Excitation Photon Energy Research Articles

Electron Correlations in Sequential Two-Photon Double Ionization of an Ar Atom

Sequential two-photon ionization is a process that is experimentally accessible due to the use of new free-electron laser sources for excitation. For the prototypical rare Ar gas atoms, a photoelectron spectrum (PES) corresponding to the second step of the sequential two-photon double ionization (2PDIII) at a photon excitation energy of 65.3 eV was studied theoretically with a focus on the consequences of electron correlations in the considered process. The calculation predicts many intense lines at low photoelectron energies, which cannot be explained on the basis of a one-electron approximation. The processes that lead to the appearance of these lines include many-electron correlations, either in the first or second step of photoionization. A significant fraction of the intensity of the low-energy part of PES is associated with the Auger decay of the excited states formed at the second step of 2PDI. The shape of the low-energy part of the 2PDIII PES is expected to be dependent on both the energy of photon excitations and the flux of the exciting beam.

(Invited, Digital Presentation) Ultrafast Spectroscopy of Inorganic Perovskite Nanocrystals and Their Assemblies: Uncovering the Multiple Exciton Generation Rate and Band-Formation

Inorganic perovskite nanocrystals (NCs) display attractive structural and optical properties, and have perspective in a wide range of optoelectronic applications. One interesting feature is their relatively slow hot carrier cooling rate, which allows to follow carrier dynamics in great detail with ultrafast spectroscopic techniques.In this talk, we present studies of the ultrafast carrier dynamics of perovskite NCs and assembled structures. Typically, when the excitation photon energy is increased, and thus the excess energy of the created carriers, the cooling time of the carriers towards the bandedge increases along. However, for CsPbI3 NCs, when the photon energy exceeds a certain threshold energy the cooling time starts to decrease, indicating that a competing relaxation pathway opens up which funnels carriers towards the bandedge. This threshold energy indicates the onset of a carrier multiplication process, in which absorption of a single photon leads to the creation of multiple electron-hole pairs. This process can also be inferred by following the carrier concentration, which shows a delayed build-up following the excitation pulse. The carrier dynamics in this system can be modeled within a framework of two competing cooling mechanisms. With the experimentally determined carrier cooling rate and threshold energy it is possible to extract the time-constant associated with the carrier multiplication process.Experiments on highly ordered CsPbBr3 NCs, so-called supercrystals, revealed how the photophysics are altered due to the inter-NC coupling as compared to the individual NCs. Next to a red-shift of the absorption and photoluminescence peak, the supercrystals show signatures of band-like states. The observation of a reduced Stokes-shift, decreased biexciton binding energy and increased carrier cooling rates, support the formation of delocalized states resulting from the coupling between individual NCs. These results open perspectives for assembled NCs for application in optoelectronic devices, with design opportunities exceeding the level of nanocrystal and bulk material.

All-optical switching of magnetization in atomically thin CrI3.

Control of magnetism has attracted interest in achieving low-power and high-speed applications such as magnetic data storage and spintronic devices. Two-dimensional magnets allow for control of magnetic properties using the electric field, electrostatic doping and strain. In two-dimensional atomically thin magnets, a non-volatile all-optical method would offer the distinct advantage of switching magnetic states without application of an external field. Here, we demonstrate such all-optical magnetization switching in the atomically thin ferromagnetic semiconductor, CrI3, triggered by circularly polarized light pulses. The magnetization switching behaviour strongly depends on the exciting photon energy and polarization, in correspondence with excitonic transitions in CrI3, indicating that the switching process is related to spin angular momentum transfer from photoexcited carriers to local magnetic moments. Such an all-optical magnetization switching should allow for further exploration of magneto-optical interactions and open up applications in high-speed and low-power spintronic devices.

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H2S+ Cations.

A comprehensive understanding of dissociation mechanisms is of fundamental importance in the photochemistry of small molecules. Here, we investigated the detailed photodissociation dynamics of H2S+ near 337 nm by using the velocity map ion imaging technique together with the theoretical characterizations by developing global full-dimensional potential energy surfaces (PESs). Rotational state resolved images were acquired for the S+(4S) + H2 product channel. Significant changes in product total kinetic energy release distributions and angular distributions have been observed within a small excitation photon energy range of 5 wavenumbers. Analysis based on the full-dimensional PESs reveals that two nonadiabatic pathways determined by the transition state connecting two minima on the 12A' state are responsible for the dramatic variation of observed product distributions. The current study has directly witnessed the competitive photodissociation mechanisms controlled by a critical energy point on the PES, thereby providing in-depth insight into the nonadiabatic dynamics in photochemistry.

Singlet Fission, Polaron Generation and Intersystem Crossing in Hexaphenyl Film.

The ultrafast dynamics of triplet excitons and polarons in hexaphenyl film was investigated by time-resolved fluorescence and femtosecond transient absorption techniques under various excitation photon energies. Two distinct pathways of triplet formation were clearly observed. Long-lived triplet states are populated within 4.5 ps via singlet fission-intersystem crossing, while the short-lived triplet states (1.5 ns) are generated via singlet fission from vibrational electronic states. In the meantime, polarons were formed from hot excitons on a timescale of <30 fs and recombined in ultrafast lifetime (0.37 ps). In addition, the characterization of hexaphenyl film suggests the morphologies of crystal and aggregate to wide applications in organic electronic devices. The present study provides a universally applicable film fabrication in hexaphenyl system towards future singlet fission-based solar cells.

Disentangling Many-Body Effects in the Coherent Optical Response of 2D Semiconductors.

In single-layer (1L) transition metal dichalcogenides, the reduced Coulomb screening results in strongly bound excitons which dominate the linear and the nonlinear optical response. Despite the large number of studies, a clear understanding on how many-body and Coulomb correlation effects affect the excitonic resonances on a femtosecond time scale is still lacking. Here, we use ultrashort laser pulses to measure the transient optical response of 1L-WS2. In order to disentangle many-body effects, we perform exciton line-shape analysis, and we study its temporal dynamics as a function of the excitation photon energy and fluence. We find that resonant photoexcitation produces a blue shift of the A exciton, while for above-resonance photoexcitation the transient response at the optical bandgap is largely determined by a reduction of the exciton oscillator strength. Microscopic calculations based on excitonic Heisenberg equations of motion quantitatively reproduce the nonlinear absorption of the material and its dependence on excitation conditions.

Optimum excitation wavelength and photon energy threshold for spintronic terahertz emission from Fe/Pt bilayer

SummaryTerahertz emission from ferromagnetic/non-magnetic spintronic heterostructures had been demonstrated as pump wavelength-independent. We report, however, the pump wavelength dependence of terahertz emission from an optimized Fe/Pt spintronic bilayer on MgO substrate. Maximum terahertz generation per total pump power was observed in the 1200- to 1800-nm pump wavelength range, and a marked decrease in the terahertz emission efficiency beyond 2500 nm (pump photon energies <0.5 eV) suggests a ∼0.35-eV threshold pump photon energy for effective spintronic terahertz emission. The inferred threshold is supported by previous theoretical results on the onset energy of significant spin-filtering at the Fe-Pt interface, and confirmed by Fe/Pt electronic structure calculations in this present work. The results of terahertz time-domain emission spectroscopy show the sensitivity of spintronic terahertz emission to both the optical absorptance of the heterostructure and the energy-dependent spin transport, as dictated by the properties of the metallic thin films.

Quantifying Hot Electron Energy Contributions in Plasmonic Photocatalysis Using Electrochemical Surface-Enhanced Raman Spectroscopy.

Due to the challenge in measuring hot electron energy under reaction conditions, very few studies focus on experimental determination of hot carrier energy. Here, we adjust the energy state of free electrons in Au nanoparticles to quantify the hot electron energy in plasmonic photocatalysis. Reactant molecules with different reduction potentials such as 4-nitrothiophenol (4-NTP), 4-iodothiophenol (4-ITP), etc. are chosen as molecular probes to investigate the reducing ability of hot electrons. By comparing the voltage required to achieve the same conversion of photo- and electro-reaction pathways, we calibrate the maximum energy efficiency of hot electrons in 4-NTP reduction to be 0.32 eV, which is much lower than the excitation photon energy of 1.96 eV. Our work provides insight into the energy distribution of hot electrons and will be helpful for rational design of highly efficient plasmon-mediated chemical reactions.

Photocycle of point defects in highly- and weakly-germanium doped silica revealed by transient absorption measurements with femtosecond tunable pump

We report pump-probe transient absorption measurements addressing the photocycle of the Germanium lone pair center (GLPC) point defect with an unprecedented time resolution. The GLPC is a model point defect with a simple and well-understood electronic structure, highly relevant for several applications. Therefore, a full explanation of its photocycle is fundamental to understand the relaxation mechanisms of such molecular-like systems in solid state. The experiment, carried out exciting the sample resonantly with the ultraviolet (UV) GLPC absorption band peaked at 5.1 eV, gave us the possibility to follow the defect excitation-relaxation dynamics from the femto-picosecond to the nanosecond timescale in the UV–visible range. Moreover, the transient absorption signal was studied as a function of the excitation photon energy and comparative experiments were conducted on highly- and weakly-germanium doped silica glasses. The results offer a comprehensive picture of the relaxation dynamics of GLPC and allow observing the interplay between electronic transitions localized on the defect and those related to bandgap transitions, providing a clear evidence that the role of dopant high concentration is not negligible in the earliest dynamics.

Anti-Stokes photoluminescence from CsPbBr3 nanostructures embedded in a Cs4PbBr6 crystal

Lead halide perovskites possess high photoluminescence (PL) efficiency and strong electron-phonon interactions, and therefore the optical cooling using up-conversion PL has been expected. We investigate anti-Stokes PL from green-luminescent Cs$_4$PbBr$_6$, whose origin is attributable to CsPbBr3 nanostructures embedded in a Cs$_4$PbBr$_6$ crystal. Because of the high transparency, low refractive index, and high stability of Cs$_4$PbBr$_6$, the green PL displays high external quantum efficiency without photo-degradation. Time-resolved PL spectroscopy reveals the excitonic behaviors in recombination process. The shape of the PL spectrum is almost independent of excitation photon energy, which means that the spectral width is determined by homogeneous broadening. We demonstrate that the phonon-assisted process dominates the Urbach tail of optical absorption and anti-Stokes PL at room temperature. Anti-Stokes PL is observed down to 70 K. We determine the temperature dependence of the Urbach energy and estimate the strength of the electron-phonon coupling. Our spectroscopic data show that CsPbBr3 nanostructures have potentially useful features for optical cooling.

Nonlinear optical properties of spherical MoS2/TiO2 composite at visible wavelengths

Optical nonlinear absorption and refraction of spherical MoS2/TiO2 nanocomposites were measured using Z-scan and spatial self-phase modulation (SSPM) at different wavelengths. The linear absorption spectra showed that MoS2/TiO2 nanocomposite had obvious absorption at 500–700 nm, which was mainly attributed to the shape of MoS2 and demonstrated by the finite-difference time-domain method. For nonlinear absorption, MoS2/TiO2 composite showed enhanced two-photon absorption with high photon energy excitation (400 nm), and a tunable saturated single-photon absorption with low photon energy excitation (700 nm). For nonlinear refraction, it had no SSPM signal with short wavelength, but enhanced SSPM signal with long wavelength in visible band. These unconventional phenomena can be explained by the change of main absorber and the reversal of carriers transfer direction together.

Fabrication and characterization of Se/WO3 heterojunctions designed as terahertz/gigahertz dielectric resonators

In this work, Selenium (Se) thin film substrates are coated with tungsten oxide thin layers. The Se/WO3 interfaces are fabricated using a vacuum deposition technique. The substrates displayed stable polycrystalline structure of hexagonal selenium when coated with amorphous WO3. The surface morphology revealed preferred growth of Se nanowires. The coating of Se with WO3 enhanced the light absorbability in the visible and infrared ranges of light spectrum. In addition, the Se/WO3 heterojunctions exhibited conduction and valence band offsets of values of 1.31 eV and 0.0.09 eV, respectively. The band offsets are sufficiently large to force quantum confinement at the interface. It was observed that Se/WO3 behaves as good dielectric resonator revealing resonance peaks in the infrared, visible and ultraviolet ranges of light. Moreover, computing the optical conductivity parameters for these dielectric oscillators revealed drift mobility and plasmon frequency values that are suitable for optical communications. Furthermore, as a terahertz resonator, the Se/WO3 dielectric media displayed terahertz cutoff frequency values in the range of 0.6–75 THz depending on the exciting photon energy. As practical application, when photo-excited with daylight light, the carbon contacted planner Se/WO3 interfaces displayed a light power dependent photosensitivity. The photosensitivity increases 38 times upon irradiation of 0.9 W. With these features, the Se/WO3 heterojunction devices can be nominated for applications in optical communications.

Interfacing g-C3N4 Nanosheets with CdS Nanorods for Enhanced Photocatalytic Hydrogen Evolution: An Ultrafast Investigation.

Effective separation of electron-hole and utilization of hot charge carriers are known to be the most important factors influencing the activity of a good photocatalyst. Herein, we developed a 1D/2D heterojunction in the composite of CdS nanorod and g-C3N4 (CN) nanosheets. These two form a quasi-type-II junction at the heterointerface. The photoexcited electrons are supposed to be transferred from CN to CdS, as observed from the enhanced photoluminescence of CdS. Transient studies revealed an absolute dominance of CdS exciton formation even in the composite system, although the dynamics were substantially modified in the presence of CN. The rise time of CdS band edge excitons were increased in the composite material, owing to the migration of hot electrons from CN to CdS. The hot electron transfer time was found to be ∼0.5 ps (rate constant ∼1.98 ps-1). The excitons decay in a much slower manner than that of the pristine CdS, confirming enhanced electron population in CdS. This migration of charge carriers was found to be immensely dependent on the applied excitation photon energy. Efficient migration of charge carriers leads to enhanced photocatalytic activity in the composite and an increased evolution of H2 evolution rate was witnessed. This detailed spectroscopic study toward the mechanistic pathway of the catalytic activity of an 1D/2D heterocomposite would be immensely helpful in fabricating many other effective heterojunctions which will advance the catalysis research.

Time-resolved luminescence spectroscopy of ultrafast emissions in BaGeF6

Phase-pure crystalline micropowder samples of BaGeF6 were prepared and studied under excitation by tuneable synchrotron radiation and 10 keV electron beam. Time-resolved photoluminescence emission and excitation spectra and a set of single emission decay curves were recorded at 7 K for the exciting photon energy region of 4.3–45 eV. Several intrinsic emissions were revealed in BaGeF6 and their origin investigated. A single broad emission band peaking at 455 nm is assigned to be of excitonic origin due to its long decay time in the μs range and due to the presence of an intense excitation peak at 10.1 eV right in the region of the host absorption onset. The energy gap width of BaGeF6 was determined experimentally from the photoluminescence excitation spectra of the 455 nm emission to be 10.9 eV. Several emission bands, including distinct peaks at 270 and 455 nm, with the main decay component of ∼180 ps were revealed across the wavelength range of 200–500 nm. The revealed ultrafast emissions were studied by means of time-resolved photoluminescence spectroscopy and their origin was assigned to cross-luminescence resulting from radiative transitions between the Ba 5p core level and sub-bands of the valence band (Ge 4s, Ge 4p and F 2p hybridized states) and to intraband luminescence between the valence band sub-bands. Photoluminescence excitation spectra of the ultrafast emissions revealed a gently sloping onset at 17 eV, related to transitions from the Ge 4s states. It is followed by a distinct peak at 19.4 eV, which corresponds to the ionization of the Ba 5p cation states and is related to the excitation threshold of cross-luminescence.

Anisotropic Second-Harmonic Generation Induced by Reduction of In-Plane Symmetry in 2D Materials with Strain Engineering.

Strain engineering is an attractive method to induce and control anisotropy for polarized optoelectronic applications with two-dimensional (2D) materials. Herein, we have investigated the nonlinear optical coefficient dispersion relationship and the second-harmonic generation (SHG) pattern evolution under the uniaxial strains for graphene, WS2, GaSe, and In2Se3 monolayers. The uniaxial strain can break the in-plane symmetry of 2D materials, leading to both trade-off breaking of the nonlinear coefficient and new emergent nonlinear coefficients. In such a case, a classical sixfold ϕ-dependent SHG pattern is transformed into a distorted sixfold SHG pattern under the strain. Due to the lattice symmetry breaking and the uneven charge density distribution in strained 2D materials, the SHG patterns also depend on the excitation photon energy. The results could give a guide for the SHG pattern analysis in experiments, suggesting strain engineering on 2D materials for the tunable anisotropy in polarized and flexible nonlinear optical devices.

Expanding the momentum field of view in angle-resolved photoemission systems with hemispherical analyzers.

In photoelectron spectroscopy, the measured electron momentum range is intrinsically related to the excitation photon energy. Low photon energies <10 eV are commonly encountered in laser-based photoemission and lead to a momentum range that is smaller than the Brillouin zones of most materials. This can become a limiting factor when studying condensed matter with laser-based photoemission. An additional restriction is introduced by widely used hemispherical analyzers that record only electrons photoemitted in a solid angle set by the aperture size at the analyzer entrance. Here, we present an upgrade to increase the effective solid angle that is measured with a hemispherical analyzer. We achieve this by accelerating the photoelectrons toward the analyzer with an electric field that is generated by a bias voltage on the sample. Our experimental geometry is comparable to a parallel plate capacitor, and therefore, we approximate the electric field to be uniform along the photoelectron trajectory. With this assumption, we developed an analytic, parameter-free model that relates the measured angles to the electron momenta in the solid and verify its validity by comparing with experimental results on the charge density wave material TbTe3. By providing a larger field of view in momentum space, our approach using a bias potential considerably expands the flexibility of laser-based photoemission setups.

Using the inelastic background in hard x-ray photoelectron spectroscopy for a depth-resolved analysis of the CdS/Cu(In,Ga)Se2 interface

The inelastic background of hard x-ray photoelectron spectroscopy data is analyzed to paint a depth-resolved picture of the CdS/Cu(In,Ga)Se2 (CdS/CIGSe) layer structure. The CdS/CIGSe interface is the central component in next-generation chalcopyrite thin-film photovoltaic devices. By analyzing both, the (unscattered) core-level peaks and the inelastic background, and by varying the excitation photon energy from 2.1 up to 14 keV, we can derive photoemission information over a broad range of electron kinetic energies and, hence, sampling depths. With this complementary information, the CdS film thickness of a CdS/CIGSe interface can be accurately determined as a function of the CdS deposition time. For the thinner CdS films, the film thickness can be shown to vary laterally. Furthermore, small amounts of Se and process-related Rb can be detected in a thin (∼2 nm) surface layer of all investigated CdS films.

High-yield helicity-resolved Raman scattering with in-plane propagation of light in monolayer MoS2

In-plane propagation of excited light in layered materials boosts the observation of novel phenomena, which differ from out-of-plane propagation. In this work, we perform the Raman study with light propagation parallel to the plane of layered MoS2. The Raman signal is unveiled at least an order of magnitude larger than that perpendicular to the plane when the excitation photon energy at ∼2.81 eV. We attribute this high-yield Raman spectra to the stronger photon–exciton coupling with in-plane propagation of light. Furthermore, we show that the exciton-mediated phonon excitation in the first-order Raman process is dominant with consideration of angular momentum transfer between phonons and photons through the measurements of the circularly polarized Raman spectra. This experimental setup configuration paves a way with high efficiency to investigate the phonon information in layered materials.

Reversible photochromic and photoluminescence in iodide perovskites

Color imaging experiment demonstrates a photochromic behavior of mixed-halide perovskites upon dark and light excitation, while the color emitted by the crystals changes from red to yellow and vice versa with the intensity of excitation light source. Unlike the photochromic property commonly observed in solution-state polymer materials, solid-state perovskite materials with photochromic behavior might open wide applications in consumer products and electronic devices. In the next part, we report on a reversible photoluminescence (PL) peak in iodide-based organic-inorganic lead halide perovskite materials under a 2-photon absorption process, while tuning the excitation wavelength. Intriguingly, two shorter wavelength peaks are visible and become prominent when the excitation photon energy is being tuned in the high energy spectrum, while laser power is remained constant. The same phenomenon of reversible PL peak is also observed in various iodine-based organic-inorganic halides as well as all-inorganic perovskite single crystals and polycrystals. We attribute to the reversible PL peak phenomenon to the photoinduced structural deformation and the associated change in the optical bandgap of iodide perovskites under the femtosecond laser excitation. Our findings will introduce a degree of freedom in future research as well as adding functionalities to optoelectronic applications in these emerging perovskite materials-based devices.

First-principles and experiment investigation of Bi2O3/Bi2WO6 heterojunctions

In this study, a one-step hydrothermal synthesis method was used to prepare Bi2O3/Bi2WO6 heterojunction photocatalyst, and modern advanced characterization methods were used to characterize the material composition and physical properties of the material. 10%-Bi2O3/Bi2WO6 showed the best photocatalytic ability at 240 min, which was 68.16%, which was a big improvement compared to Bi2O3(43.86%) and Bi2WO6(48.33%). Through the first-order reaction kinetics simulation, the reaction rates of Bi2O3, Bi2WO6, and 10%-Bi2O3/Bi2WO6 are k = 0.00282 min−1, k = 0.00283 min−1 and k = 0.00468 min−1. 10%-Bi2O3/Bi2WO6, respectively the reaction rate is 1.66 times that of the former two, and it still has high catalytic activity after 4 cycles of experiments. In addition, using the density functional theory method, the Bi2O3, Bi2WO6 and Bi2O3(001)/Bi2WO6(0 0 1) heterojunction models were constructed, and the energy band structures of Bi2O3, Bi2WO6 and Bi2O3/Bi2WO6 heterojunctions were systematically calculated band structure and density of states. The results show that the band gap of Bi2O3/Bi2WO6 heterojunction is significantly lower than that of intrinsic Bi2O3 and Bi2WO6, which is conducive to reducing the photon excitation energy and improving the light absorption capacity. Theoretical calculation combined with experimental analysis shows that the formation of heterojunction leads to a narrower band gap, enhances the absorption in the visible light region, improves the separation efficiency of photo-generated electrons and holes, and enhances the photocatalytic performance.