K-point longitudinal acoustic phonons are responsible for ultrafast intervalley scattering in monolayer MoSe2.

In transition metal dichalcogenides, valley depolarization through intervalley carrier scattering by zone-edge phonons is often unavoidable. Although valley depolarization processes related to various acoustic phonons have been suggested, their optical verification is still vague due to nearly degenerate phonon frequencies on acoustic phonon branches at zone-edge momentums. Here we report an unambiguous phonon momentum determination of the longitudinal acoustic (LA) phonons at the K point, which are responsible for the ultrafast valley depolarization in monolayer MoSe2. Using sub-10-fs-resolution pump-probe spectroscopy, we observed coherent phonons signals at both even and odd-orders of zone-edge LA mode involved in intervalley carrier scattering process. Our phonon-symmetry analysis and first-principles calculations reveal that only the LA phonon at the K point, as opposed to the M point, can produce experimental odd-order LA phonon signals from its nonlinear optical modulation. This work will provide momentum-resolved descriptions of phonon-carrier intervalley scattering processes in valleytronic materials.

2-step reaction kinetics for hydrogen absorption into bulk material via dissociative adsorption on the surface.

We have demonstrated that the process of hydrogen absorption into a solid experimentally follows a Langmuir-type (hyperbolic) function instead of Sieverts law. This can be explained by independent two theories. One is the well-known solubility theory which is the basis of Sieverts law. It explains that the amount of hydrogen absorption can be expressed as a Langmuir-type (hyperbolic) function of the square root of the hydrogen pressure. We have succeeded in drawing the same conclusion from the other theory. It is a 2-step reaction kinetics (2sRK) model that expresses absorption into the bulk via adsorption on the surface. The 2sRK model has an advantage to the solubility theory: Since it can describe the dynamic process, it can be used to discuss both the amount of hydrogen absorption and the absorption rate. Some phenomena with absorption via adsorption can be understood in a unified manner by the 2sRK model.

Model of local hydrogen permeability in stainless steel with two coexisting structures.

The dynamics of hydrogen in metals with mixed grain structure is not well understood at a microscopic scale. One of the biggest issues facing the hydrogen economy is "hydrogen embrittlement" of metal induced by hydrogen entering and diffusing into the material. Hydrogen diffusion in metallic materials is difficult to grasp owing to the non-uniform compositions and structures of metal. Here a time-resolved "operando hydrogen microscope" was used to interpret local diffusion behaviour of hydrogen in the microstructure of a stainless steel with austenite and martensite structures. The martensite/austenite ratios differed in each local region of the sample. The path of hydrogen permeation was inferred from the time evolution of hydrogen permeation in several regions. We proposed a model of hydrogen diffusion in a dual-structure material and verified the validity of the model by simulations that took into account the transfer of hydrogen at the interfaces.

Terahertz-induced acceleration of massive Dirac electrons in semimetal bismuth.

Dirac-like electrons in solid state have been of great interest since they exhibit many peculiar physical behaviors analogous to relativistic mechanics. Among them, carriers in graphene and surface states of topological insulators are known to behave as massless Dirac fermions with a conical band structure in the two-dimensional momentum space, whereas electrons in semimetal bismuth (Bi) are expected to behave as massive Dirac-like fermions in the three-dimensional momentum space, whose dynamics is of particular interest in comparison with that of the massless Dirac fermions. Here, we demonstrate that an intense terahertz electric field transient accelerates the massive Dirac-like fermions in Bi from classical Newtonian to the relativistic regime; the electrons are accelerated approaching the effective "speed of light" with the "relativistic" beta ß = 0.89 along the asymptotic linear band structure. As a result, the effective electron mass is enhanced by a factor of 2.4.

Terahertz-field-induced nonlinear electron delocalization in Au nanostructures.

Improved control over the electromagnetic properties of metal nanostructures is indispensable for the development of next-generation integrated nanocircuits and plasmonic devices. The use of terahertz (THz)-field-induced nonlinearity is a promising approach to controlling local electromagnetic properties. Here, we demonstrate how intense THz electric fields can be used to modulate electron delocalization in percolated gold (Au) nanostructures on a picosecond time scale. We prepared both isolated and percolated Au nanostructures deposited on high resistivity Si(100) substrates. With increasing the applied THz electric fields, large opacity in the THz transmission spectra takes place in the percolated nanostructures; the maximum THz-field-induced transmittance difference, 50% more, is reached just above the percolation threshold thickness. Fitting the experimental data to a Drude-Smith model, we found furthermore that the localization parameter and the damping constant strongly depend on the applied THz-field strength. These results show that ultrafast nonlinear electron delocalization proceeds via strong electric field of THz pulses; the intense THz electric field modulates the backscattering rate of localized electrons and induces electron tunneling between Au nanostructures across the narrow insulating bridges without any material breakdown.

Stress inversion from initial tensile to compressive side during ultrathin oxide growth of the Si(100) surface.

We report the real-time observation of the stress change during sub-nanometer oxide growth on the Si(100) surface. Oxidation initially induced a rapid buildup of tensile stress up to -1.9 × 10(8) N m(-2) with an oxide thickness of 0.25 nm, followed by gradual compensation by a compressive stress. The compressive stress saturated at 5 × 10(7) N m(-2) for an oxide thickness of 1.2 nm. The analysis, assisted by theoretical study, indicates that the observed initial tensile stress is caused by oxygen bridge-bonding between the Si dimers. Atomistic model calculations considering mutually orthogonal orientations of the Si(100) surface structure reproduce the stress inversion from the tensile to the compressive side.

The effect of n- and p-type doping on coherent phonons in GaN.

The effect of doping on the carrier-phonon interaction in wurtzite GaN is investigated by pump-probe reflectivity measurements using 3.1 eV light in near resonance with the fundamental band gap of 3.39 eV. Coherent modulations of the reflectivity due to the E2 and A1(LO) modes, as well as the 2A1(LO) overtone are observed. Doping of acceptor and donor atoms enhances the dephasing of the polar A1(LO) phonon via coupling with plasmons, with the effect of donors being stronger. Doping also enhances the relative amplitude of the coherent A1(LO) phonon with respect to that of the high-frequency E2 phonon, though it does not affect the relative intensity in Raman spectroscopic measurements. We attribute this enhanced coherent amplitude to the transient depletion field screening (TDFS) excitation mechanism, which, in addition to impulsive stimulated Raman scattering (ISRS), contributes to the generation of coherent polar phonons even for sub-band gap excitation. Because the TDFS mechanism requires photoexcitation of carriers, we argue that the interband transition is made possible at a surface with photon energies below the bulk band gap through the Franz-Keldysh effect.

Spatial distribution of enhanced optical fields in one-dimensional linear arrays of gold nanoparticles studied by scanning near-field optical microscopy.

We visualized the enhanced optical field distributions in one-dimensional linear array structures of gold nanospheres by using scanning near-field optical microscopy. The characteristic field distribution depends on the chain length of the one-dimensional structures. The distribution of optical field is reproduced qualitatively by model calculations based upon finite-difference time-domain (FDTD) method. From the analysis, we have found that the characteristic distribution of the enhanced field arises from interparticle interactions, which cause propagation of the plasmon excitation in the inner part of the linear array, and trapping of it by a localized mode at the edges.

Ultrafast dynamics of surface-enhanced Raman scattering due to Au nanostructures.

Ultrafast dynamics of surface-enhanced Raman scattering (SERS) was investigated at cleaved graphite surfaces bearing deposited gold (Au) nanostructures (∼10 nm in diameter) by using sensitive pump-probe reflectivity spectroscopy with ultrashort (7.5 fs) laser pulses. We observed enhancement of phonon amplitudes (C═C stretching modes) in the femtosecond time domain, considered to be due to the enhanced electromagnetic (EM) field around the Au nanostructures. Finite-difference time-domain (FDTD) calculations confirmed the EM enhancement. The enhancement causes drastic increase of coherent D-mode (40 THz) phonon amplitude and nanostructure-dependent changes in the amplitude and dephasing time of coherent G-mode (47 THz) phonons. This methodology should be suitable to study the basic mechanism of SERS and may also find application in nanofabrication.

Transcriptional regulation of the terephthalate catabolism operon in Comamonas sp. strain E6.

Two almost identical gene clusters, tphR(I)C(I)A2(I)A3(I)B(I)A1(I) and tphR(II)C(II)A2(II)A3(II)B(II)A1(II), are responsible for the conversion of terephthalate (TPA) to protocatechuate in Comamonas sp. strain E6. In the present study, we investigated the transcriptional regulation of the tphR(II)C(II)A2(II)A3(II)B(II)A1(II) gene cluster. Reverse transcription-PCR analysis suggested that the tphR(II)C(II)A2(II)A3(II)B(II)A1(II) genes form two transcriptional units, the tphC(II)A2(II)A3(II)B(II)A1(II) catabolism operon and tphR(II), with the latter encoding an IclR-type transcriptional regulator (ITTR). The transcription start site of the tph(II) catabolism operon was mapped at 21 nucleotides upstream of the initiation codon of tphC(II). The lacZ transcriptional fusion experiments showed that tphR(II) encodes a transcriptional activator of the tph(II) catabolism operon and that TPA acts as an inducer. On the other hand, TphR(II) appeared to repress its own transcription regardless of the presence of TPA. The analysis of mutant derivatives of E6 indicated that tphR(II) is essential for the transcriptional activation of the tph(II) catabolism operon and the growth on TPA of a tph(I)-deficient derivative of E6. Purified His-tagged TphR(II) bound specifically to the tphR(II)-tphC(II) intergenic region containing a 21-bp inverted repeat sequence. Alignment of the inverted repeat sequences in the binding sites for TphR(II) and other members of ITTRs revealed highly conserved nucleotides. The substitution of conserved nucleotides resulted in significantly reduced TPA-dependent transcriptional activation from the tphC(II) promoter and reduced binding to His-tagged TphR(II). These results clearly indicate that the conserved nucleotides are required for the inducible expression of the tph(II) catabolism operon regulated by TphR(II).

Interaction of coherent phonons with defects and elementary excitations.

We present an overview of the feasibility of using coherent phonon spectroscopy to study interaction dynamics of excited lattice vibrations with their environments. By exploiting the features of coherent phonons with a pump-probe technique, one can study lattice motions in a sub-picosecond time range. The dephasing properties tell us not only about interaction dynamics with carriers (electrons and holes) or thermal phonons but also about point defects in crystals. Modulations of the coherent phonon amplitude by more than two modes are closely related to phonon-carrier or phonon-phonon interferences. Related to this phenomenon, formation of coherent phonons at higher harmonics gives direct evidence for phonon-phonon couplings. A combined study of coherent phonons and ultrafast carrier response can be useful for understanding phonon-carrier interaction dynamics. For metals like zinc, nonequilibrium electrons may dominate the dynamics of both relaxation and generation of coherent phonons. The frequency chirp of coherent phonons can be a direct measure of how and when phonon-phonon and phonon-carrier couplings occur. Carbon nanotubes show some complicated behavior due to the existence of many modes with different symmetries, resulting in superposition or interference. To illustrate one of the most interesting applications, the selective excitation of specific phonon modes through the use of a pulse train technique is shown.

Coherent phonon anisotropy in aligned single-walled carbon nanotubes.

By time-resolved reflectivity measurements with sub-10 fs laser pulses at 395 nm, the coherent phonons of aligned bundles of single-walled carbon nanotubes are observed for various polarization directions of the pump and probe pulses. In the isotropic reflectivity measurement, we observe the radial breathing modes, G, and even D modes, while in the anisotropic reflectivity mode, only the G mode appears. A complex polarization dependence of the G band phonon amplitude in the isotropic reflectivity is explained by the superposition of G band phonons with different symmetries.

Near-field Raman imaging and electromagnetic field confinement in the self-assembled monolayer array of gold nanoparticles.

Spatial distribution of surface enhanced Raman activity is visualized for two-dimensional (2D) nearly close-packed and well-ordered monolayer array of gold nanoparticles by using scanning near-field optical microscope. The 2D arrays exhibit highly nonuniform enhancement in Raman scattering, i.e., the regions along the edge of the 2D array are preferentially enhanced. We demonstrate that the spatial distribution of the localized electric field is also nonuniform and agrees well with that of the Raman enhancement.

Visualization of localized intense optical fields in single gold-nanoparticle assemblies and ultrasensitive Raman active sites.

We demonstrate visualization of localized intense electromagnetic fields in real space in well-tailored dimeric and trimeric gold nanospheres by using near-field optical techniques. With two-photon induced luminescence and Raman measurements, we show that the electric field is confined at an interstitial site in the aggregate. We also demonstrate optical switching operations for the electric-field localized sites in the trimer structure.

Effects of strain on the dissociation dynamics of O2 on Si(001).

There are two distinctive channels in the dissociation reaction of O2 on Si(001)-(2 x 1): a trapping-mediated channel and a direct-activated channel. Externally applied tensile strain along the <110> direction on the (001) surface is found to suppress the dissociation via a direct-activated channel and to enhance that via a trapping-mediated channel in the temperature range between 200 and 300 K. It has been demonstrated that the dissociation dynamics involving elementary processes such as inelastic scattering and trapping, desorption and/or dissociation from a trapping precursor, and direct dissociation are sensitively influenced by the strain to change the branching ratio of the dissociation reaction.

The birth of a quasiparticle in silicon observed in time-frequency space.

The concept of quasiparticles in solid-state physics is an extremely powerful tool for describing complex many-body phenomena in terms of single-particle excitations. Introducing a simple particle, such as an electron, hole or phonon, deforms a many-body system through its interactions with other particles. In this way, the added particle is 'dressed' or 'renormalized' by a self-energy cloud that describes the response of the many-body system, so forming a new entity--the quasiparticle. Using ultrafast laser techniques, it is possible to impulsively generate bare particles and observe their subsequent dressing by the many-body interactions (that is, quasiparticle formation) on the time and energy scales governed by the Heisenberg uncertainty principle. Here we describe the coherent response of silicon to excitation with a 10-femtosecond (10(-14) s) laser pulse. The optical pulse interacts with the sample by way of the complex second-order nonlinear susceptibility to generate a force on the lattice driving coherent phonon excitation. Transforming the transient reflectivity signal into frequency-time space reveals interference effects leading to the coherent phonon generation and subsequent dressing of the phonon by electron-hole pair excitations.

Dynamics of coherent anharmonic phonons in bismuth using high density photoexcitation.

We have investigated the dynamical properties of the coherent anharmonic phonons generated in Bi under high density excitation. The time-resolved reflectivity in the intensely photoexcited Bi film is modulated by the coherent A(1g) phonon oscillation with a time-dependent oscillation period. As the pump power density is increased, the line shape of the A(1g) mode in the Fourier transformed spectra becomes asymmetric, and the redshift of the phonon frequency is observed. Analysis of the transient redshift with a wavelet transform reveals that the frequency of the A(1g) mode depends on the squared amplitude of the oscillation, which is attributed to an anharmonicity of the lattice potential.