dimensional (3D) single-mode initial perturbations. The results of these experiments were found to be in good agreement with the results of the theoretical model and numerical simulations. In another set of experiments a bubble-competition phenomenon, which was observed in previous work for 2D initial perturbation (Sadot et al., 1998), was shown to exist also when the initial perturbation is of a 3D nature.

Phase-and-polarization coherent control is applied to control the nonlinear response of a quantum system. We use it to obtain high-resolution background-free single-pulse coherent anti-Stokes Raman spectra. The ability to control both the spectral phase and the spectral polarization enables measurement of a specific off-diagonal susceptibility tensor element while exploiting the different spectral response of the resonant Raman signal and the nonresonant background to achieve maximal background suppression.

We demonstrate third-harmonic microscopy of thin biological objects using a Ti:sapphire laser source. A very simple modification to the collection and detection systems of the microscope allows for the detection of the third-harmonic signal near 270 nm. We show that, using a Ti:sapphire laser, we can combine third-harmonic imaging with two-photon excitation fluorescence simultaneously. Compared to other possible laser sources for third-harmonic microscopy, the Ti:sapphire laser provides better optical resolution, better power availability, and is less absorbed in water. We find that the Ti:sapphire laser is the most suitable laser source for third-harmonic microscopy for thin biological specimens.

The coherent transient enhancement of optically induced resonant transitions was discussed. Using pulse shaping techniques, the total transient population was enhanced by inducing constructive interference, and for 100 fs pulses, an enhancement by a factor of about 2.5 was demonstrated. The results showed that the population transient peak remains nearly constant, even when the absorption coefficient was increased by over three order of magnitude.

Using a statistical mechanics bubble competition model, Alon et al. (1994,1995) have shown that the two-dimensional Rayleigh-Taylor (RT) mixing zone bubble and spike fronts evolves as h=α_B/S·A·g·t² with α_B∼0.05 and α_S∼α_S· (1+A). The Richtmyer-Meshkov (RM) mixing zone fronts have been found to evolve as h=a₀·t^θ with different θ's for bubble and spikes. The model predictions were θ_B∼0.4 and θ_S∼θ_B at low A's and rises to 1.0 for A close to 1. Full 2D numerical simulations confirmed these scaling laws. Recent experimental results (Dimonte, 1999,2000) have indicated similar scaling laws of the mixing zone evolution, but there were some discrepancies in the values of the scaling parameters, mainly in the value of θ_B and the similarity parameter, h/〈λ〉. It will be shown, based on full 3D numerical simulations, a Layzer type model and a 3D statistical-mechanics model that these discrepancies are mainly the effect of dimensionality. Accounting for the 3D nature of the problem results in scaling parameters that are very similar to the experimental values. The 3D single mode evolution, used in this model, was confirmed by shock tube experiments.

A statistical model predicting the evolution of turbulent mixing zone fronts was developed recently by Alon et al. It suggests that the three physical elements that govern the Rayleigh-Taylor and Richtmyer-Meshkov mixing zone evolution are the single-bubble evolution, the single-spike evolution, and the interaction between neighboring bubbles. In this paper we present an experimental investigation of these three elements in the Richtmyer-Meshkov case. The experiments were performed in a double-diaphragm shock tube. The interface evolution was studied both before and after the arrival of a secondary reflected shock. Experimental results for the single-bubble and two-bubble cases show distinct bubble and spike evolution. The results of the bubble competition, which determines the front evolution, were found to be in good agreement with both full numerical simulations and a simple potential flow model. These results strengthen the assumptions on which the statistical model is based.

A theoretical model for the ablatively driven RayleighTaylor (RT) instability single-mode and multimode mixing fronts is presented. The effect of ablation is approximately included in a Layzer-type potential flow model, yielding the description of both the single-mode evolution and the two-bubble nonlinear competition. The reduction factor of the linear growth rate due to ablative stabilization obtained by the model is similar to the Takabe formula. The single-bubble terminal velocity is found to be similarly reduced by ablation, in good agreement with numerical simulations. Two-bubble competition is calculated, and a statistical mechanics model for multimode fronts is presented. The asymptotic ablation correction to the classical RT [formula omitted] mixing zone growth law is derived. The effect of ablative stabilization on the allowed in-flight aspect ratio of inertial confinement fusion pellets is estimated using the results of the statistical mechanics model.