Direct and real-time observation of hole transport dynamics in anatase TiO2 using X-ray free-electron laser.

Carrier dynamics affects photocatalytic systems, but direct and real-time observations in an element-specific and energy-level-specific manner are challenging. In this study, we demonstrate that the dynamics of photo-generated holes in metal oxides can be directly probed by using femtosecond X-ray absorption spectroscopy at an X-ray free-electron laser. We identify the energy level and life time of holes with a long life time (230 pico-seconds) in nano-crystal materials. We also observe that trapped holes show an energy distribution in the bandgap region with a formation time of 0.3 pico-seconds and a decay time of 8.0 pico-seconds at room temperature. We corroborate the dynamics of the electrons by using X-ray absorption spectroscopy at the metal L-edges in a consistent explanation with that of the holes.

Hole Dynamics in Photoexcited Hematite Studied with Femtosecond Oxygen K-edge X-ray Absorption Spectroscopy.

Hematite (α-Fe2O3) is a photoelectrode for the water splitting process because of its relatively narrow bandgap and abundance in the earth's crust. In this study, the photoexcited state of a hematite thin film was investigated with femtosecond oxygen K-edge X-ray absorption spectroscopy (XAS) at the PAL-XFEL in order to follow the dynamics of its photoexcited states. The 200 fs decay time of the hole state in the valence band was observed via its corresponding XAS feature.

Investigation of Nonequilibrium Electronic Dynamics of Warm Dense Copper with Femtosecond X-Ray Absorption Spectroscopy.

Ultrafast optical excitation of matter leads to highly excited states that are far from equilibrium. In this study, femtosecond x-ray absorption spectroscopy was used to visualize the ultrafast dynamics in photoexcited warm dense Cu. The rich dynamical features related to d vacancies are observed on femtosecond timescales. Despite the success in explaining x-ray absorption data in the picosecond regime, the new femtosecond data are poorly understood through the traditional two-temperature model based on the fast thermalization concept and the static electronic structure for high-temperature metals. An improved understanding can be achieved by including the recombination dynamics of nonthermal electrons and changes in the screening of the excited d block. The population balance between the 4sp and 3d bands is mainly determined by the recombination rate of nonthermal electrons, and the underpopulated 3d block is initially strongly downshifted and recovered in several hundreds of femtoseconds.

Femtosecond Charge Density Modulations in Photoexcited CuWO4.

Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.

Carrier-specific dynamics in 2H-MoTe2 observed by femtosecond soft x-ray absorption spectroscopy using an x-ray free-electron laser.

Femtosecond carrier dynamics in layered 2H-MoTe2 semiconductor crystals have been investigated using soft x-ray transient absorption spectroscopy at the x-ray free-electron laser (XFEL) of the Pohang Accelerator Laboratory. Following above-bandgap optical excitation of 2H-MoTe2, the photoexcited hole distribution is directly probed via short-lived transitions from the Te 3d 5/2 core level (M5-edge, 572-577 eV) to transiently unoccupied states in the valence band. The optically excited electrons are separately probed via the reduced absorption probability at the Te M5-edge involving partially occupied states of the conduction band. A 400 ± 110 fs delay is observed between this transient electron signal near the conduction band minimum compared to higher-lying states within the conduction band, which we assign to hot electron relaxation. Additionally, the transient absorption signals below and above the Te M5 edge, assigned to photoexcited holes and electrons, respectively, are observed to decay concomitantly on a 1-2 ps timescale, which is interpreted as electron-hole recombination. The present work provides a benchmark for applications of XFELs for soft x-ray absorption studies of carrier-specific dynamics in semiconductors, and future opportunities enabled by this method are discussed.

Time-resolved resonant elastic soft x-ray scattering at Pohang Accelerator Laboratory X-ray Free Electron Laser.

Resonant elastic x-ray scattering has been widely employed for exploring complex electronic ordering phenomena, such as charge, spin, and orbital order, in particular, in strongly correlated electronic systems. In addition, recent developments in pump-probe x-ray scattering allow us to expand the investigation of the temporal dynamics of such orders. Here, we introduce a new time-resolved Resonant Soft X-ray Scattering (tr-RSXS) endstation developed at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). This endstation has an optical laser (wavelength of 800 nm plus harmonics) as the pump source. Based on the commissioning results, the tr-RSXS at PAL-XFEL can deliver a soft x-ray probe (400 eV-1300 eV) with a time resolution of ∼100 fs without jitter correction. As an example, the temporal dynamics of a charge density wave on a high-temperature cuprate superconductor is demonstrated.

Femtosecond soft X-ray absorption spectroscopy of warm dense matter at the PAL-XFEL.

Free-electron laser pulse-based X-ray absorption spectroscopy measurements on warm dense copper are presented. The incident X-ray pulse energies were measured with a detector assembly consisting of a photocathode membrane and microchannel plates, and the transmitted energies were measured simultaneously with a photodiode detector. The precision of the absorption measurements was evaluated. For a warm dense copper foil irradiated by an intense femtosecond laser pulse, the enhanced X-ray absorption below the L3-edge, followed by the rapid evolution of highly excited Fermi liquid within a picosecond, were successfully measured. This result demonstrates a unique capability to study femtosecond non-equilibrium electron-hole dynamics in extreme states of matter.

Direct observation of the electronic states of photoexcited hematite with ultrafast 2p3d X-ray absorption spectroscopy and resonant inelastic X-ray scattering.

Hematite, α-Fe2O3, is an important semiconductor for photoelectrochemical water splitting. Its low charge carrier mobility and the presence of midgap states provide favourable conditions for electron-hole recombination, hence affecting the semiconductor's photoelectrochemical efficiency. The nature of the excited state and charge carrier transport in hematite is strongly debated. In order to further understand the fundamental properties of the hematite photoexcited state, we conducted femtosecond 2p (L3) X-ray absorption (XAS) and 2p3d resonant inelastic scattering (RIXS) measurements on hematite thin-films at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). The observed spectral changes and kinetic processes are in agreement with previous 3p XAS reports. The potential additional information that could be acquired from 2p3d RIXS experiments is also discussed.

Scientific instruments for soft X-ray photon-in/photon-out spectroscopy on the PAL-XFEL.

An overview is given of the soft X-ray photon-in/photon-out instruments on the free-electron laser (FEL) beamline at the Pohang Accelerator Laboratory, and selected commissioning results are presented. The FEL beamline provides a photon energy of 270 to 1200 eV, with an energy bandwidth of 0.44%, an energy of 200 µJ per pulse and a pulse width of <50 fs (full width at half-maximum). The estimated total time resolution between optical laser and X-ray pulses is <100 fs. Instruments for X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) have been set up. X-ray magnetic circular dichroism spectra for a Co/Pt multilayer film and RIXS spectra for α-Fe2O3(100) have been obtained and the performance of the spectrometer has been evaluated.

Closing the Surface Bandgap in Thin Bi2Se3/Graphene Heterostructures.

Topological insulator (TI), a band insulator with topologically protected edge states, is one of the most interesting materials in the field of condensed matter. Bismuth selenide (Bi2Se3) is the most spotlighted three-dimensional TI material; it has a Dirac cone at each top and bottom surface and a relatively wide bandgap. For application, suppression of the bulk effect is crucial, but in ultrathin TI materials, with thicknesses less than 3 QL, the finite size effect works on the linear dispersion of the surface states, so that the surface band has a finite bandgap because of the hybridization between the top and bottom surface states and Rashba splitting, resulting from the structure inversion asymmetry. Here, we studied the gapless top surface Dirac state of strained 3 QL Bi2Se3/graphene heterostructures. A strain caused by the graphene layer reduces the bandgap of surface states, and the band bending resulting from the charge transfer at the Bi2Se3-graphene interface induces localization of surface states to each top and bottom layer to suppress the overlap of the two surface states. In addition, we verified the independent transport channel of the top surface Dirac state in Bi2Se3/graphene heterostructures by measuring the magneto-conductance. Our findings suggest that the strain and the proximity effect in TI/non-TI heterostructures may be feasible ways to engineer the topological surface states beyond the physical and topological thickness limit.

PAL-XFEL soft X-ray scientific instruments and X-ray optics: First commissioning results.

We report an overview of soft X-ray scientific instruments and X-ray optics at the free electron laser (FEL) of the Pohang Accelerator Laboratory, with selected first-commissioning results. The FEL exhibited a pulse energy of 200 µJ/pulse, a pulse width of <50 fs full width at half maximum, and an energy bandwidth of 0.44% at a photon energy of 850 eV. Monochromator resolving power of 10 500 was achieved. The estimated total time resolution between optical laser and X-ray pulses was <270 fs. A resonant inelastic X-ray scattering spectrometer was set up; its commissioning results are also reported.

Modeling angle-resolved photoemission of graphene and black phosphorus nano structures.

Angle-resolved photoemission spectroscopy (ARPES) data on electronic structure are difficult to interpret, because various factors such as atomic structure and experimental setup influence the quantum mechanical effects during the measurement. Therefore, we simulated ARPES of nano-sized molecules to corroborate the interpretation of experimental results. Applying the independent atomic-center approximation, we used density functional theory calculations and custom-made simulation code to compute photoelectron intensity in given experimental setups for every atomic orbital in poly-aromatic hydrocarbons of various size, and in a molecule of black phosphorus. The simulation results were validated by comparing them to experimental ARPES for highly-oriented pyrolytic graphite. This database provides the calculation method and every file used during the work flow.

Dynamics of Molecular Orientation Observed Using Angle Resolved Photoemission Spectroscopy during Deposition of Pentacene on Graphite.

A real-time method to observe both the structural and the electronic configuration of an organic molecule during deposition is reported for the model system of pentacene on graphite. Structural phase transition of the thin films as a function of coverage is monitored by using in situ angle resolved photoemission spectroscopy (ARPES) results to observe the change of the electronic configuration at the same time. A photoemission theory that uses independent atomic center approximations is introduced to identify the molecular orientation from the ARPES technique. This study provides a practical insight into interpreting ARPES data regarding dynamic changes of molecular orientation during initial growth of molecules on a well-defined surface.

Tuning the Fermi level with topological phase transition by internal strain in a topological insulator Bi2Se3 thin film.

In a three-dimensional topological insulator Bi2Se3, a stress control for band gap manipulation was predicted but no systematic investigation has been performed yet due to the requirement of large external stress. We report herein on the strain-dependent results for Bi2Se3 films of various thicknesses that are grown via a self-organized ordering process. Using small angle X-ray scattering and Raman spectroscopy, the changes of d-spacings in the crystal structure and phonon vibration shifts resulted from stress are clearly observed when the film thickness is below ten quintuple layers. From the UV photoemission/inverse photoemission spectroscopy (UPS/IPES) results and ab initio calculations, significant changes of the Fermi level and band gap were observed. The deformed band structure also exhibits a Van Hove singularity at specific energies in the UV absorption experiment and ab initio calculations. Our results, including the synthesis of a strained ultrathin topological insulator, suggest a new direction for electronic and spintronic applications for the future.

Wafer-scale synthesis of thickness-controllable MoS2 films via solution-processing using a dimethylformamide/n-butylamine/2-aminoethanol solvent system.

The wafer-scale synthesis of two-dimensional molybdenum disulfide (MoS2) films, with high layer-controllability and uniformity, remains a significant challenge in the fields of nano and optoelectronics. Here, we report the highly thickness controllable growth of uniform MoS2 thin films on the wafer-scale via a spin-coating route. Formulation of a dimethylformamide-based MoS2 precursor solution mixed with additional amine- and amino alcohol-based solvents (n-butylamine and 2-aminoethanol) allowed for the formation of a uniform coating of MoS2 thin films over a 2 inch wafer-scale SiO2/Si substrate. In addition, facile control of the average number of stacking layers is demonstrated by simply manipulating the concentration of the precursor solution. Various characterization results reveal that the synthesized MoS2 film has wafer-scale homogeneity with excellent crystalline quality and a stoichiometric chemical composition. To further demonstrate possible device applications, a mostly penta-layered MoS2 thin film was integrated into a top-gated field-effect transistor as the channel layer and we also successfully transferred our films onto transparent/flexible substrates.

Reversible Fermi Level Tuning of a Sb2Te3 Topological Insulator by Structural Deformation.

For three-dimensional (3D) topological insulators that have a layered structure, strain was used to control critical physical properties. Here, we show that tensile strain decreases bulk carrier density while accentuating transport of topological surface state using temperature-dependent resistance and magneto-resistance measurements, terahertz-time domain spectroscopy and density functional theory calculations. The induced strain was confirmed by transmittance X-ray scattering measurements. The results show the possibility of reversible topological surface state device control using structural deformation.

Hydrogen sensing under ambient conditions using SnO2 nanowires: synergetic effect of Pd/Sn codeposition.

Semiconducting SnO2 nanowires deposited with Pd and Sn nanoparticles on their surface are shown to be a highly sensitive hydrogen sensor with fast response time at room temperature. Compared with the SnO2 nanowire deposited with Pd or Sn nanoparticles alone, the Pd/Sn-deposited SnO2 nanowire exhibits a significant improvement in the sensitivity and reversibility of sensing hydrogen gas in the air at room temperature. Our investigation indicates that two factors are responsible for the synergistic effect of Pd/Sn codeposition on SnO2 nanowires. One is that in the presence of Pd the oxidation of Sn nanoparticles on the surface of the SnO2 nanowire is incomplete leading only to suboxides SnOx (1 ≤ x < 2), and the other is that the surface of the Pd/Sn-deposited SnO2 nanowire is almost perfectly hydrophobic.

Improved growth behavior of atomic-layer-deposited high-k dielectrics on multilayer MoS2 by oxygen plasma pretreatment.

We report on the effect of oxygen plasma treatment of two-dimensional multilayer MoS2 crystals on the subsequent growth of Al2O3 and HfO2 films, which were formed by atomic layer deposition (ALD) using trimethylaluminum and tetrakis-(ethylmethylamino)hafnium metal precursors, respectively, with water oxidant. Due to the formation of an ultrathin Mo-oxide layer on the MoS2 surface, the surface coverage of Al2O3 and HfO2 films was significantly improved compared to those on pristine MoS2, even at a high ALD temperature. These results indicate that the surface modification of MoS2 by oxygen plasma treatment can have a major impact on the subsequent deposition of high-k thin films, with important implications on their integration in thin film transistors.

Folic acid-tethered Pep-1 peptide-conjugated liposomal nanocarrier for enhanced intracellular drug delivery to cancer cells: conformational characterization and in vitro cellular uptake evaluation.

BACKGROUND: A novel dual ligand-modified liposome, folic acid-tethered Pep-1 peptide-conjugated liposomal nanocarrier (FP-Lipo), was designed to overcome the nonselectivity of conventional penetrating peptide-tagged nanoparticulates and to provide the advantage of selective targeting of the folic acid receptor, which is frequently overexpressed on epithelial cancer cells. METHODS: FP-Lipo was prepared by a sequential process of formation of a maleimide-derivatized small unilamellar vesicle, postinsertion of distearoyl phosphatidyl ethanolamine-polyethylene glycol 2000-folate to the vesicle, and Pep-1 peptide conjugation via thiol-maleimide linkage. Conformational and physical characteristics of the FP-Lipo nanocarriers were investigated for the extent of Pep-1 peptide and folic acid on the surface, vesicle size, and zeta potential. In vitro cellular uptake behaviors of the novel carrier containing a fluorescein dextran isothiocyanate probe were examined by spectrophotometry or by confocal laser scanning microscopy. RESULTS: A novel nanocarrier bearing approximately 750 folate ligands and 100 penetrating peptides per vesicle was successfully prepared. The physical properties were as follows: 140 nm in size; 5 mV in zeta potential; less than 0.3 in polydispersity index. An in vitro cellular uptake study revealed that the FP-Lipo nanocarrier system exhibited more than twofold enhanced translocation into the folic acid receptor-positive HeLa cells compared with the single Pep-1 peptide-modified liposome. Meanwhile, its cellular association and internalization into the folic acid receptor-negative normal HaCaT cells was comparable with that of Pep-1 peptide-modified liposome. CONCLUSION: An advanced dual ligand-modified liposome is potentially useful for the treatment of folic acid receptor-positive tumors with high translocation capability of the penetrating peptide-modified liposome.

Tat peptide-admixed elastic liposomal formulation of hirsutenone for the treatment of atopic dermatitis in NC/Nga mice.

BACKGROUND: The aim of the present study was to enhance a topical delivery of hirsutenone (HST), a naturally occuring immunomodulator, employing Tat peptide-admixed elastic liposomes (EL/T). METHODS: HST-loaded EL, consisting of phosphatidylcholine and Tween 80 (85:15 w/w%), were prepared using thin film hydration method. By adding Tat peptide to EL (0.16 w/w%), EL/T were formulated. The in vitro skin permeation of HST was examined using a Franz diffusion cell mounted with depilated mouse skin. Lesions for atopic dermatitis (AD) were induced by a topical application of diphenylcyclopropenone to NC/Nga mice. Therapeutic improvements of AD were evaluated by clinical skin severity scores. Immunological analyses on inducible nitric oxide synthase and cyclooxygenase-2 levels in the skin and interleukin (IL)-4, IL-13, immunoglobulin E, and eosinophil levels in the blood were also performed. RESULTS: EL systems were superior to conventional cream, revealing greater flux values in a permeation study. The addition of Tat peptide further increased the skin permeation of HST. In an efficacy study with AD-induced NC/Nga mice, an HST-containing EL/T formulation brought a significant improvement in both skin severity score and immune-related responses for the levels of nitric oxide synthase, cyclooxygenase-2, IL-4, IL-13, immunoglobulin E, and eosinophils. CONCLUSION: A novel EL/T formulation was successfully developed for topical delivery of HST to treat AD.