Abstract: Most studied two-dimensional (2D) materials exhibit isotropic behavior due to high lattice symmetry; however, lower-symmetry 2D materials such as phosphorene and other elemental 2D materials exhibit very interesting anisotropic properties. In this work, we report the atomic structure, electronic properties, and vibrational modes of few-layered PdSe2 exfoliated from bulk crystals, a pentagonal 2D layered noble transition metal dichalcogenide with a puckered morphology that is air-stable. Micro-absorption optical spectroscopy and first-principles calculations reveal a wide band gap variation in this material from 0 (bulk) to 1.3 eV (monolayer). The Raman-active vibrational modes of PdSe2 were identified using polarized Raman spectroscopy, and a strong interlayer interaction was revealed from large, thickness-dependent Raman peak shifts, agreeing with first-principles Raman simulations. Field-effect transistors made from the few-layer PdSe2 display tunable ambipolar charge carrier conduction with a high elec...

Abstract: In this Letter, we experimentally report an achromatic metalens (AML) operating over a continuous bandwidth in the visible. This is accomplished via dispersion engineering of dielectric phase shifters: titanium dioxide nanopillars tiled on a dielectric spacer layer above a metallic mirror. The AML works in reflection mode with a focal length independent of wavelength from λ = 490 to 550 nm. We also design a metalens with reverse chromatic dispersion, where the focal length increases as the wavelength increases, contrary to conventional diffractive lenses. The ability to engineer the chromatic dispersion of metalenses at will enables a wide variety of applications that were not previously possible. In particular, for the AML design, we envision applications such as imaging under LED illumination, fluorescence, and photoluminescence spectroscopy.

Abstract: Two-dimensional (2D) organolead halide perovskites are promising for various optoelectronic applications. Here we report a unique spontaneous charge (electron/hole) separation property in multilayered (BA)2(MA)n−1PbnI3n+1 (BA = CH3(CH2)3NH3+, MA = CH3NH3+) 2D perovskite films by studying the charge carrier dynamics using ultrafast transient absorption and photoluminescence spectroscopy. Surprisingly, the 2D perovskite films, although nominally prepared as “n = 4”, are found to be mixture of multiple perovskite phases, with n = 2, 3, 4 and ≈ ∞, that naturally align in the order of n along the direction perpendicular to the substrate. Driven by the band alignment between 2D perovskites phases, we observe consecutive photoinduced electron transfer from small-n to large-n phases and hole transfer in the opposite direction on hundreds of picoseconds inside the 2D film of ∼358 nm thickness. This internal charge transfer efficiently separates electrons and holes to the upper and bottom surfaces of the films, whi...

Abstract: We report the modification of graphene oxide (GO) by thermal reduction to obtain reduced graphene oxide (RGO) and subsequent modification by sulfophenyl groups as well as the characterization of these materials by thermogravimetric analysis coupled with mass spectroscopy (TGA-MS) The chemical modification of RGO was carried out by the spontaneous reaction of RGO with in situ generated sulfophenyl diazonium ions The three different types of materials were also characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) The characteristic absorption band at 1034 and 1160 cm−1 in the FTIR spectrum of the sulfophenyl-modified RGO (SRGO), as well as Raman spectroscopy and TGA-MS data indicated that sulfophenyl groups were successfully grafted on RGO The presence of organic molecules at the SRGO surface was also demonstrated by elemental analysis, transmission electron microscopy, energy dispersive X-ray spectroscopy and XPS TGA data and elemental analysis results showed that the loading of sulfophenyl groups was about 12 wt% and UV-visible-near IR spectroscopy confirms the slight increase of the optical band gap of RGO after covalent grafting of sulfophenyl groups on its surface

Abstract: Nuclear magnetic resonance (NMR) spectroscopy is a key analytical technique in chemistry, biology, and medicine However, conventional NMR spectroscopy requires an at least nanoliter-sized sample volume to achieve sufficient signal We combined the use of a quantum memory and high magnetic fields with a dedicated quantum sensor based on nitrogen vacancy centers in diamond to achieve chemical shift resolution in 1H and 19F NMR spectroscopy of 20-zeptoliter sample volumes We demonstrate the application of NMR pulse sequences to achieve homonuclear decoupling and spin diffusion measurements The best measured NMR linewidth of a liquid sample was ~1 part per million, mainly limited by molecular diffusion To mitigate the influence of diffusion, we performed high-resolution solid-state NMR by applying homonuclear decoupling and achieved a 20-fold narrowing of the NMR linewidth

Abstract: Despite the popular use of UV-Vis spectroscopy for dissolved organic matter (DOM) studies, many of the derived parameters and the related methods have been rather limitedly used for certain areas o...

Abstract: The transport of excitation energy in molecular aggregates is of crucial importance for the function of organic optoelectronic devices and next-generation solar cells. First, this review summarizes the theoretical background of the nature of the electronically excited states of molecular aggregates. For these systems, the electronic interaction between the monomers leads to the formation of exciton states. This goes along with a shift of the excitation energies and a redistribution of the oscillator strength with respect to the monomers. Next, a brief overview is provided over experimental techniques that allow to study the properties of excitons in molecular aggregates. This includes single-molecule spectroscopy, coherent two-dimensional (2D) spectroscopy, and single-molecule coherent spectroscopy. Finally, examples of molecular aggregates spanning the range from natural systems that act in photosynthesis as light-harvesting antennas to artificial aggregates built from synthetic chromophores are illustrated.

Abstract: Defects play a significant role in tailoring the optical properties of two-dimensional materials. Optical signatures of defect-bound excitons are important tools to probe defective regions and thus interrogate the optical quality of as-grown semiconducting monolayer materials. We have performed a systematic study of defect-bound excitons using photoluminescence (PL) spectroscopy combined with atomically resolved scanning electron microscopy and first-principles calculations. Spatially resolved PL spectroscopy at low temperatures revealed bound excitons that were present only on the edges of monolayer tungsten disulfide and not in the interior. Optical pumping of the bound excitons was sublinear, confirming their bound nature. Atomic-resolution images reveal that the areal density of monosulfur vacancies is much larger near the edges (0.92 ± 0.45 nm−2) than in the interior (0.33 ± 0.11 nm−2). Temperature-dependent PL measurements found a thermal activation energy of ~36 meV; surprisingly, this is much smaller than the bound-exciton binding energy of ~300 meV. We show that this apparent inconsistency is related to a thermal dissociation of the bound exciton that liberates the neutral excitons from negatively charged point defects. First-principles calculations confirm that sulfur monovacancies introduce midgap states that host optical transitions with finite matrix elements, with emission energies ranging from 200 to 400 meV below the neutral-exciton emission line. These results demonstrate that bound-exciton emission induced by monosulfur vacancies is concentrated near the edges of as-grown monolayer tungsten disulfide.

Abstract: Revealing the crystal structure of lead halide perovskite nanocrystals is essential for the optimization of stability of these emerging materials in applications such as solar cells, photodetectors, and light-emitting devices. We use magneto-photoluminescence spectroscopy of individual perovskite CsPbBr3 nanocrystals as a unique tool to determine their crystal structure, which imprints distinct signatures in the excitonic sublevels of charge complexes at low temperatures. At zero magnetic field, the identification of two classes of photoluminescence spectra, displaying either two or three sublevels in their exciton fine structure, shows evidence for the existence of two crystalline structures, namely tetragonal D4h and orthorhombic D2h phases. Magnetic field shifts, splitting, and coupling of the sublevels provide a determination of the diamagnetic coefficient and valuable information on the exciton g-factor and its anisotropic character. Moreover, this spectroscopic study reveals the optical properties o...

Abstract: Metal nanoclusters (NCs) as a new type of fluorescent material have been extensively explored because of their attractive set of features such as their ultrafine size, low toxicity, and excellent photostability. However, little progress has been made in producing water-soluble, homogeneous, and ultrabright metal NCs. In this study, gold NCs (AuNCs) with a photoluminescence quantum yield (QY) as high as 65% are synthesized in water through a simple blending route. Weak emission is observed from the 6-aza-2-thiothymine-protected AuNCs (ATT-AuNCs); however, the fluorescence intensity can be prominently enhanced by introducing l-arginine (Arg) into the capping layer. The fluorescence enhancement mechanism is systematically investigated by the measurements of ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, fluorescence lifetime spectroscopy, transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, 1H nuclear magnetic resonance, and calculations ...

Abstract: Solar hydrogen generation from water represents a compelling component of a future sustainable energy portfolio. Recently, chemically robust heptazine-based polymers known as graphitic carbon nitrides (g-C3N4) have emerged as promising photocatalysts for hydrogen evolution using visible light while withstanding harsh chemical environments. However, since g-C3N4 electron-transfer dynamics are poorly understood, rational design rules for improving activity remain unclear. Here, we use visible and near-infrared femtosecond transient absorption (TA) spectroscopy to reveal an electron-transfer cascade that correlates with a near-doubling in photocatalytic activity from 2050 to 3810 μmol h–1 g–1 when we infuse a suspension of bulk g-C3N4 with 10% mass loading of chemically exfoliated carbon nitride. TA spectroscopy indicates that exfoliated carbon nitride quenches photogenerated electrons on g-C3N4 at rates approaching the molecular diffusion limit. The TA signal for photogenerated electrons on g-C3N4 decays wi...

Abstract: The structural and photophysical characteristics of MAPbBr3 single crystals prepared using the inverse temperature crystallization method are evaluated using temperature-dependent X-ray diffraction (XRD) and optical spectroscopy. Contrary to previous research reports on perovskite materials, we study phase transitions in crystal lattice structures accompanied with changes in optical properties expand throughout a wide temperature range of 300–1.5 K. The XRD studies reveal several phase transitions occurred at ~210 K, ~145 K, and ~80 K, respectively. The coexistence of two different crystallographic phases was observed at a temperature below 145 K. The emission peaks in the PL spectra are all asymmetric in line shape with weak and broad shoulders near the absorption edges, which are attributed to the Br atom vacancy on the surface of the crystals. The time-resolved PL measurements reveal the effect of the desorption/adsorption of gas molecules on the crystal surface on the PL lifetimes. Raman spectroscopy results indicate the strong interplays between cations and different halide atoms. Lastly, no diamagnetic shift or split in emission peaks can be observed in the magneto-PL spectra even at an applied magnetic field up to 5 T and at a temperature as low as 1.5 K.

Abstract: In planar n-i-p heterojunction perovskite solar cells, the electron transport layer (ETL) plays important roles in charge extraction and determine the morphology of the perovskite film. Here, we report a solution-processed carbon quantum dots (CQDs)/TiO2 composite that has negligible absorption in the visible spectral range, a very attractive feature for perovskite solar cells. Using this novel CQDs/TiO2 ETL in conjunction with a planar n-i-p heterojunction, we achieved an unprecedented efficiency of ∼19% under standard illumination test conditions. It was found that a CQDs/TiO2 combination increases both the open circuit voltage and short-circuits current density as compared to using TiO2 alone. Various advanced spectroscopic characterizations including ultrafast spectroscopy, ultraviolet photoelectron spectroscopy, and electronic impedance spectroscopy elucidate that the CQDs increases the electronic coupling between the CH3NH3PbI3–xClx and TiO2 ETL interface as well as energy levers that contribute to ...

Abstract: Surface-enhanced infrared absorption (SEIRA) spectroscopy has outstanding potential in chemical detection as a complement to surface-enhanced Raman spectroscopy (SERS), yet it has historically lagged well behind SERS in detection sensitivity. Here we report a new ultrasensitive infrared antenna designed to bring SEIRA spectroscopy into the few-molecule detection range. Our antenna consists of a bowtie-shaped Au structure with a sub-3 nm gap, positioned to create a cavity above a reflective substrate. This three-dimensional geometry tightly confines incident mid-infrared radiation into its ultrasmall junction, yielding a hot spot with a theoretical SEIRA enhancement factor of more than 107, which can be designed to span the range of frequencies useful for SEIRA. We quantitatively evaluated the IR detection limit of this antenna design using mixed monolayers of 4-nitrothiophenol (4-NTP) and 4-methoxythiolphenol (4-MTP). The optimized antenna structure allows the detection of as few as ∼500 molecules of 4-NT...

Abstract: The present work focuses on the synthesis, characterization and photocatalytic activity of a nanosized Fe-doped TiO2 photocatalyst. The samples were synthesized by the sol–gel method and characterized by using techniques such as x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDS), UV–visible spectroscopy, photoluminescence (PL) spectroscopy, Raman spectroscopy and Fourier-transform infrared (FTIR). The powder XRD spectra revealed that the synthesized samples are pure and crystalline in nature and show a tetragonal anatase phase of TiO2. The Raman spectroscopy also confirmed the formation of an anatase phase structure in both pure and Fe-doped TiO2 nanoparticles (NPs). The UV–visible and PL spectra illustrated the red shift in Fe-doped TiO2 NPs. The FTIR spectra indicated the vibrational band of the Ti–O lattice. The photocatalytic experimental results demonstrate that Fe-doped TiO2 NPs effectively degrade MB under visible-light illumination. Interestingly, the prepared TiO2 NPs with a dopant concentration of 3.0 mole% showed the maximum photocatalytic activity under investigation.

Abstract: Vertical-external-cavity surface-emitting lasers (VECSELs) are the most versatile laser sources, combining unique features such as wide spectral coverage, ultrashort pulse operation, low noise properties, high output power, high brightness and compact form-factor. This paper reviews the recent technological developments of VECSELs in connection with the new milestones that continue to pave the way towards their use in numerous applications. Significant attention is devoted to the fabrication of VECSEL gain mirrors in challenging wavelength regions, especially at the yellow and red wavelengths. The reviewed fabrication approaches address wafer-bonded VECSEL structures as well as the use of hybrid mirror structures. Moreover, a comprehensive summary of VECSEL characterization methods is presented; the discussion covers different stages of VECSEL development and different operation regimes, pointing out specific characterization techniques for each of them. Finally, several emerging applications are discussed, with emphasis on the unique application objectives that VECSELs render possible, for example in atom and molecular physics, dermatology and spectroscopy.

Abstract: Understanding the reactivity and spectroscopy of aqueous solutions at the atomistic level is crucial for the elucidation and design of chemical processes. However, the simulation of these systems requires addressing the formidable challenges of treating the quantum nature of both the electrons and nuclei. Exploiting our recently developed methods that provide acceleration by up to 2 orders of magnitude, we combine path integral simulations with on-the-fly evaluation of the electronic structure at the hybrid density functional theory level to capture the interplay between nuclear quantum effects and the electronic surface. Here we show that this combination provides accurate structure and dynamics, including the full infrared and Raman spectra of liquid water. This allows us to demonstrate and explain the failings of lower-level density functionals for dynamics and vibrational spectroscopy when the nuclei are treated quantum mechanically. These insights thus provide a foundation for the reliable investigat...

Abstract: Previous studies have shown that hydrogen treatment leads to the formation of blue to black TiO2, which exhibits photocatalytic activity different from that of white pristine TiO2. However, the underlying mechanism remains poorly understood. Herein, density functional theory is combined with comprehensive analytical approaches such as X-ray absorption near edge structure spectroscopy and transient absorption spectroscopy to gain fundamental understanding of the correlation among the oxygen vacancy, electronic band structure, charge separation, charge carrier lifetime, reactive oxygen species (ROS) generation, and photocatalytic activity. The present work reveals that hydrogen treatment results in chemical reduction of TiO2, inducing surface and subsurface oxygen vacancies, which create shallow and deep sub-band gap Ti(III) states below the conduction band. This leads to a blue color but limited enhancement of visible light photocatalytic activity up to 440 nm at the cost of reduced ultraviolet photocataly...

Abstract: Second-order nonlinear spectroscopy has proven to be a powerful tool in elucidating key chemical and structural characteristics at a variety of interfaces. However, the presence of interfacial potentials may lead to complications regarding the interpretation of second harmonic and vibrational sum frequency generation responses from charged interfaces due to mixing of absorptive and dispersive contributions. Here, we examine by means of mathematical modeling how this interaction influences second-order spectral lineshapes. We discuss our findings in the context of reported nonlinear optical spectra obtained from charged water/air and solid/liquid interfaces and demonstrate the importance of accounting for the interfacial potential-dependent \c{hi}(3) term in interpreting lineshapes when seeking molecular information from charged interfaces using second-order spectroscopy.

Abstract: In this study, BiVO4 was prepared by a hydrothermal synthesis route in the presence of sodium dodecyl sulfate using aqueous NH3 as precipitant. g-C3N4 was prepared by a combustion method using melamine. In order to develop highly efficient photocatalyst, a heterojunction catalyst based on g-C3N4 and BiVO4 was prepared. Different amounts of BiVO4 and g-C3N4 were mixed and annealed to obtain heterojunction photocatalysts. FeVO4 and LaVO4 were also prepared for the comparative catalytic investigation. Catalysts were characterized by a series of complementary combinations of powder X-ray diffraction, thermogravimetric analysis, elemental analysis, N2 adsorption–desorption, scanning electron microscopy, transmission electron microscopy, temperature-programmed desorption of NH3 and CO2, diffuse reflectance ultraviolet visible spectroscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and photoelectrochemical studies. Catalysts were investigated in the visible light driven oxidation of benzy...

Abstract: Mid-infrared dual-comb spectroscopy has the potential to supplant conventional high-resolution Fourier transform spectroscopy in applications that require high resolution, accuracy, signal-to-noise ratio, and speed. Until now, dual-comb spectroscopy in the mid-infrared has been limited to narrow optical bandwidths or to low signal-to-noise ratios. Using a combination of digital signal processing and broadband frequency conversion in waveguides, we demonstrate a mid-infrared dual-comb spectrometer that can measure comb-tooth resolved spectra across an octave of bandwidth in the mid-infrared from 2.6-5.2 $\mu$m with sub-MHz frequency precision and accuracy and with a spectral signal-to-noise ratio as high as 6500. As a demonstration, we measure the highly structured, broadband cross-section of propane (C3H8) in the 2860-3020 cm-1 region, the complex phase/amplitude spectrum of carbonyl sulfide (COS) in the 2000 to 2100 cm-1 region, and the complex spectra of methane, acetylene, and ethane in the 2860-3400 cm-1 region.

Abstract: Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm-3 Separate electron and hole relaxation times are observed as a function of hot carrier energies A first-order electron and hole decay of ∼1 ps suggests a Shockley-Read-Hall recombination mechanism The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions

Abstract: Exciton many-body interaction is the fundamental light–matter interaction that determines the optical response of the new class of colloidal perovskite nanocrystals of the general formula CsPbX3 [X = Cl, Br, or I]. However, the understanding of exciton many-body interactions manifested through the transient biexcitonic Stark effect at the early time scales and the Auger recombination process in this new class of materials still remains rather incomplete. In this Article, we studied the many-body exciton interactions under controlled conditions through ultrafast transient absorption spectroscopy. A large biexcitonic redshift ∼30 meV to the effect of hot excitations on the excitonic resonance is observed at the early time scales. From the fluence-dependent studies, it is evident that the samples have only single and biexciton lifetimes, suggesting that the band edges are 2-fold degenerate. This explicit experimental evidence for the exciton many-body interactions in CsPbBr3 nanocrystals provides a powerful ...