Synthesis of Well-Ordered Functionalized Silicon Microwires Using Displacement Talbot Lithography for Photocatalysis.

Metal-assisted chemical etching (MACE) is a cheap and scalable method that is commonly used to obtain silicon nano- or microwires but lacks spatial control. Herein, we present a synthesis method for producing vertical and highly periodic silicon microwires, using displacement Talbot lithography before wet etching with MACE. The functionalized periodic silicon microwires show 65% higher PEC performance and 2.3 mA/cm2 higher net photocurrent at 0 V compared to functionalized, randomly distributed microwires obtained by conventional MACE at the same potentials.

Constructing ZnTe Spherical Quantum Well for Efficient Light Emission.

ZnTe colloidal semiconductor nanocrystals (NCs) have shown promise for light-emitting diodes (LEDs) and displays, because they are free from toxic heavy metals (Cd). However, so far, their low photoluminescence (PL) efficiency (∼30%) has hindered their applications. Herein, we devised a novel structure of ZnTe NCs with the configuration of ZnSe (core)/ZnTe (spherical quantum well, SQW)/ZnSe (shell). The inner layer ZnTe was grown at the surface of ZnSe core with avoiding using highly active and high-risk Zn sources. Due to the formation of coherently strained heterostructure which reduced the lattice mismatch, and the thermodynamic growth of ZnTe, the surface or interface defects were suppressed. A high PL efficiency of >60% was obtained for the green light-emitting ZnSe/ZnTe/ZnSe SQWs after ZnS outer layer passivation, which is the highest value for colloidal ZnTe-based NCs. This work paves the way for the development of novel semiconductor NCs for luminescent and display applications.

Temperature-Dependent Intensity Modulated Two-Photon Excited Fluorescence Microscopy for High Resolution Mapping of Charge Carrier Dynamics.

We present a temperature-dependent intensity modulated two-photon excited fluorescence microscopy technique that enables high-resolution quantitative mapping of charge carrier dynamics in perovskite microcrystal film. By disentangling the emission into harmonics of the excitation modulation frequency, we analyze the first and second order charge carrier recombination processes, including potential accumulation effects. Our approach allows for a quantitative comparison of different emission channels at a micrometer resolution. To demonstrate the effectiveness of the method, we applied it to a methylammonium lead bromide perovskite microcrystal film. We investigated the temperature-dependent modulated imaging, encompassing the exciton dissociation-association and charge carrier trapping-detrapping equilibrium. Additionally, we explored the potential freezing out of traps and the phase transition occurring at low temperatures.

Nature of Self-Trapped Exciton Emission in Zero-Dimensional Cs2ZrCl6 Perovskite Nanocrystals.

Low dimensional perovskite-inspired materials with self-tapped exciton (STE) emission have stimulated a surge of cutting-edge research in optoelectronics. Despite numerous efforts on developing versatile low-dimensional perovskite-inspired materials with efficient STE emissions, there is little emphasis on the intrinsic dynamics of STE-based broad emission in these materials. Here, we investigated the excited state dynamics in zero-dimensional (0D) Cs2ZrCl6 nanocrystals (NCs) with efficient blue STE emission. By using femtosecond transient absorption (fs-TA) spectroscopy, the ultrafast STE formation process within 400 fs is directly observed. Then, the formed STEs relax to an intermediate STE state with a lifetime of ∼180 ps before reaching the emissive STE state with a lifetime of ∼15 µs. Our work offers a comprehensive and precise dynamic picture of STE emission in low-dimensional metal halides and sheds light on extending their potential applications.

Pulse overlap artifacts and double quantum coherence spectroscopy.

The double quantum coherence (DQC) signal in nonlinear spectroscopy gives information about the many-body correlation effects not easily available by other methods. The signal is short-lived, consequently, a significant part of it is generated during the pulse overlap. Since the signal is at two times the laser frequency, one may intuitively expect that the pulse overlap-related artifacts are filtered out by the Fourier transform. Here, we show that this is not the case. We perform explicit calculations of phase-modulated two-pulse experiments of a two-level system where the DQC is impossible. Still, we obtain a significant signal at the modulation frequency, which corresponds to the DQC, while the Fourier transform over the pulse delay shows a double frequency. We repeat the calculations with a three-level system where the true DQC signal occurs. We conclude that with realistic dephasing times, the pulse-overlap artifact can be significantly stronger than the DQC signal. Our results call for great care when analyzing such experiments. As a rule of thumb, we recommend that only delays larger than 1.5 times the pulse length should be used.

Non-Hermitian Hamiltonians for linear and nonlinear optical response: A model for plexcitons.

In polaritons, the properties of matter are modified by mixing the molecular transitions with light modes inside a cavity. Resultant hybrid light-matter states exhibit energy level shifts, are delocalized over many molecular units, and have a different excited-state potential energy landscape, which leads to modified exciton dynamics. Previously, non-Hermitian Hamiltonians have been derived to describe the excited states of molecules coupled to surface plasmons (i.e., plexcitons), and these operators have been successfully used in the description of linear and third order optical response. In this article, we rigorously derive non-Hermitian Hamiltonians in the response function formalism of nonlinear spectroscopy by means of Feshbach operators and apply them to explore spectroscopic signatures of plexcitons. In particular, we analyze the optical response below and above the exceptional point that arises for matching transition energies for plasmon and molecular components and study their decomposition using double-sided Feynman diagrams. We find a clear distinction between interference and Rabi splitting in linear spectroscopy and a qualitative change in the symmetry of the line shape of the nonlinear signal when crossing the exceptional point. This change corresponds to one in the symmetry of the eigenvalues of the Hamiltonian. Our work presents an approach for simulating the optical response of sublevels within an electronic system and opens new applications of nonlinear spectroscopy to examine the different regimes of the spectrum of non-Hermitian Hamiltonians.

Localized Bound Multiexcitons in Engineered Quasi-2D Perovskites Grains at Room Temperature for Efficient Lasers.

Reducing the excitation threshold to minimize the Joule heating is critical for the realization of perovskite laser diodes. Although bound excitons are promising for low threshold laser, how to generate them at room temperature for laser applications is still unclear in quasi-2D perovskite-based devices. In this work, via engineering quasi-2D perovskite PEA2 (CH3 NH3 )n -1 Pbn Br3 n +1 microscopic grains by the anti-solvent method, room-temperature multiexciton radiative recombination is successfully demonstrated at a remarkably low pump density of 0.97 µJ cm-2 , which is only one-fourth of that required in 2D CdSe nanosheets. In addition, the well-defined translational momentum in quasi-2D perovskite grains can restrict the Auger recombination which is detrimental to radiative emission. Furthermore, the quasi-2D perovskite grains are favorable for increasing binding energies of excitons and biexcitons and so as the related radiative recombination. Consequently, the prepared phase quasi-2D perovskite film renders a threshold of room-temperature stimulated emission as low as 13.7 µJ cm-2 , reduced by 58.6% relative to the amorphous counterpart with larger grains. The findings in this work are expected to facilitate the development of solution-processable perovskite multiexcitonic laser diodes.

Slower Auger Recombination in 12-Faceted Dodecahedron CsPbBr3 Nanocrystals.

Over the past two decades, intensive research efforts have been devoted to suppressions of Auger recombination in metal-chalcogenide and perovskite nanocrystals (PNCs) for the application of photovoltaics and light emitting devices (LEDs). Here, we have explored dodecahedron cesium lead bromide perovskite nanocrystals (DNCs), which show slower Auger recombination time compared to hexahedron nanocrystals (HNCs). We investigate many-body interactions that are manifested under high excitation flux density in both NCs using ultrafast spectroscopic pump-probe measurements. We demonstrate that the Auger recombination rate due to multiexciton recombinations are lower in DNCs than in HNCs. At low and intermediate excitation density, the majority of carriers recombine through biexcitonic recombination. However, at high excitation density (>1018 cm-3) a higher number of many-body Auger process dominates over biexcitonic recombination. Compared to HNCs, high PLQY and slower Auger recombinations in DNCs are likely to be significant for the fabrication of highly efficient perovskite-based photonics and LEDs.

External electric field-dependent photoinduced charge transfer in non-fullerene organic solar cells.

Based on Marcus theory, the photoinduced electron transfer properties of D-A type non-fullerene acceptor organic solar cells (OSCs) under the dependence of external electric field (Fext) were investigated. The research results shown that the charge transfer mode under different Fext intensities changes with certain regularity. Focusing on the important parameters (ΔG, λ, and VDA) that affect the charge transfer rate, it was found that both charge separation (|ΔGCS|>λ(1.3019 vs 0.8275 eV at Fext = 0) and charge recombiation (|ΔGCR|>λ, (1.9633 vs 0.8275 eV)) processes occur in the Marcus inverted region. The ΔGCS is relatively sensitive to Fext, and the calculated ΔGCS at different Fext intensities yields an increment of 0.0073 eV, which is also the main reason for the increase in the rate of charge separation. The ΔGCR ranges between -1.9633 and -1.9637 eV, is insensitive to Fext, and ΔGCR is significantly smaller than ΔGCS, which makes the charge recombination rate significantly smaller than the charge separation rate. For VDA, it is found that VDA will transition to a new level only when the Fext intensity reaches a certain intensity, which also enables to obtain a faster charge separation rate. By studying the charge transfer parameters in different polar solvents, it is found that polar solvents can indeed increase the charge transfer rate. To a certain extent, our results also demonstrate that the addition of Fext can further improve the performance of non-fullerene acceptor OSCs.

Optical cavity-mediated exciton dynamics in photosynthetic light harvesting 2 complexes.

Strong light-matter interaction leads to the formation of hybrid polariton states and alters the photophysical dynamics of organic materials and biological systems without modifying their chemical structure. Here, we experimentally investigated a well-known photosynthetic protein, light harvesting 2 complexes (LH2) from purple bacteria under strong coupling with the light mode of a Fabry-Perot optical microcavity. Using femtosecond pump probe spectroscopy, we analyzed the polariton dynamics of the strongly coupled system and observed a significant prolongation of the excited state lifetime compared with the bare exciton, which can be explained in terms of the exciton reservoir model. Our findings indicate the potential of tuning the dynamic of the whole photosynthetic unit, which contains several light harvesting complexes and reaction centers, with the help of strong exciton-photon coupling, and opening the discussion about possible design strategies of artificial photosynthetic devices.

Direct Observation of Size-Dependent Phase Transition in Methylammonium Lead Bromide Perovskite Microcrystals and Nanocrystals.

Methylammonium (MA) lead halide perovskites have been widely studied as active materials for advanced optoelectronics. As crystalline semiconductor materials, their properties are strongly affected by their crystal structure. Depending on their applications, the size of MA lead halide perovskite crystals varies by several orders of magnitude. The particle size can lead to different structural phase transitions and optoelectronic properties. Herein, we investigate the size effect for phase transition of MA lead bromide (MAPbBr3) by comparing the temperature-dependent neutron powder diffraction patterns of microcrystals and nanocrystals. The orthorhombic-to-tetragonal phase transition occurs in MAPbBr3 microcrystals within the temperature range from 100 to 310 K. However, the phase transition is absent in nanocrystals in this temperature range. In this work, we offer a persuasive and direct evidence of the relationship between the particle size and the phase transition in perovskite crystals.

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.

Organo-Metal Halide Scintillator with Weak Thermal Quenching Up to 200 °C.

The prominent thermal quenching (TQ) effect of organic-inorganic metal halides limits their applications for lighting and imaging. Herein, we report an organo-metal halide scintillator (TTPhP)2MnCl4 (TTPhP+ = tetraphenylphosphonium cation), which exhibits a weak TQ effect up to 200 °C under ultraviolet-visible light (efficiency loss of 5.5%) and X-ray radiation (efficiency loss of 37%). The light yield of the (TTPhP)2MnCl4 scintillator (37 000 photons MeV-1 at 200 °C) under X-ray radiation is >2 times that of the commercial scintillator LuAG:Ce (15 000 photons MeV-1 at 200 °C). The microscopic mechanism of the weak TQ effect is demonstrated to be the scintillator having the ability to compensate for the emission losses from trapped charges and the large Mn-Mn distance (10.233 Å) suppressing nonradiative recombination at high temperatures. We further demonstrate the applications of (TTPhP)2MnCl4 as high-power white-light-emitting diodes operated at currents of ≤300 mA and X-ray imaging at 200 °C with a high spatial resolution.

Two-photon absorption in halide perovskites and their applications.

Active research on halide perovskites has given us a deep understanding of this family of materials and their potential for applications in advanced optoelectronic devices. One of the prominent outcomes is the use of perovskite materials for nonlinear optical applications. Two-photon absorption in perovskites, in particular their nanostructures, has been extensively studied and shows huge promise for many applications. However, we are still far from a thorough understanding of two-photon absorption in halide perovskites from a micro to macro perspective. Here we summarize different techniques for studying the two-photon absorption in nonlinear optical materials. We discuss the in-depth photophysics in two-photon absorption in halide perovskites. A comprehensive summary about the factors which influence two-photon absorption provides the direction to improve the two-photon absorption properties of halide perovskites. A summary of the recent applications of two-photon absorption in halide perovskites provides inspirations for engineers to utilize halide perovskites in two-photon absorption device development. This review will help readers to have a comprehensive and in-depth understanding of the research field of two-photon absorption of halide perovskites from microscopic mechanisms to applications. The article can serve as a manual and give inspiration for future researchers.

Morphology-Dependent One- and Two-Photon Absorption Properties in Blue Emitting CsPbBr3 Nanocrystals.

The linear and nonlinear optical parameters and morphologic dependence of CsPbBr3 nanocrystals (NCs) are crucial for device engineering. In particular, such information in asymmetric nanocrystals is still insufficient. We characterized the OPLA (σ1) and TPA cross sections (σ2) of a series CsPbBr3 nanocrystals with various aspect ratios (AR) using femtosecond transient absorption spectroscopy (TAS). The σ1 presents a linear volume dependence of all the samples, which agrees with the previous behavior in CsPbBr3 QDs. However, the σ2 values do not exhibit conventional power dependency of the crystal volume but are also modulated by the shape-dependent local field factors. In addition, the local field effect in CsPbBr3 NCs is contributed by their asymmetric morphologies and polar ionic lattices, which is more pronounced than in conventional semiconductor NCs. Finally, we revealed that the lifetimes of photogenerated multiexcitonic species of those nanocrystals feature identical morphology independence in both OPLA and TPA.

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives.

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI3 nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn2+ doping (1) enlarges the longitudinal optical (LO)-acoustic phonon bandgap, (2) enhances the electron-LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn2+ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier-phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron-LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Ultrafast charge transfer dynamics in 2D covalent organic frameworks/Re-complex hybrid photocatalyst.

Rhenium(I)-carbonyl-diimine complexes have emerged as promising photocatalysts for carbon dioxide reduction with covalent organic frameworks recognized as perfect sensitizers and scaffold support. Such Re complexes/covalent organic frameworks hybrid catalysts have demonstrated high carbon dioxide reduction activities but with strong excitation energy-dependence. In this paper, we rationalize this behavior by the excitation energy-dependent pathways of internal photo-induced charge transfer studied via transient optical spectroscopies and time-dependent density-functional theory calculation. Under band-edge excitation, the excited electrons are quickly injected from covalent organic frameworks moiety into catalytic RheniumI center within picosecond but followed by fast backward geminate recombination. While under excitation with high-energy photon, the injected electrons are located at high-energy levels in RheniumI centers with longer lifetime. Besides those injected electrons to RheniumI center, there still remain some long-lived electrons in covalent organic frameworks moiety which is transferred back from RheniumI. This facilitates the two-electron reaction of carbon dioxide conversion to carbon monoxide.

Excited States and Their Dynamics in CdSe Quantum Dots Studied by Two-Color 2D Spectroscopy.

Quantum dots (QDs) form a promising family of nanomaterials for various applications in optoelectronics. Understanding the details of the excited-state dynamics in QDs is vital for optimizing their function. We apply two-color 2D electronic spectroscopy to investigate CdSe QDs at 77 K within a broad spectral range. Analysis of the electronic dynamics during the population time allows us to identify the details of the excitation pathways. The initially excited high-energy electrons relax with the time constant of 100 fs. Simultaneously, the states at the band edge rise within 700 fs. Remarkably, the excited-state absorption is rising with a very similar time constant of 700 fs. This makes us reconsider the earlier interpretation of the excited-state absorption as the signature of a long-lived trap state. Instead, we propose that this signal originates from the excitation of the electrons that have arrived in the conduction-band edge.

Implementing an intermittent spin-coating strategy to enable bottom-up crystallization in layered halide perovskites.

Two-dimensional halide perovskites (2D PVSKs) have drawn tremendous attentions owing to their outstanding ambient stability. However, the random orientation of layered crystals severely impedes the out-of-plane carrier transport and limits the solar cell performance. An in-depth understanding coupled with an effective control of the crystallization in 2D PVSKs is the crux for highly efficient and durable devices. In this contribution, we accidentally discovered that the crystallization of 2D PVSKs can be effectively regulated by so-called 'intermittent spin-coating (ISC)' process. Combined analyses of in(ex)-situ grazing-incidence wide-angle X-ray scattering with time-of-flight secondary ion mass spectrometry distinguish the interface initialized bottom-up crystallization upon ISC treatment from the bi-directional one in the conventional spin-coating process, which results in significantly enhanced crystal orientation and thus facilitated carrier transport as confirmed by both electrical measurements and ultrafast spectroscopies. As a result, the p-i-n architecture planar solar cells based on ISC fabricated paradigm PEA2MA3Pb4I13 deliver a respectable efficiency of 11.2% without any treatment, which is three-fold improvement over their spin-coated counterparts and can be further boosted up to 14.0% by NH4Cl addition, demonstrating the compatibility of ISC method with other film optimization strategies.

Charge Carrier Diffusion Dynamics in Multisized Quaternary Alkylammonium-Capped CsPbBr3 Perovskite Nanocrystal Solids.

CsPbBr3 quantum dots (QDs) are promising candidates for optoelectronic devices. The substitution of oleic acid (OA) and oleylamine (OLA) capping agents with a quaternary alkylammonium such as di-dodecyl dimethyl ammonium bromide (DDAB) has shown an increase in external quantum efficiency (EQE) from 0.19% (OA/OLA) to 13.4% (DDAB) in LED devices. The device performance significantly depends on both the diffusion length and the mobility of photoexcited charge carriers in QD solids. Therefore, we investigated the charge carrier transport dynamics in DDAB-capped CsPbBr3 QD solids by constructing a bi-sized QD mixture film. Charge carrier diffusion can be monitored by quantitatively varying the ratio between two sizes of QDs, which varies the mean free path of the carriers in each QD cluster. Excited-state dynamics of the QD solids obtained from ultrafast transient absorption spectroscopy reveals that the photogenerated electrons and holes are difficult to diffuse among small-sized QDs (4 nm) due to the strong quantum confinement. On the other hand, both photoinduced electrons and holes in large-sized QDs (10 nm) would diffuse toward the interface with the small-sized QDs, followed by a recombination process. Combining the carrier diffusion study with a Monte Carlo simulation on the QD assembly in the mixture films, we can calculate the diffusion lengths of charge carriers to be ∼239 ± 16 nm in 10 nm CsPbBr3 QDs and the mobility values of electrons and holes to be 2.1 (± 0.1) and 0.69 (± 0.03) cm2/V s, respectively. Both parameters indicate an efficient charge carrier transport in DDAB-capped QD films, which rationalized the perfect performance of their LED device application.