Orientational ordering of nonplanar phthalocyanines on Cu(111): strength and orientation of the electric dipole moment.

In order to investigate the orientational ordering of molecular dipoles and the associated electronic properties, we studied the adsorption of chlorogallium phthalocyanine molecules (GaClPc, Pc=C32N8H16(-2) on Cu(111) by using the x-ray standing wave technique, photoelectron spectroscopy, and quantum mechanical calculations. We find that for submonolayer coverages on Cu(111) the majority of GaClPc molecules adsorb in a Cl-down configuration by forming a covalent bond to the substrate. For bilayer coverages the x-ray standing wave data indicate a coexistence of the Cl-down and Cl-up configurations on the substrate. The structural details established for both cases and supplementary calculations of the adsorbate system allow us to analyze the observed change of the work function.

Structure and morphology of coevaporated pentacene-perfluoropentacene thin films.

The structural properties of coevaporated thin films of pentacene (PEN) and perfluoropentacene (PFP) on SiO(2) were studied using x-ray reflectivity and grazing incidence x-ray diffraction. Reciprocal space maps of the coevaporated thin films with different volume fractions reveal the coexistence of two different molecular mixed PEN-PFP phases together with the pure PEN and PFP crystallites. The crystal structure of PEN:PFP blends does not change continuously with volume fraction, instead the proportion of the appropriate phases changes, as seen from the diffraction analysis. Additional temperature dependent experiments reveal that the fraction of the two mixed PEN-PFP phases varies with growth temperature. The λ-phase (molecular plane parallel to the substrate) is metastable and induced by low growth temperature. The σ-phase (molecular plane nearly perpendicular to the substrate) is thermally stable and nucleates predominantly at high growth temperatures.

Site-specific geometric and electronic relaxations at organic-metal interfaces.

The correlation between the geometric and electronic structures of Zn-phthalocyanine (ZnPc) and F16ZnPc on Cu(111) were studied by x-ray standing wave and angle-resolved photoemission spectroscopy. We found evidence for a distortion of the planar molecules upon adsorption, with the central Zn atom in the molecule protruding towards the substrate. This modifies the energy levels of both the molecule and the substrate, which appear as interface states. The site-specific geometric and electronic relaxations are an important effect for organic-metal interface energetics.

Well-Ordered 4CzIPN ((4s,6s)-2,4,5,6-Tetra(9-H-carbazol-9-yl)isophthalonitrile) Layers: Molecular Orientation, Electronic Structure, and Angular Distribution of Photoluminescence.

We fabricated a well-ordered homogeneous monolayer of disk-shaped, carbazolyl dicyanobenzene (CDCB)-based thermally activated delayed fluorescence (TADF) molecule, i.e., 4CzIPN((4s,6s)-2,4,5,6-tetra(9Hcarbazol-9-yl)isophthalonitrile) at room temperature on flat Ag(111), Au(111), and Cu(111) surfaces. The second layer of the 4CzIPN was also found to be well ordered. The electronic states of the well-ordered monolayer and multilayer of 4CzIPN were found to be nearly unchanged from that of the isolated molecule calculated by the density functional theory (DFT), suggesting that the ordered layers retain the TADF properties. Indeed, we demonstrated the delayed fluorescence and the nearly perfect in-plane alignment of the transition dipole moment of a 4CzIPN thin film on glass substrate even in an ambient condition. These results indicate that the well-ordered films of the disc-shaped carbazole-based TADF molecules could potentially be utilized in organic light-emitting diode (OLED) devices with high light outcoupling efficiency.

Control of the interchain pi-pi interaction and electron density distribution at the surface of conjugated poly(3-hexylthiophene) thin films.

Interchain interaction, i.e., pi-pi stacking, can benefit the carrier transport in conjugated regio-regular poly(3-hexylthiophene) (P3HT) thin films. However, the existence of the insulating side hexyl chains in the surface region may be detrimental to the charge transfer between the polymer backbone and overlayer molecules. The control of the molecular orientation in the surface region is expected to alter the distribution of the pi electron density at the surface to solve such problems, which can be achieved by controlling the solvent removal rate during solidification. The evidence that the pi-electron density distribution at the outermost surface can be controlled is demonstrated by the investigation using the powerful combination of near edge X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, and the most surface-sensitive technique: Penning ionization electron spectroscopy. From the spectroscopic studies, it can be deduced that the slower removal rate of the solvent makes the polymer chains even at the surface have sufficient time to adopt a more nearly equilibrium structure with edge-on conformation. Thus, the side hexyl chains extend outside the surface, which buries the pi-electron density contributed from the polymer backbone. Contrarily, the quench of obtaining a thermo-equilibrium structure in the surface region due to the faster removal of the solvent residual can lead to the surface chain conformation without persisting to the strong bulk orientation preference. Therefore, the face-on conformation of the polymer chain at the surface of thin films coated with high spin coating speed facilitate the electron density of the polymer backbone exposed outside the surface. Finally, thickness dependence of the surface electronic structure of P3HT thin films is also discussed.

Orientation-Dependent Work-Function Modification Using Substituted Pyrene-Based Acceptors.

The adsorption of molecular acceptors is a viable method for tuning the work function of metal electrodes. This, in turn, enables adjusting charge injection barriers between the electrode and organic semiconductors. Here, we demonstrate the potential of pyrene-tetraone (PyT) and its derivatives dibromopyrene-tetraone (Br-PyT) and dinitropyrene-tetraone (NO2-PyT) for modifying the electronic properties of Au(111) and Ag(111) surfaces. The systems are investigated by complementary theoretical and experimental approaches, including photoelectron spectroscopy, the X-ray standing wave technique, and density functional theory simulations. For some of the investigated interfaces the trends expected for Fermi-level pinning are observed, i.e., an increase of the metal work function along with increasing molecular electron affinity and the same work function for Au and Ag with monolayer acceptor coverage. Substantial deviations are, however, found for Br-PyT/Ag(111) and NO2-PyT/Ag(111), where in the latter case an adsorption-induced work function increase of as much as 1.6 eV is observed. This behavior is explained as arising from a face-on to edge-on reorientation of molecules in the monolayer. Our calculations show that for an edge-on orientation much larger work-function changes can be expected despite the prevalence of Fermi-level pinning. This is primarily ascribed to a change of the electron affinity of the adsorbate layer that results from a change of the molecular orientation. This work provides a comprehensive understanding of how changing the molecular electron affinity as well as the adsorbate structure impacts the electronic properties of electrodes.

Note: Single-shot time-domain spectroscopy and spatial profiling of terahertz pulses from intense laser systems.

Single-shot terahertz time-domain spectroscopy is presented with directly encoded spatial resolution. A single reflective echelon and multiple semi-cylindrical lenses are used to obtain both the temporal waveform and the spatial distribution of the terahertz field. This system can be used to rapidly characterize terahertz pulses generated by high power pulsed laser systems, which themselves suffer from large pulse energy and spectrum fluctuations.

Highly efficient terahertz radiation from a thin foil irradiated by a high-contrast laser pulse.

Radially polarized intense terahertz (THz) radiation behind a thin foil irradiated by ultrahigh-contrast ultrashort relativistic laser pulse is recorded by a single-shot THz time-domain spectroscopy system. As the thickness of the target is reduced from 30 to 2 µm, the duration of the THz emission increases from 5 to over 20 ps and the radiation energy increases dramatically, reaching ∼10.5mJ per pulse, corresponding to a laser-to-THz radiation energy conversion efficiency of 1.7%. The efficient THz emission can be attributed to reflection (deceleration and acceleration) of the laser-driven hot electrons by the target-rear sheath electric field. The experimental results are consistent with that of a simple model as well as particle-in-cell simulation.

Electron acceleration by a nonlinear wakefield generated by ultrashort (23-fs) high-peak-power laser pulses in plasma.

We study experimentally the interaction of the shortest at present (23-fs) , relativistically intense (20-TW), tightly focused laser pulses with underdense plasma. MeV electrons constitute a two-temperature distribution due to different plasma wave-breaking processes at a plasma density of 10(20) cm(-3). These two groups of electrons are shown numerically to constitute bunches with very distinctive time durations.

Nonlinear increase of X-ray intensities from thin foils irradiated with a 200 TW femtosecond laser.

We report, for the first time, that the energy of femtosecond optical laser pulses, E, with relativistic intensities I > 10(21) W/cm(2) is efficiently converted to X-ray radiation, which is emitted by "hot" electron component in collision-less processes and heats the solid density plasma periphery. As shown by direct high-resolution spectroscopic measurements X-ray radiation from plasma periphery exhibits unusual non-linear growth ~E(4-5) of its power. The non-linear power growth occurs far earlier than the known regime when the radiation reaction dominates particle motion (RDR). Nevertheless, the radiation is shown to dominate the kinetics of the plasma periphery, changing in this regime (now labeled RDKR) the physical picture of the laser plasma interaction. Although in the experiments reported here we demonstrated by observation of KK hollow ions that X-ray intensities in the keV range exceeds ~10(17) W/cm(2), there is no theoretical limit of the radiation power. Therefore, such powerful X-ray sources can produce and probe exotic material states with high densities and multiple inner-shell electron excitations even for higher Z elements. Femtosecond laser-produced plasmas may thus provide unique ultra-bright X-ray sources, for future studies of matter in extreme conditions, material science studies, and radiography of biological systems.

Optical-field-ionization effects on the propagation of an ultraintense laser pulse in high- Z gas jets.

Interaction of an ultraintense, a(0) >>1, laser pulse with an underdense Ar plasma is analyzed via a two-dimensional particle-in-cell simulation which self-consistently includes optical-field ionization. In spite of rapid growth of ion charge Z and, hence, electron density at the laser front, relativistic self-focusing is shown to persist owing to a reduction of the expected plasma defocusing resulting from the weak radial dependence of the ion charge on laser intensity (even for Z/gamma>1 where gamma is the electron relativistic factor).

Charged and metallic molecular monolayers through surface-induced aromatic stabilization.

Large π-conjugated molecules, when in contact with a metal surface, usually retain a finite electronic gap and, in this sense, stay semiconducting. In some cases, however, the metallic character of the underlying substrate is seen to extend onto the first molecular layer. Here, we develop a chemical rationale for this intriguing phenomenon. In many reported instances, we find that the conjugation length of the organic semiconductors increases significantly through the bonding of specific substituents to the metal surface and through the concomitant rehybridization of the entire backbone structure. The molecules at the interface are thus converted into different chemical species with a strongly reduced electronic gap. This mechanism of surface-induced aromatic stabilization helps molecules to overcome competing phenomena that tend to keep the metal Fermi level between their frontier orbitals. Our findings aid in the design of stable precursors for metallic molecular monolayers, and thus enable new routes for the chemical engineering of metal surfaces.

High-resolution gamma-ray radiography produced by a laser-plasma driven electron source.

An electron beam from a laser-plasma accelerator is converted into a gamma-ray source using bremsstrahlung radiation in a dense material. The gamma-ray beam has a pointlike source size because it is generated by a high quality electron beam with a small source size and a low divergence. Using this gamma-ray source, the radiography of complex and dense objects with submillimeter resolution is performed. It is the first evidence of a gamma-ray source size of a few hundreds micrometers produced with laser-driven accelerators. This size is consistent with results from Monte Carlo simulations.

Observation of laser-pulse shortening in nonlinear plasma waves.

We have measured the temporal shortening of an ultraintense laser pulse interacting with an underdense plasma. When interacting with strongly nonlinear plasma waves, the laser pulse is shortened from 38 +/- 2 fs to the 10-14 fs level, with a 20% energy efficiency. The laser ponderomotive force excites a wakefield, which, along with relativistic self-phase modulation, broadens the laser spectrum and subsequently compresses the pulse. This mechanism is confirmed by 3D particle in cell simulations.

Optical guidance of terrawatt laser pulses by the implosion phase of a fast Z-pinch discharge in a gas-filled capillary.

A new method of optical guidance by the implosion phase of a fast Z-pinch discharge in a gas-filled capillary is proposed. An imploding plasma column has a concave electron-density profile in the radial direction, just before a stagnation phase driven by a converging current sheet and a shock wave. The feasibility of optical guidance of a high-intensity (>1 x 10(17) W/cm(2)) Ti:sapphire laser pulse by use of this method over a distance of 2 cm, corresponding to 12.5 times the Rayleigh length, has been experimentally demonstrated. The guiding-channel formation process was directly probed with a He-Ne laser beam. The electron density in the fully ionized channel was estimated to be 2.0 x 10(17) cm(-3) on the axis and 7.0 x 10(17) cm(-3) on the peaks of the channel edge, with a diameter of 70 mum, as indicated by the experimental results, which were corroborated by a magnetohydrodynamics simulation.

Energetic protons from a few-micron metallic foil evaporated by an intense laser pulse.

With detailed experimental studies and hydrodynamics and particle-in-cell simulations we investigate the role of the prepulse in laser proton acceleration. The prepulse or pedestal (amplified spontaneous emission) can completely evaporate the irradiated region of a sufficiently thin foil; therefore, the main part of the laser pulse interacts with an underdense plasma. The multiparametric particle-in-cell simulations demonstrate that the main pulse generates the quasistatic magnetic field, which in its turn produces the long-lived charge separation electrostatic field, accelerating the ions.