Publications

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.

Impulsive stimulated Raman scattering (ISRS) using a single short femtosecond pump pulse to excite molecular vibrations offers an elegant pump-probe approach to perform vibrational imaging below 200cm-1. One shortcoming of ISRS is its inability to offer vibrational selectivity as all the vibrational bonds whose frequencies lie within the short pump-pulse bandwidth are excited. To date, several coherent control techniques have been explored to address this issue and selectively excite a specific molecular vibration by shaping the pump pulse. There has not been any systematic work that reports an analogous shaping of the probe pulse to implement preferential detection. In this work, we focus on vibrational imaging and report vibrational selective detection by shaping the probe pulse in time. We demonstrate numerically and experimentally two pulse-shaping strategies with one functioning as a vibrational notch filter and the other functioning as a vibrational low-pass filter. This enables fast (25μs/pixel) and selective hyperspectral imaging in the low-frequency regime (

Coupled colloidal quantum dot molecules (CQDMs) are an emerging class of nanomaterials, manifesting two coupled emission centers and thus introducing additional degrees of freedom for designing quantum-dot-based technologies. The properties of multiply excited states in these CQDMs are crucial to their performance as quantum light emitters, but they cannot be fully resolved by existing spectroscopic techniques. Here we study the characteristics of biexcitonic species, which represent a rich landscape of different configurations essentially categorized as either segregated or localized biexciton states. To this end, we introduce an extension of Heralded Spectroscopy to resolve the different biexciton species in the prototypical CdSe/CdS CQDM system. By comparing CQDMs with single quantum dots and with nonfused quantum dot pairs, we uncover the coexistence and interplay of two distinct biexciton species: A fast-decaying, strongly interacting biexciton species, analogous to biexcitons in single quantum dots, and a long-lived, weakly interacting species corresponding to two nearly independent excitons. The two biexciton types are consistent with numerical simulations, assigning the strongly interacting species to two excitons localized at one side of the quantum dot molecule and the weakly interacting species to excitons segregated to the two quantum dot molecule sides. This deeper understanding of multiply excited states in coupled quantum dot molecules can support the rational design of tunable single- or multiple-photon quantum emitters.

Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.

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.

We revisit low frequency coherent Raman spectroscopy (LF-CRS) and present a unified theoretical background that provides consistent physical pictures of LF-CRS signal generation. Our general framework allows to compute the signal to noise ratio in the multitude of possible LF-CRS, and more generally CRS, experimental implementations both in the spectral and time domain.

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.

Recent studies of optical reflectors as part of the vision apparatus in the eyes of decapod crustaceans revealed assemblies of nanoscale spherulites - spherical core-shell nanoparticles with radial birefringence. Simulations performed on the system highlighted the advantages of optical anisotropy in enhancing the functionality of these structures. So far, calculations of the nanoparticle optical properties have relied on refractive indices obtained using ab-initio calculations. Here we describe a direct measurement of the tangential refractive index of the spherulites, which corresponds to the in-plane refractive index of crystalline isoxanthopterin nanoplatelets. We utilize measurements of scattering spectra of individual spherulites and determine the refractive index by analyzing the spectral signatures of scattering resonances. Our measurements yield a median tangential refractive index of 1.88, which is in reasonable agreement with theoretical predictions. Furthermore, our results indicate that the optical properties of small spherulite assemblies are largely determined by the tangential index.

Correlations between excitons, that is, electron-hole pairs, have a great impact on the optoelectronic properties of semiconductor quantum dots and thus are relevant for applications such as lasers and photovoltaics. Upon multiphoton excitation, these correlations lead to the formation of multiexciton states. It is challenging to observe these states spectroscopically, especially higher multiexciton states, because of their short lifetimes and nonradiative decay. Moreover, solvent contributions in experiments with coherent signal detection may complicate the analysis. Here we employ multiple-quantum two-dimensional (2D) fluorescence spectroscopy on colloidal CdSe1-xS x /ZnS alloyed core/shell quantum dots. We selectively map the electronic structure of multiexcitons and their correlations by using two- and three-quantum 2D spectroscopy, conducted in a simultaneous measurement. Our experiments reveal the characteristics of biexcitons and triexcitons such as transition dipole moments, binding energies, and correlated transition energy fluctuations. We determine the binding energies of the first six biexciton states by simulating the two-quantum 2D spectrum. By analyzing the line shape of the three-quantum 2D spectrum, we find strong correlations between biexciton and triexciton states. Our method contributes to a more comprehensive understanding of multiexcitonic species in quantum dots and other semiconductor nanostructures.

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 demonstrate the formation of uniform and oriented metal-organic frameworks using a combination of anion-effects and surface-chemistry. Subtle but significant morphological changes result from the nature of the coordinative counter-anion of the following metal salts: NiX2 with (X = Br-, Cl-, NO3-, and OAc-). Crystals could be obtained in solution or by template surface growth. The latter resulting in truncated crystals that resemble a half-structure of the solution-grown ones. The oriented surface-bound metal-organic frameworks (sMOFs) are obtained via a one-step solvothermal approach, rather than in a layer-by-layer approach. The MOFs are grown on Si/SiOx substrates modified with an organic monolayer or on glass substrates covered with a transparent conductive oxide (TCO). Regardless of the different morphologies, the crystallographic packing is nearly identical and is not affected by the type of anion, nor by solution versus the surface chemistry. A propeller-type arrangement of the non-chiral ligands around the metal center affords a chiral structure with two geometrically different helical channels in a 2:1 ratio with the same handedness. To demonstrate the accessibility and porosity of the macroscopically-oriented channels, a chromophore (resorufin sodium salt) was successfully embedded into the channels of the crystals by diffusion from solution, resulting in fluorescent crystals. These "colored" crystals displayed polarized emission (red) with a high polarization ratio because of the alignment of these dyes imposed by the crystallographic structure. A second-harmonic generation (SHG) study revealed Kleinman-symmetry forbidden non-linear optical properties. These surface-bound and oriented SHG-active MOFs have the potential for use as single non-linear optical (NLO) devices.

The induction of homogeneous and oriented ice nucleation has to date not been achieved. Here, we report induced nucleation of ice from millimeter sized supercooled water drops illuminated by ns-optical laser pulses well below the ionization threshold making use of particular laser beam configurations and polarizations. Employing a 100 ps synchrotron x-ray pulse 100 ns after each laser pulse, an unambiguous correlation was observed between the directions and the symmetry of the laser fields and that of the H-bonding arrays of the induced ice crystals. Moreover, an analysis of the x-ray diffraction data indicates that, in the main, the induced nucleation of ice is homogeneous at temperatures well above the observed and predicted values for supercooled water.

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

The evolution of experimental superresolution microscopy has been accompanied by the development of advanced computational imaging capabilities. Recently introduced, quantum image scanning microscopy (Q-ISM) has successfully harnessed quantum correlations of light to establish an improved viable imaging modality that builds upon the preceding image scanning microscopy (ISM) superresolution method. While offering improved resolution, at present the inherently weak signal demands exhaustively long acquisition periods. Here we exploit the fact that the correlation measurement in Q-ISM is complementary to the standard ISM data, acquired simultaneously, and demonstrate joint sparse recovery from Q-ISM and ISM images. Reconstructions from images of fluorescent quantum dots are validated through correlative electron microscope measurements, and exhibit superior resolution enhancement as compared to Q-ISM images. In addition, the algorithmic fusion facilitates a drastic reduction in the requisite measurement duration, since low signal-to-noise-ratio Q-ISM measurements suffice for augmenting ISM images. Finally, we obtain enhanced superresolved reconstructions from short scans of a biological sample labeled with quantum dots, demonstrating the potential of our method for quantum imaging in life science microscopy.

Colloidal PbS quantum dots (QDs) have been successfully employed as additives in halide perovskite solar cells (PSCs) acting as nucleation centers in the perovskite crystallization process. For this strategy, the surface functionalization of the QDs, controlled via the use of different capping ligands, is likely of key importance. In this work, we examine the influence of the PbS QD capping on the photovoltaic performance of methylammonium lead iodide PSCs. We test PSCs fabricated with PbS QD additives with different capping ligands including methylammonium lead iodide (MAPI), cesium lead iodide (CsPI) and 4-aminobenzoic acid (ABA). Both the presence of PbS QDs and the specific capping used have a significant effect on the properties of the deposited perovskite layer, which affects, in turn, the photovoltaic performance. For all capping ligands used, the inclusion of PbS QDs leads to the formation of perovskite films with larger grain size, improving, in addition, the crystalline preferential orientation and the crystallinity. Yet, differences between the capping agents were observed. The use of QDs with ABA capping had a higher impact on the morphological properties while the employment of the CsPI ligand was more effective in improving the optical properties of the perovskite films. Taking advantage of the improved properties, PSCs based on the perovskite films with embedded PbS QDs exhibit an enhanced photovoltaic performance, showing the highest increase with ABA capping. Moreover, bulk recombination via trap states is reduced when the ABA ligand is used for capping of the PbS QD additives in the perovskite film. We demonstrate how surface chemistry engineering of PbS QD additives in solution-processed perovskite films opens a new approach towards the design of high quality materials, paving the way to improved optoelectronic properties and more efficient photovoltaic devices.

We demonstrate focusing and imaging through a scattering medium without access to the fluorescent object by using wavefront shaping. Our concept is based on utilizing the spatial fluorescence contrast which naturally exists in the hidden target object. By scanning the angle of incidence of the illuminating laser beam and maximizing the variation of the detected fluorescence signal from the object, as measured by a bucket detector at the front of the scattering medium, we are able to generate a tightly focused excitation spot. Thereafter, an image is obtained by scanning the focus over the object within the memory effect range. The requirements for applicability of the method and the comparison with speckle-correlation based focusing methods are discussed. (C) 2019 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

Quasi-two-dimensional (2D) CdSe nanoplatelets (NPLs) are distinguished by their unique optical properties in comparison to classical semiconductor nano crystals, such as extremely narrow emission line widths, reduced Auger recombination, and relatively high absorption cross sections. Inherent to their anisotropic 2D structure, however, is the loss of continuous tunability of their photoluminescence (PL) properties due to stepwise growth. On top of that, limited experimental availability of NPLs of different thicknesses and ultimately the bulk band gap of CdSe constrain the achievable PL wavelengths. Here, we report on the doping of CdSe NPLs with mercury, which gives rise to additional PL in the red region of the visible spectrum and in the near-infrared region. We employ a seeded-growth method with injection solutions containing cadmium, selenium, and mercury. The resulting NPLs retain their anisotropic structure, are uniform in size and shape, and present significantly altered spectroscopic characteristics due to the existence of additional energetic states. We conclude that doping takes place by employing elemental analysis in combination with PL excitation spectroscopy, X-ray photoelectron spectroscopy, and single particle fluorescence spectroscopy, confirming single emitters being responsible for multiple distinct emission signals.

Herein, an in situ solution growth method to prepare preferentially assembled and well-distributed alpha-CsPbI3 nanocrystals (NCs)/reduced graphene oxide (rGO) heterostructures is presented. Owing to its excellent thermal conductivity, carrier mobility, hydrophobic nature and passivation effect, rGO could reduce the number of ligands on the surface of alpha-CsPbI3 NCs, provide protection against air and moisture, and enhance the carrier separation and carrier transport properties of nanocrystals. The homogeneous growth of nanocrystals and their distribution along the surface of rGO also improved the stability and carrier transport quality compared to that of alpha-CsPbI3 NCs. Particularly, alpha-CsPbI3 NCs/rGO heterostructures show a suitable band gap of B1.74 eV, an acceptable photoluminescence (PL) intensity and a PL quantum yield (PLQY) of similar to 10.7%. The decay lifetime of these heterostructures was maintained at similar to 43.5 ns and PLQY was maintained at similar to 68% of the initial value when stored in ambient conditions for similar to 4 weeks. Finally, we demonstrate the inkjet printing of these heterostructures, manifesting their favorable dispersibility in organic solvents, and showing their utility as optically active materials for applications in optoelectronic devices.

The principles of quantum optics have yielded a plethora of ideas to surpass the classical limitations of sensitivity and resolution in optical microscopy. While some ideas have been applied in proof-of-principle experiments, imaging a biological sample has remained challenging, mainly due to the inherently weak signal measured and the fragility of quantum states of light. In principle, however, these quantum protocols can add new information without sacrificing the classical information and can therefore enhance the capabilities of existing super-resolution techniques. Image scanning microscopy, a recent addition to the family of super-resolution methods, generates a robust resolution enhancement without reducing the signal level. Here, we introduce quantum image scanning microscopy: combining image scanning microscopy with the measurement of quantum photon correlation allows increasing the resolution of image scanning microscopy up to twofold, four times beyond the diffraction limit. We introduce the Q-ISM principle and obtain super-resolved optical images of a biological sample stained with fluores-cent quantum dots using photon antibunching, a quantum effect, as a resolution-enhancing contrast mechanism.

Vibrational spectroscopic imaging is useful and important in biological and medical studies. Yet, vibrational imaging in the terahertz region (

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

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.

We present a new method for the measurement of the stimulated Raman spectrum based on time-dependent spatial modulation of a laser beam as it passes through a Raman active medium. This effect is similar to the instantaneous Kerr lensing and Kerr deflection yet involves resonant vibrations which result in a time-dependent refractive index change. We use sub-nanojoule pulses together with a sensitive pump-probe measurement apparatus to excite and detect the fine (10(-5)-10(-4)) temporal and spatial variations in intensity resulting from the Raman-induced Kerr effect. We demonstrate the effect by changing the spatial overlap between the pump and probe at the sample and measuring the time-dependent deformation of the probe beam's cross section. This method is particularly useful for detection of low-frequency Raman lines, as we demonstrate by measuring the Raman spectrum of neat liquids in a cuvette.

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.

Supercontinuum generation using photonic crystal fibers is a useful technique to generate light spanning a broad wavelength range, using femtosecond laser pulses. For some applications, one may desire higher power density at specific wavelengths. Increasing the pump power results primarily in further broadening of the output spectrum and is not particularly useful for this purpose. In this paper we demonstrate that by applying a periodic spectral phase modulation to the input pulse using a pulse shaper, the spectral energy density of the output supercontinuum can be enhanced by nearly an order of magnitude at specific wavelengths, which are tunable. (C) 2018 Optical Society of America under the terms of the OSA Open Access Publishing Agreement

Stimulated Raman scattering (SRS) has recently become useful for chemically selective bioimaging. It is usually measured via modulation transfer from the pump beam to the Stokes beam. Impulsive stimulated Raman spectroscopy, on the other hand, relies on the spectral shift of ultrashort pulses as they propagate in a Raman active sample. This method was considered impractical with low energy pulses since the observed shifts are very small compared to the excitation pulse bandwidth, spanning many terahertz. Here we present a new apparatus, using tools borrowed from the field of precision measurement, for the detection of low-frequency Raman lines via stimulated-Raman-scattering-induced spectral shifts. This method does not require any spectral filtration and is therefore an excellent candidate to resolve low-lying Raman lines (

The combination of perovskite solar cells and quantum dot solar cells has significant potential due to the complementary nature of the two constituent materials. In this study, solar cells (SCs) with a hybrid CH3NH3PbI3/SnS quantum dots (QDs) absorber layer are fabricated by a facile and universal in situ crystallization method, enabling easy embedding of the QDs in perovskite layer. Compared with SCs based on CH3NH3PbI3, SCs using CH3NH3PbI3/SnS QDs hybrid films as absorber achieves a 25% enhancement in efficiency, giving rise to an efficiency of 16.8%. The performance improvement can be attributed to the improved crystallinity of the absorber, enhanced photo-induced carriers' separation and transport within the absorber layer, and improved incident light utilization. The generality of the methods used in this work paves a universal pathway for preparing other perovskite/QDs hybrid materials and the synthesis of entire nontoxic perovskite/QDs hybrid structure.

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 bather 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 growth of horizontal nanowires (NWs) guided by epitaxial and graphoepitaxial relations with the substrate is becoming increasingly attractive owing to the possibility of controlling their position, direction, and crystallographic orientation. In guided NWs, as opposed to the extensively characterized vertically grown NWs, there is an increasing need for understanding the relation between structure and properties, specifically the role of the epitaxial relation with the substrate. Furthermore, the uniformity of crystallographic orientation along guided NWs and over the substrate has yet to be checked. Here we perform highly sensitive second harmonic generation (SHG) polarimetry of polar and nonpolar guided ZnO NWs grown on R-plane and M-plane sapphire. We optically map large areas on the substrate in a nondestructive way and find that the crystallographic orientations of the guided NWs are highly selective and specific for each growth direction with respect to the substrate lattice. In addition, we perform SHG polarimetry along individual NWs and find that the crystallographic orientation is preserved along the NW in both polar and nonpolar NWs. While polar NWs show highly uniform SHG along their axis, nonpolar NWs show a significant change in the local nonlinear susceptibility along a few micrometers, reflected in a reduction of 40% in the ratio of the SHG along different crystal axes. We suggest that these differences may be related to strain accumulation along the nonpolar wires. We find SHG polarimetry to be a powerful tool to study both selectivity and uniformity of crystallographic orientations of guided NWs with different epitaxial relations.

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 mu H-0 = 0.3 T with individual laser pulses of 40 mW power and 50 ns duration with a laser spot size of 3 mu m (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/N719QD/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 mm 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. (C) 2016 Elsevier Ltd. All rights reserved.

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. (C) 2014 Optical Society of America

The optical and electronic properties of suspensions of inorganic fullerene-like nanopartides 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 nanopartide size, shape, and surface charge, as well as solvent refractive index, suggests that this transition arises from a plasmon resonance.

The formation of donor/acceptor junctions in hybrid nanomaterials is predicted to enhance photocatalytic activity as compared to single-component semiconductor systems. Specifically, nanomaterials containing a junction of n-type cadmium sulfide (CdS) and p-type copper sulfide (Cu2S) formed via cation exchange have been proposed as potential photocatalysts for reactions such as water splitting. Herein, we study the elemental distribution of Cu within these nanostructures using analytical transmission electron microscopy techniques. The resulting effects of this elemental distribution on photocatalytic activity and charge dynamics were further studied using a model photoreduction reaction and transient absorption spectroscopy. We find that copper diffusion in the hybrid nanostructure quenches the exciton lifetime and results in low photocatalytic activity; however, this effect can be partially mitigated via selective extraction. These results provide a deeper understanding of the physical processes within these hybrid nanostructures and will lead to more rational design of photocatalyst materials.

An inorganic layer and dye molecules have synergistically suppressed the recombination in a quantum dot sensitized solar cell (QDSSC), by the design of a structure featured TiO2-CdS-ZnS-N3 (N3: RuL2(NCS) 2 (L = 2,20-bipyridyl-4,40-dicarboxylic acid)) hybrid photoanode. When fabricated into solar cells, a cobalt complex-based electrolyte rather than an iodine-based one was employed to obtain an impressive photostability for the devices. Raman and Photoluminescence (PL) measurements revealed that not only the CdS QDs were passivated by both the inorganic layer of ZnS and dye molecule of N3, but also N3 served as an efficient hole scavenger for the CdS QDs due to a type-II energetic alignment between the two sensitizers. This role of N3 as an intermediary in hole extraction from CdS QDs to the electrolyte was further proven by the significant photovoltaic performance improvement of the CdS sensitized solar cell after ZnS deposition and N3 co-sensitization. The overall efficiency of the solar cell incorporated with TiO2-CdS-ZnS-N3 film exceeded the sum of the single CdS QDs and N3 dye sensitized solar cells. This enhancement is ascribed mainly to the synergistic recombination suppression by the inorganic layer ZnS and N3 co-sensitization, leading to inhibited recombination and increased electron lifetime, as illustrated by the electrochemical impedance spectroscopy (EIS) analysis.

The use of wavefront shaping to generate extended optical excitation patterns which are confined to a predetermined volume has become commonplace on various microscopy applications. For multiphoton excitation, three-dimensional confinement can be achieved by combining the technique of temporal focusing of ultra-short pulses with different approaches for lateral light shaping, including computer generated holography or generalized phase contrast. Here we present a theoretical and experimental study on the effect of scattering on the propagation of holographic beams with and without temporal focusing. Results from fixed and acute cortical slices show that temporally focused spatial patterns are extremely robust against the effects of scattering and this permits their three-dimensionally confined excitation for depths more than 500 mu m. Finally we prove the efficiency of using temporally focused holographic beams in two-photon stimulation of neurons expressing the red-shifted optogenetic channel C1V1. (C) 2013 Optical Society of America

Type-II heterostructure CdTe/CdSe core/shell nanocrystals (quantum dots, QDs) are explored as sensitizers in a QD-sensitized photoelectrochemical solar cell. These QDs comprise a hole-localizing core and an electron-localizing shell. Among their advantages is the significant red shift of the absorption edge of the heterostructured QD relative to its two constituents due to spatially indirect absorption leading to improved absorption characteristics, intraparticle exciton dissociation upon photoexcitation, and a relatively small content of the less abundant tellurium element. Upon incorporation in a sensitized solar cell utilizing a porous TiO2 and a polysulfide electrolyte, these QDs exhibited efficient charge separation and high internal quantum efficiency despite hole localization in the CdTe core. Monochromatic incident photon-to-current conversion efficiency (IPCE) measurement shows a spectrally broad photoresponse spanning the whole visible spectrum and reaching up to similar to 900 nm.

A high photovoltage is an essential ingredient for the construction of a high-efficiency quantum dot sensitized solar cell (QDSSC). In this paper we present a novel configuration of QDSSC which incorporates the photoinduced dipole (PID) phenomenon for improved open circuit voltage (V-oc). This configuration, unlike previously studied ones with molecular dipoles, is based on a dipole moment which is created only under illumination and is a result of exciton dissociation. The generation of photodipoles was achieved by the creation of long-lived trapped holes inside a core of type-II ZnSe/CdS colloidal core/shell QDs, which are placed on top of the standard CdS QD sensitizer layer. Upon photoexcitation, the created photodipole negatively shifts the TiO2 energy bands, resulting in a photovoltage that is higher by similar to 100 mV compared to the standard cell, without type-II QDs. The extra photovoltage gained diminishes the excessive overpotential losses caused by the energetic difference between the CdS sensitizer layer and the TiO2, without harming the charge injection processes. Moreover, we show that the extent of the additional photovoltage is controlled by the illumination intensity. This work provides new understanding regarding the operation mechanisms of photoelectrochemical cells, while presenting a new strategy for constructing a high-voltage QDSSCs. In addition, the PID effect has the potential to be implemented in other promising photovoltaic technologies.

We demonstrate the existence of the spectral phase shift a pulse experiences when it is subjected to spectral focusing. This pi/2 phase shift is the spectral analog of the Gouy phase shift a 2D beam experiences when it crosses its focal plane. This spectral Gouy phase shift is measured using spectral interference between a reference pulse and a negatively chirped parabolic pulse experiencing spectral focusing in a nonlinear photonic crystal fiber. To avoid inherent phase instability in the measurement, both reference and parabolic pulses are generated with a 4-f pulse shaper and copropagate in the same fiber. We measure a spectral phase shift of pi/2, reaffirming its generality as a consequence of wave confinement in the spatial, temporal and spectral domains.

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 et 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 TiO2/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 TiO2 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 QD's 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 strong QD-electrode interaction. That interaction is the origin for the highly efficient QD to 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

Spectral compression by self-phase modulation of amplitude-and phase-shaped pulses is demonstrated as superior compared to pulses that have only been phase shaped. We synthesize linearly negatively chirped parabolic pulses, which we send through a nonlinear photonic crystal fiber, in which self-phase modulation compresses the spectrum of the pulses to within 20% of the Fourier transform limit. (C) 2011 Optical Society of America

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 similar to 1 photon per pulse, a regime in which nonlinear techniques are impractical, at a temporal resolution of similar to 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.

A new design of dye-sensitized solar cells involves colloidal semiconductor quantum dots that serve as antennas, funneling absorbed light to the charge separating dye molecules via nonradiative energy transfer. The colloidal quantum dot donors are incorporated into the solid titania electrode resulting in high energy transfer efficiency and significant improvement of the cell stability. This design practically separates the processes of light absorption and charge carrier injection, enabling us to optimize each of these separately. Incident photon-to-current efficiency measurements show a full coverage of the visible spectrum despite the use of a red absorbing dye, limited only by the efficiency of charge injection from the dye to the titania electrode. Time resolved luminescence measurements clearly relate this to Forster resonance energy transfer from the quantum dots to the dye. The presented design introduces new degrees of freedom in the utilization of quantum dot sensitizers for photovoltaic cells. In particular, it opens the way toward the utilization of new materials whose band offsets do not allow direct charge injection.

Surface plasmon resonance exhibited by noble metal nanoparticles makes them attractive agents for advanced microscopic imaging applications. In this work we study third harmonic generation in gold nanorods under conditions of resonance of the laser frequency with the longitudinal plasmon mode. Large resonant enhancement and the symmetry properties of third harmonic generation allow for background-free, orientation sensitive optical imaging of individual nanoparticles.

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/AgNO(3) 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.

Multiple energy scales contribute to the radiative properties of colloidal quantum dots, including magnetic interactions, crystal field splitting, Pauli exclusion, and phonons. Identification of the exact physical mechanism which couples first to the dark ground state of colloidal quantum dots, inducing a significant reduction in the radiative lifetime at low temperatures, has thus been under significant debate. Here we present measurements of this phenomenon on a variety of materials as well as on colloidal heterostructures. These show unambiguously that the dominant mechanism is coupling of the ground state to a confined acoustic phonon, and that this mechanism is universal.

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. 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 10(5)W/cm(2)) are required to generate this nonlinear response. Depending on the quantum dot parameters, the effective two-photon cross section can be as large as 10(10) 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.

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.

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. (C) 2008 Optical Society of America

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 105 W/cm(2). 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. (C) 2008 Optical Society of America

We studied the optical gain characteristics of CdSe/ZnS core/shell colloidal quantum rods, investigated their temperature dependence, and compared the gain properties with quantum dots (QD). The gain was measured systematically for close-packed films of rods and dots under quasi-CW nanosecond optical pumping, using the variable stripe length method measuring the amplified spontaneous emission (ASE). Tunable ASE can be achieved by changing the rod diameter. Optical gain factors of up to 350 cm-1 at a temperature range of 10−120 K were measured for quantum rods. Above 120 K, the gain decreased sharply, but by increasing the pump power, ASE was easily achieved also at room temperature. The temperature dependence was assigned to the Auger heating process and phonon assisted thermal relaxation. QD of similar diameters as the rods showed much smaller gain values (∼50 cm-1) and a sharp decrease in gain at lowered temperatures (∼50 K), and ASE could not be detected at room temperature even at high pump powers. The significantly improved gain values in quantum rods as compared with dots were attributed to the slower Auger relaxation rates, the higher absorption cross-section, and the reduced self-absorption due to the larger Stokes shift. The temperature dependence of the threshold power for the quantum rods, used to characterize the thermal insensitivity of the system, showed two distinct temperature regions. In the low-temperature region, a very high T0 value of 3500 K was measured, as predicted for a low-dimensional quantum confined system.

Objectives: We present a novel way to create high-resolution three-dimensional images of tooth dentin by harmonic generation scanning laser microscopy. Methods: The images were taken using a pulsed infrared laser. Three-dimensional reconstruction enables the visualization of individual tubules and the collagen fibrils mesh around them with an optical resolution of similar to 1 mu m. Results: The images show micro-morphological details of the dentinal tubules as well as the collagen fibrils at a depth of up to about 200 mu m. The data show that while collagen fibrils are organized in planes perpendicular to the tubules, close to the dentin enamel junction they lie also along the long axis of the tubules. Conclusions: The unique 3D information opens the opportunity to study the collagen fibril arrangement in relation to the tubule orientation within the dentin matrix, and may be applied to study the. micro-morphology of normal versus altered dentin. (c) 2006 Elsevier Ltd. All rights reserved.

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. (c) 2006 Elsevier B.V. All rights reserved.

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 pi 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. (c) 2005 Optical Society of America

In most coherent control experiments with femtosecond pulses, the temporal shape of the pulses is maintained throughout the interaction region. Here we show how pulses can be controlled such that their shapes vary rapidly even when propagating very short distances of a few micrometers. This changing pulse shape has a significant effect on coherent nonlinear optical processes. Here we study third-harmonic generation induced by a coherently controlled excitation pulse whose temporal profile changes along the axial coordinate. We show how such manipulations can be used to improve the axial resolution in a multiphoton optical microscope. (c) 2005 Optical Society of America

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 10(5) effective pixels using a standard Ti: Sapphire laser oscillator. (C) 2005 Optical Society of America.

In spectroscopy, the fingerprint of a substance is usually comprised of a sequence of spectral lines with characteristic frequencies and strengths. Identification of substances often involves postprocessing, where the measured spectrum is compared with tabulated fingerprint spectra. Here we suggest a scheme for nonlinear spectroscopy, where, through coherent control of the nonlinear process, the information from the entire spectrum can be practically collected into a single coherent entity. We apply this for all-optical analysis of coherent Raman spectra and demonstrate enhanced detection and effective background suppression using coherent processing.

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. (C) 2004 Optical Society of America.

The three-dimensional (31)) 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.

Molecular vibrations have oscillation periods that reflect the molecular structure, and are hence being used as a spectroscopic fingerprint for detection and identification. At present, all nonlinear spectroscopy schemes use two or more laser beams to measure such vibrations(1). The availability of ultrashort (femtosecond) optical pulses with durations shorter than typical molecular vibration periods has enabled the coherent excitation of molecular vibrations using a single pulse(2). Here we perform single-pulse vibrational spectroscopy on several molecules in the liquid phase, where both the excitation and the readout processes are performed by the same pulse. The main difficulty with single-pulse spectroscopy is that all vibrational levels with energies within the pulse bandwidth are excited. We achieve high spectral resolution, nearly two orders of magnitude better than the pulse bandwidth, by using quantum coherent control techniques. By appropriately modulating the spectral phase of the pulse we are able to exploit the quantum interference between multiple paths to selectively populate a given vibrational level, and to probe this population using the same pulse. This scheme, using a single broadband laser source, is particularly attractive for nonlinear microscopy applications, as we demonstrate by constructing a coherent anti-Stokes Raman (CARS) microscope operating with a single laser beam.

Using femtosecond pulse-shaping techniques, we are able to control several useful parameters of coherent anti-Stokes Raman spectroscopy (CARS). By shaping both the pump and the Stokes pulses with an appropriate spectral phase function, we eliminated the nonresonant CARS background. In addition, we designed pulses which selectively excite one of two neighboring Raman levels, even when both are well within the excitation spectrum. High-resolution CARS spectra were recorded in spite of the broad femtosecond pulse spectrum.

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.