Nanosecond compressive fluorescence lifetime microscopy imaging via the RATS method with a direct reconstruction of lifetime maps.

The RAndom Temporal Signals (RATS) method has proven to be a useful and versatile method for measuring photoluminescence (PL) dynamics and fluorescence lifetime imaging (FLIM). Here, we present two fundamental development steps in the method. First, we demonstrate that by using random digital laser modulation in RATS, it is possible to implement the measurement of PL dynamics with temporal resolution in units of nanoseconds. Secondly, we propose an alternative approach to evaluating FLIM measurements based on a single-pixel camera experiment. In contrast to the standard evaluation, which requires a lengthy iterative reconstruction of PL maps for each timepoint, here we use a limited set of predetermined PL lifetimes and calculate the amplitude maps corresponding to each lifetime. The alternative approach significantly saves post-processing time and, in addition, in a system with noise present, it shows better stability in terms of the accuracy of the FLIM spectrogram. Besides simulations that confirmed the functionality of the extension, we implemented the new advancements into a microscope optical setup for mapping PL dynamics on the micrometer scale. The presented principles were also verified experimentally by mapping a LuAG:Ce crystal surface.

On-chip digital holographic interferometry for measuring wavefront deformation in transparent samples.

This paper describes on-chip digital holographic interferometry for measuring the wavefront deformation of transparent samples. The interferometer is based on a Mach-Zehnder arrangement with a waveguide in the reference arm, which allows for a compact on-chip arrangement. The method thus exploits the sensitivity of digital holographic interferometry and the advantages of the on-chip approach, which provides high spatial resolution over a large area, simplicity, and compactness of the system. The method's performance is demonstrated by measuring a model glass sample fabricated by depositing SiO2 layers of different thicknesses on a planar glass substrate and visualizing the domain structure in periodically poled lithium niobate. Finally, the results of the measurement made with the on-chip digital holographic interferometer were compared with those made with a conventional Mach-Zehnder type digital holographic interferometer with lens and with a commercial white light interferometer. The comparison of the obtained results indicates that the on-chip digital holographic interferometer provides accuracy comparable to conventional methods while offering the benefits of a large field of view and simplicity.

High-precision FoM measurement setup for Ti:sapphire crystals.

The figure of merit (FoM) of Ti:sapphire (Ti:Sa) crystals is a generally used means to evaluate the quality of the crystals. Despite the importance of Ti:Sa, the question of FoM measurement precision stayed out of focus, while the commercially available spectrometers provide unsatisfactory 3σ precision reaching ±60%. In this paper, we present a setup for a single-pass high-precision transmission measurement for three different wavelengths (532, 780, and 1560 nm) based on Nd:YAG and Er:YAG lasers. A synchronous detection via a double integrated sphere enabled us to achieve the transmission uncertainty of 0,01-0,03%. With the presented setup, we show that it is possible to determine the FoM values with 3σ precision of ±7,5%. Owing to the high FoM precision, we were able to trace spatial inhomogeneities of an unannealed Ti:Sa crystal produced by a commercial manufacturer Crytur. Our measurements demonstrate that the FoM values can be significantly affected by the crystal inhomogeneities and angular mismatch between the c axis of the Ti:Sa and polarization orientation.

Spatially encoded hyperspectral compressive microscope for ultrabroadband VIS/NIR hyperspectral imaging.

Hyperspectral imaging (HSI) has become a valuable tool in sample characterization in various scientific fields. While many approaches have been tested, specific applications and technology usually lead to only a narrow part of the spectrum being studied. We demonstrate the use of a broadband HSI setup based on compressed sensing capable of capturing data in visible (VIS), near-infrared (NIR), and short-wave infrared (SWIR) spectral regions. Using a tested design, we developed a dual configuration and tested its performance on a set of samples demonstrating spatial resolution and spectral reconstruction. Samples showing a potential use of the setup in optical defect detection are also tested. The setup showcases a dual single-pixel camera configuration capable of combining various detectors with a shared spatial modulation, further improving data efficiency and providing an affordable instrument from broadband spectral studies.

Compact lensless Fizeau holographic interferometry for imaging domain patterns in ferroelectric single crystals.

Domain patterns in ferroelectric single crystals are physical systems that are fascinating from a theoretical point of view and essential for many applications. A compact lensless method for imaging domain patterns in ferroelectric single crystals based on a digital holographic Fizeau interferometer has been developed. This approach provides a large field-of-view image while maintaining a high spatial resolution. Furthermore, the double-pass approach increases the sensitivity of the measurement. The performance of the lensless digital holographic Fizeau interferometer is demonstrated by imaging the domain pattern in periodically poled lithium niobate. To display the domain patterns in the crystal, we have used an electro-optic phenomenon, which, when an external uniform electric field is applied to the sample, produces a difference in refractive index values in domains with different polarization states of the crystal lattice. Finally, the constructed digital holographic Fizeau interferometer is used to measure the difference in the index of refraction in the antiparallel ferroelectric domains in the external electric field. The lateral resolution of the developed method for ferroelectric domain imaging is discussed.

Noise effect on 2D photoluminescence decay analysis using the RATS method in a single-pixel camera configuration.

Using a random temporal signal for sample excitation (RATS method) is a new, capable approach to measuring photoluminescence (PL) dynamics. The method can be used in single-point measurement (0D), but also it can be converted to PL decay imaging (2D) using a single-pixel camera configuration. In both cases, the reconstruction of the PL decay and PL snapshot is affected by ubiquitous noise. This article provides a detailed analysis of the noise effect on the RATS method and possible strategies for its suppression. We carried out an extensive set of simulations focusing on the effect of noise introduced through the random excitation signal and the corresponding PL waveform. We show that the PL signal noise level is critical for the method. Furthermore, we analyze the role of acquisition time, where we demonstrate the need for a non-periodic excitation signal. We show that it is beneficial to increase the acquisition time and that increasing the number of measurements in the single-pixel camera configuration has a minimal effect above a certain threshold. Finally, we study the effect of a regularization parameter used in the deconvolution step, and we observe that there is an optimum value set by the noise present in the PL dataset. Our results provide a guideline for optimization of the RATS measurement, but we also study effects generally occurring in PL decay measurements methods relying on the deconvolution step.

Versatile compressive microscope for hyperspectral transmission and fluorescence lifetime imaging.

Increasing demand for multimodal characterization and imaging of new materials entails the combination of various methods in a single microscopic setup. Hyperspectral imaging of transmission spectra or photoluminescence (PL) decay imaging count among the most used methods. Nevertheless, these methods require very different working conditions and instrumentation. Therefore, combining the methods into a single microscopic system is seldom implemented. Here we demonstrate a novel versatile microscope based on single-pixel imaging, where we use a simple optical configuration to measure the hyperspectral information, as well as fluorescence lifetime imaging (FLIM). The maps are inherently spatially matched and can be taken with spectral resolution limited by the resolution of the used spectrometer (3 nm) or temporal resolution set by PL decay measurement (120 ps). We verify the system's performance by its comparison to the standard FLIM and non-imaging transmission spectroscopy. Our approach enabled us to switch between a broad field-of-view and micrometer resolution without changing the optical configuration. At the same time, the used design opens the possibility to add a variety of other characterization methods. This article demonstrates a simple, affordable way of complex material studies with huge versatility for the imaging parameters.

Beating signals in CdSe quantum dots measured by low-temperature 2D spectroscopy.

Advances in ultrafast spectroscopy can provide access to dynamics involving nontrivial quantum correlations and their evolutions. In coherent 2D spectroscopy, the oscillatory time dependence of a signal is a signature of such quantum dynamics. Here, we study such beating signals in electronic coherent 2D spectroscopy of CdSe quantum dots (CdSe QDs) at 77 K. The beating signals are analyzed in terms of their positive and negative Fourier components. We conclude that the beatings originate from coherent LO-phonons of CdSe QDs. No evidence for the QD size dependence of the LO-phonon frequency was identified.

Influence of the delay line jitter on the SHG FROG reconstruction.

Frequency-resolved optical gating (FROG) counts among the most used methods to characterize complex femtosecond pulses. The multishot FROG experiment, studied in this work, relies on varying a delay between two replicas of the measured pulse, where the delay accuracy can suffer from delay line imperfections, setup instability, or minimization of the acquisition time. We present a detailed study on the effect of the delay line jitter on the pulse retrieval. We carried out simulations with the jitter values ranging from high-precision delay lines (100 nm) up to extremely unstable measurements (>1000 nm). For three sets of pulses, we quantified criteria assuring reliable reconstruction, using ptychographic algorithm, of a complex pulse based on the experimentally available FROG trace error. We observe that the effect of the jitter scales together with the spectral bandwidth. However, the pulse reconstruction is relatively robust against the jitter and, even for a severe distortion of the FROG trace (e.g., a jitter of 500 nm for broadband pulses), the main features of all pulses are retrieved with high fidelity. Our results provide guidance for the limitations based on the delay imperfections in the FROG experiment.

Calibration of the pixel crosstalk in spatial light modulators for 4f pulse shaping.

The targeted shaping of femtosecond pulses in 4f pulse shapers is complicated by, among other factors, the crosstalk between adjacent pixels of a spatial light modulator (SLM). Current methods for the crosstalk evaluation require setting up a different experiment, which is highly inconvenient. Here, we propose a simple procedure to extract the pixel crosstalk within the standard SLM calibration used in pulse shaping. The calibration is based on an analysis of the contrast of a periodic modulation in the spectra induced via SLM. We demonstrate the calibration procedure on a liquid-crystal-based SLM and show that we attain a constant crosstalk effect represented by a Gaussian function with σ=1.0 pix over a broad operational range of the SLM.

Differential single-pixel camera enabling low-cost microscopy in near-infrared spectral region.

The optical microscope for wavelengths above 1100 nm is a very important tool for characterizing the microstructure of a broad range of samples. The availability of the technique is, however, limited because special detectors with temperature stabilization, which are costly, must be used. We present the construction of a low-cost near-infrared microscope (800-1700 nm) based on the principles of compressed sensing. The presented setup is very simple and robust. It requires no temperature stabilization and can be used under standard laboratory conditions. We demonstrate that such a microscope, which uses a simple pair of balanced photodiodes as a detector, can acquire microscopic images of the sample that are comparable with those acquired by a standard microscope. Owing to its simplicity, the presented setup can provide access to infrared transmission microscopy and to a broad range of laboratories.

Compressive imaging of transient absorption dynamics on the femtosecond timescale.

Femtosecond spectroscopy is an important tool used for tracking rapid photoinduced processes in a variety of materials. To spatially map the processes in a sample would substantially expand the method's capabilities. This is, however, difficult to achieve, due to the necessity of using low-noise detection and maintaining feasible data acquisition time. Here, we demonstrate realization of an imaging pump-probe setup, featuring sub-100 fs temporal resolution, by using a straightforward modification of a standard pump-probe technique, which uses a randomly structured probe beam. The structured beam, made by a diffuser, enabled us to computationally reconstruct the maps of transient absorption dynamics based on the concept of compressed sensing. We demonstrate the setup's functionality in two proof-of-principle experiments, where we achieve spatial resolution of 20 µm. The presented concept provides a feasible route to imaging, by using the pump-probe technique and ultrafast spectroscopy in general.

Time-resolved terahertz spectroscopy reveals the influence of charged sensitizing quantum dots on the electron dynamics in ZnO.

Photoinitiated charge carrier dynamics in ZnO nanoparticles sensitized by CdSe quantum dots is studied using transient absorption spectroscopy and time-resolved terahertz spectroscopy. The evolution of the transient spectra shows that electron injection occurs in a two-step process, where the formation of a charge transfer state (occurring in several picoseconds) is followed by its dissociation within tens of picoseconds. The photoconductivity of electrons injected into the ZnO nanoparticles is lower than that of charges photogenerated directly in ZnO. We conclude that the motion of injected electrons in ZnO nanoparticles is strongly influenced by their interaction with positive charges left in the sensitizing quantum dots.

Hot electron and hole dynamics in thiol-capped CdSe quantum dots revealed by 2D electronic spectroscopy.

Colloidal quantum dots (QDs) have attracted interest as materials for opto-electronic applications, wherein their efficient energy use requires the understanding of carrier relaxation. In QDs capped by bifunctional thiols, used to attach the QDs to a surface, the relaxation is complicated by carrier traps. Using 2D spectroscopy at 77 K, we follow excitations in thiol-capped CdSe QDs with state specificity and high time resolution. We unambiguously identify the lowest state as an optically allowed hole trap, and identify an electron trap with excited-state absorption. The presence of traps changes the initial dynamics entirely by offering a different relaxation channel. 2D electronic spectroscopy enables us to pinpoint correlations between states and to easily separate relaxation from different starting states. We observe the direct rapid trapping of 1S3/2, 2S3/2, and 1S1/2 holes, and several competing electron relaxation processes from the 1Pe state.

Design and characterisation of bodipy sensitizers for dye-sensitized NiO solar cells.

A series of photosensitizers for NiO-based dye-sensitized solar cells is presented. Three model compounds containing a triphenylamine donor appended to a boron dipyrromethene (bodipy) chromophore have been successfully prepared and characterised using emission spectroscopy, electrochemistry and spectroelectrochemistry, to ultimately direct the design of dyes with more complex structures. Carboxylic acid anchoring groups and thiophene spacers were appended to the model compounds to provide five dyes which were adsorbed onto NiO and integrated into dye-sensitized solar cells. Solar cells incorporating the simple Bodipy-CO2H dye were surprisingly promising relative to the more complex dye 4. Cell performances were improved with dyes which had increased electronic communication between the donor and acceptor, achieved by incorporating a less hindered bodipy moiety. Further increases in performances were obtained from dyes which contained a thiophene spacer. Thus, the best performance was obtained for 7 which generated a very promising photocurrent density of 5.87 mA cm(-2) and an IPCE of 53%. Spectroelectrochemistry combined with time-resolved transient absorption spectroscopy were used to determine the identity and lifetime of excited state species. Short-lived (ps) transients were recorded for 4, 5 and 7 which are consistent with previous studies. Despite a longer lived (25 ns) charge-separated state for 6/NiO, there was no increase in the photocurrent generated by the corresponding solar cell.

Correction: Design and characterisation of bodipy sensitizers for dye-sensitized NiO solar cells.

Correction for 'Design and characterisation of bodipy sensitizers for dye-sensitized NiO solar cells' by Gareth H. Summers et al., Phys. Chem. Chem. Phys., 2016, DOI: 10.1039/c5cp05177k.

Directed energy transfer in films of CdSe quantum dots: beyond the point dipole approximation.

Understanding of Förster resonance energy transfer (FRET) in thin films composed of quantum dots (QDs) is of fundamental and technological significance in optimal design of QD based optoelectronic devices. The separation between QDs in the densely packed films is usually smaller than the size of QDs, so that the simple point-dipole approximation, widely used in the conventional approach, can no longer offer quantitative description of the FRET dynamics in such systems. Here, we report the investigations of the FRET dynamics in densely packed films composed of multisized CdSe QDs using ultrafast transient absorption spectroscopy and theoretical modeling. Pairwise interdot transfer time was determined in the range of 1.5 to 2 ns by spectral analyses which enable separation of the FRET contribution from intrinsic exciton decay. A rational model is suggested by taking into account the distribution of the electronic transition densities in the dots and using the film morphology revealed by AFM images. The FRET dynamics predicted by the model are in good quantitative agreement with experimental observations without adjustable parameters. Finally, we use our theoretical model to calculate dynamics of directed energy transfer in ordered multilayer QD films, which we also observe experimentally. The Monte Carlo simulations reveal that three ideal QD monolayers can provide exciton funneling efficiency above 80% from the most distant layer. Thereby, utilization of directed energy transfer can significantly improve light harvesting efficiency of QD devices.

Dispersion scan frequency resolved optical gating for consistency check of pulse retrieval.

Many methods commonly used to characterize ultrafast laser pulses, such as the frequency-resolved optical gating (FROG) or the dispersion scan (d-scan), face problems when they are used on pulses with a spectrum or phase varying within the laser beam cross section or the acquisition time. The presence of such pulse shape variation leads to discrepancy between the measured FROG trace and its reconstructed counterparts. Nevertheless, it is difficult to reliably discern this shape variation because even the distorted experimental FROG trace can be reasonably reproduced by a realistic pulse shape. In this work, we examine and discern the variation of the pulse shape based on a new method, dispersion-scan FROG (D-FROG), which combines the idea of dispersion scanning with the FROG method. This technique provides a means of careful evaluation of the laser pulse based on a set of FROG traces connected by known dispersion changes. Therefore, this method can disclose seemingly correct pulse retrievals from distorted datasets. The D-FROG method can be used as a simple extension of the FROG technique to provide a consistency check able to identify the shortcomings in the pulse characterization.

Fast monolayer adsorption and slow energy transfer in CdSe quantum dot sensitized ZnO nanowires.

A method for CdSe quantum dot (QD) sensitization of ZnO nanowires (NW) with fast adsorption rate is applied. Photoinduced excited state dynamics of the quantum dots in the case of more than monolayer coverage of the nanowires is studied. Transient absorption kinetics reveals an excitation depopulation process of indirectly attached quantum dots with a lifetime of ~4 ns. Photoluminescence and incident photon-to-electron conversion efficiency show that this process consists of both radiative e-h recombination and nonradiative excitation-to-charge conversion. We argue that the latter occurs via interdot energy transfer from the indirectly attached QDs to the dots with direct contact to the nanowires. From the latter, fast electron injection into ZnO occurs. The energy transfer time constant is found to be around 5 ns.

Ultrafast dynamics of multiple exciton harvesting in the CdSe-ZnO system: electron injection versus Auger recombination.

We study multiple electron transfer from a CdSe quantum dot (QD) to ZnO, which is a prerequisite for successful utilization of multiple exciton generation for photovoltaics. By using ultrafast time-resolved spectroscopy we observe competition between electron injection into ZnO and quenching of multiexcitons via Auger recombination. We show that fast electron injection dominates over biexcitonic Auger recombination and multiple electrons can be transferred into ZnO. A kinetic component with time constant of a few tens of picoseconds was identified as the competition between injection of the second electron from a doubly excited QD and a trion Auger recombination. Moreover, we demonstrate that the multiexciton harvesting efficiency changes significantly with QD size. Within a narrow QD diameter range from 2 to 4 nm, the efficiency of electron injection from a doubly excited QD can vary from 30% to 70% in our system.