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Promising applications in photonics are driven by the ability to fabricate crystal-quality metal thin films of controlled thickness down to a few nanometers. In particular, these materials exhibit a highly nonlinear response to optical fields owing to the induced ultrafast electron dynamics, which is however poorly understood on such mesoscopic length scales. Here, we reveal a new mechanism that controls the nonlinear optical response of thin metallic films, dominated by ultrafast electronic heat transport when the thickness is sufficiently small. By experimentally and theoretically studying electronic transport in such materials, we explain the observed temporal evolution of photoluminescence in pump-probe measurements that we report for crystalline gold flakes. Incorporating a first-principles description of the electronic band structures, we model electronic transport and find that ultrafast thermal dynamics plays a pivotal role in determining the strength and time-dependent characteristics of the nonlinear photoluminescence signal, which is largely influenced by the distribution of hot electrons and holes, subject to diffusion across the film as well as relaxation to lattice modes. Our findings introduce conceptually novel elements triggering the nonlinear optical response of nanoscale materials while suggesting additional ways to control and leverage hot carrier distributions in metallic films., Comment: 20 pages, 6 figures, 64 references

Immense field enhancement and nanoscale confinement of light are possible within nanoparticle-on-mirror (NPoM) plasmonic resonators, which enable novel optically-activated physical and chemical phenomena, and render these nanocavities greatly sensitive to minute structural changes, down to the atomic scale. Although a few of these structural parameters, primarily linked to the nanoparticle and the mirror morphology, have been identified, the impact of molecular assembly and organization of the spacer layer between them has often been left uncharacterized. Here, we experimentally investigate how the complex and reconfigurable nature of a thiol-based self-assembled monolayer (SAM) adsorbed on the mirror surface impacts the optical properties of the NPoMs. We fabricate NPoMs with distinct molecular organizations by controlling the incubation time of the mirror in the thiol solution. Afterwards, we investigate the structural changes that occur under laser irradiation by tracking the bonding dipole plasmon mode, while also monitoring Stokes and anti-Stokes Raman scattering from the molecules as a probe of their integrity. First, we find an effective decrease in the SAM height as the laser power increases, compatible with an irreversible change of molecule orientation caused by heating. Second, we observe that the nanocavities prepared with a densely packed and more ordered monolayer of molecules are more prone to changes in their resonance compared to samples with sparser and more disordered SAMs. Our measurements indicate that molecular orientation and packing on the mirror surface play a key role in determining the stability of NPoM structures and hence highlight the under-recognized significance of SAM characterization in the development of NPoM-based applications.

The accurate determination of electronic temperatures in metallic nanostructures is essential for many technological applications, like plasmon-enhanced catalysis or lithographic nanofabrication procedures. In this Letter, we demonstrate that the electronic temperature can be accurately measured by the shape of the tunnel electroluminescence emission edge in tunnel plasmonic nanocavities, which follows a universal thermal distribution with the bias voltage as the chemical potential of the photon population. A significant deviation between electronic and lattice temperatures is found below 30 K for tunnel currents larger than 15 nA. This deviation is rationalized as the result of a two-electron process in which the second electron excites plasmon modes with an energy distribution that reflects the higher temperature following the first tunneling event. These results dispel a long-standing controversy on the nature of overbias emission in tunnel junctions and adds a new method for the determination of electronic temperatures and quasiparticle dynamics., R.M. and R.O. acknowledge financial support from the Spanish Ministry for Economy and Competitiveness (Grants PGC2018-098613-B-C21, PGC2018-096047-B-I00), the regional government of Comunidad de Madrid (Grant S2018/NMT-4321), Universidad Autónoma de Madrid (UAM/48) and IMDEA Nanoscience. Both IMDEA Nanoscience and IFIMAC acknowledge support from the Severo Ochoa and Maria de Maeztu Programmes for Centres and Units of Excellence in R&D (MINECO, Grants SEV-2016-0686 and CEX2018-000805-M). R.O. acknowledges support from the excellence programme Echegaray, funded by the regional government of Madrid. A.A. and V.M.S. acknowledge support from the Spanish Ministry of Science and Innovation (Grants Nos. PID2019-103910GB-I00 and PID2019-105488GB-I00, respectively) and from the Projects of the Basque Government for consolidated groups of the Basque University, through the Department of Universities (Grant Nos. IT-1246-19 and IT-1164-19, respectively).

An effective approach to improve the detection efficiency of nanoscale light sources relies on a planar antenna configuration, which beams the emitted light into a narrow cone. Planar antennas operate like optical Yagi-Uda antennas, where reflector and director elements are made of metal films. Here we introduce and investigate, both theoretically and experimentally, a scanning implementation of a planar antenna. Using a small ensemble of molecules contained in fluorescent nanobeads placed in the antenna, we independently address the intensity, radiation pattern, and decay rate as a function of distance between a flat-tip scanning gold wire (reflector) and a thin gold film coated on a glass coverslip (director). The scanning planar antenna changes the radiation pattern of a single fluorescent bead, and it beams light into a narrow cone down to angles of 45 ∘ (full width at half maximum). Moreover, the collected signal compared to the case of a glass coverslip is larger than a factor of three, which is mainly due to the excitation enhancement. These results offer a better understanding of the modification of light–matter interaction by planar antennas, and they hold promise for applications such as sensing, imaging, and diagnostics.

Fluoride-based compounds doped with rare-earth cations are the preferred choice of materials to achieve efficient upconversion, of interest for a plethora of applications ranging from bioimaging to energy harvesting. Herein, we demonstrate a simple route to fabricate bright upconverting films that are transparent, self-standing, flexible, and emit different colors. Starting from the solvothermal synthesis of uniform and colloidally stable yttrium fluoride nanoparticles doped with Yb3+ and Er3+, Ho3+, or Tm3+, we find the experimental conditions to process the nanophosphors as optical quality films of controlled thickness between few hundreds of nanometers and several micrometers. A thorough analysis of both structural and photophysical properties of films annealed at different temperatures reveals a tradeoff between the oxidation of the matrix, which transitions through an oxyfluoride crystal phase, and the efficiency of the upconversion photoluminescence process. It represents a significant step forward in the understanding of the fundamental properties of upconverting materials and can be leveraged for the optimization of upconversion systems in general. We prove bright multicolor upconversion photoluminescence in oxyfluoride-based phosphor transparent films upon excitation with a 980 nm laser for both rigid and flexible versions of the layers, being possible to use the latter to coat surfaces of arbitrary shape. Our results pave the way toward the development of upconverting coatings that can be conveniently integrated in applications that demand a large degree of versatility.

GeSn alloys have been regarded as a potential lasing material for a complementary metal-oxide-semiconductor (CMOS)-compatible light source. Despite their remarkable progress, all GeSn lasers reported to date have large device footprints and active areas, which prevent the realization of densely integrated on-chip lasers operating at low power consumption. Here, we present a 1D photonic crystal (PC) nanobeam with a very small device footprint of 7 ${\mu}m^2$ and a compact active area of ~1.2 ${\mu}m^2$ on a high-quality GeSn-on-insulator (GeSnOI) substrate. We also report that the improved directness in our strain-free nanobeam lasers leads to a lower threshold density and a higher operating temperature compared to the compressive strained counterparts. The threshold density of the strain-free nanobeam laser is ~18.2 kW cm$^{ -2}$ at 4 K, which is significantly lower than that of the unreleased nanobeam laser (~38.4 kW cm$^{ -2}$ at 4 K). Lasing in the strain-free nanobeam device persists up to 90 K, whereas the unreleased nanobeam shows a quenching of the lasing at a temperature of 70 K. Our demonstration offers a new avenue towards developing practical group-IV light sources with high-density integration and low power consumption., Comment: 14 pages, 6 figures

The ever-stronger attention paid to enhancing safety in the workplace has led to novel sensor development and improvement. Despite the technological progress, nanostructured sensors are not being commercially transferred due to expensive and non-microelectronic compatible materials and processing approaches. In this paper, the realization of a cost-effective sensor based on ultrathin silicon nanowires (Si NWs) for the detection of nitrogen dioxide (NO2) is reported. A modification of the metal-assisted chemical etching method allows light-emitting silicon nanowires to be obtained through a fast, low-cost, and industrially compatible approach. NO2 is a well-known dangerous gas that, even with a small concentration of 3 ppm, represents a serious hazard for human health. We exploit the particular optical and electrical properties of these Si NWs to reveal low NO2 concentrations through their photoluminescence (PL) and resistance variations reaching 2 ppm of NO2. Indeed, these Si NWs offer a fast response and reversibility with both electrical and optical transductions. Despite the macro contacts affecting the electrical transduction, the sensing performances are of high interest for further developments. These promising performances coupled with the scalable Si NW synthesis could unfold opportunities for smaller sized and better performing sensors reaching the market for environmental monitoring.

International audience; 2-Dimensional metal Halide Perovskites (2D-HP) are at the limelight for their potential exploitation in light-emission related applications. In particular, the most-investigated

Luminescent multifunctional nanomaterials are important because of their potential impact on the development of key technologies such as smart luminescent sensors and solid-state lightings. To be technologically viable, the luminescent material needs to fulfil a number of requirements such as facile and cost-effective fabrication, a high quantum yield, structural robustness, and long-term material stability. To achieve these requirements, an eco-friendly and scalable synthesis of a highly photoluminescent, multistimuli responsive and electroluminescent silver-based metal-organic framework (Ag-MOF), termed "OX-2" was developed. Its exceptional photophysical and mechanically resilient properties that can be reversibly switched by temperature and pressure make this material stood out over other competing luminescent materials. The potential use of OX-2 MOF as a good electroluminescent material was tested by constructing a proof-of-concept MOF-LED (light emitting diode) device, further contributing to the rare examples of electroluminescent MOFs. The results reveal the huge potential for exploiting the Ag MOF as a multitasking platform to engineer innovative photonic technologies., 33 pages, 7 figures, Supplementary Information

Theoretical simulations are necessary to scientifically progress, envisage and gain the first hand knowledge of the properties of semiconductor quantum dot (QD) structure. The impact of dual ternary-quaternary/quaternary-ternary capping layers on the square based truncated pyramidal InAs QD and their influence on the energy band structure as well as the strain profile has been investigated in this study. A comparative analysis has been demonstrated with binary, ternary and quaternary capping layer counterparts. The capping layers are: GaAs (binary), InGaAs/GaAs (ternary), InAlGaAs/GaAs (quaternary), InGaAs/InAlGaAs/GaAs (dual ternary-quaternary) and InAlGaAs/InGaAs/GaAs (dual quaternary-ternary). The hydrostatic and biaxial strain for all the heterostructures have also been computed and compared. The biaxial strain was highest for the QD capped with InAlGaAs/GaAs and InAlGaAs/InGaAs/GaAs, leading to the red shift of the ground state emission in the photoluminescence (PL) spectrum. The possible absorption peaks were also calculated for all QDs from the electron (EL) and hole (HL) eigenstates. The lowest energy transition (EL1-HL1) at 300 K is near to the communication wavelength for the optimum (InAlGaAs/InGaAs/GaAs capped) QD, which is at 1.35 µm. The optimized QD heterostructure claimed the highest electrostatic potential of 0.4986 V. This study will be helpful in predicting few optical and electrical characteristics based on the strain distribution inside the structure. The optimized QD structure having a consistent strain profile inside it would render superior luminescence characteristics. Finally, to verify the accuracy of the simulation, the simulated transition peaks at 19 K and 300 K were validated with the experimental PL data, and the percentage error was within 5%.

Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum efficiencies of polycrystalline perovskite films from 1% to 89%, with carrier lifetimes of 32 μs and diffusion lengths of 77 μm, comparable with perovskite single crystals. Remarkably, the surface recombination velocity of holes in the treated films is 0.4 cm/s, approaching the values for fully passivated crystalline silicon, which has the lowest values for any semiconductor to date. The enhancements translate to solar cell power-conversion efficiencies of 19.2%, with a near-instant rise to stabilized power output, consistent with suppression of ion migration. We propose a mechanism in which light creates superoxide species from oxygen that remove shallow surface states. The work reveals an industrially scalable post-treatment capable of producing state-of-the-art semiconducting films. Metal halide perovskites are exciting materials for low-cost optoelectronic devices such as solar cells and LEDs. In order to reach the theoretical efficiency limits for both applications, any parasitic non-radiative charge-carrier recombination losses, such as those mediated by carrier trapping, must be eliminated. At present, perovskite materials still suffer from substantial non-radiative decay, particularly under solar illumination conditions, and are therefore yet to reach their full potential. Perovskite single crystals have very low trap concentrations but their controlled growth into devices does not lend themselves to the advantages offered by solution-processing thin films such as roll-to-roll depositions. Here, we demonstrate the use of light and atmospheric treatments on polycrystalline perovskite films, resulting in minimal non-radiative losses and properties approaching those of perovskite single crystals and even the best crystalline semiconductors reported to date. The authors demonstrate the use of light and atmospheric treatments on polycrystalline perovskite thin films, resulting in properties approaching those of the best crystalline semiconductors reported to date. The results translate to exceptional photovoltaic device performances with rapid rises to stabilized power output consistent with an inhibition of ionic migration.

The effect of the capping layer and the number of strain-coupled stacks on the optoelectrical properties of In0.5Ga0.5As quantum dot infrared photodetectors (QDIPs) are reported in this paper. GaAs-capped and InGaAs-capped bilayer, trilayer, pentalayer, and heptalayer QDIPs were grown for the first time and analyzed. The ground-state photoluminescence emission of all coupled QDIPs redshifted relative to that of the uncoupled QDIPs. All coupled InGaAs-capped QDIPs exhibited monomodal spectral response, whereas among GaAs-capped QDIPs, only the bilayer QDIP exhibited monomodal response. The optimal activation energy (339.87 meV) and full width at half maximum (FWHM; 16 meV) as well as the lowest dark current density (6.5E−8 A/cm2) at 100 K, and −1 V bias were observed for the InGaAs-capped trilayer QDIP among all due to better dot confinement, homogeneity, and also better strain coupling between the vertically stacks QD layers. The peak spectral response at 7.08 µm obtained from this QDIP had an ultranarrow FWHM of 8.67 meV, making it useful for hyperspectral applications in the infrared region.

The identification of a complete three-dimensional (3D) photonic band gap in real crystals always employs theoretical or numerical models that invoke idealized crystal structures. Thus, this approach is prone to false positives (gap wrongly assigned) or false negatives (gap missed). Therefore, we propose a purely experimental probe of the 3D photonic band gap that pertains to many different classes of photonic materials. We study position and polarization-resolved reflectivity spectra of 3D inverse woodpile structures that consist of two perpendicular nanopore arrays etched in silicon. We observe intense reflectivity peaks $(R > 90\%)$ typical of high-quality crystals with broad stopbands. We track the stopband width versus pore radius, which agrees much better with the predicted 3D photonic band gap than with a directional stop gap on account of the large numerical aperture used. A parametric plot of s-polarized versus p-polarized stopband width agrees very well with the 3D band gap and is model-free. This practical probe provides fast feedback on the advanced nanofabrication needed for 3D photonic crystals and stimulates practical applications of band gaps in 3D silicon nanophotonics and photonic integrated circuits, photovoltaics, cavity QED, and quantum information processing., 11 pages, 12 figures

From Marge Simpson’s family quilt to my Northern Irish paternal grandmother’s patchworks; from 19th century US homesteaders to rural Ulster farmers; from traditional salvage frugality to the new eco-sustainability; from poly-cotton duvets washable at 40° to ‘smart’ and intelligent textile technology...my paper examines the emotionally-rich content captured in the fabrication, materiality and design of textile quilts, and indicate how their combinations of cerebral and ‘felt’ substance and affect provides a template for emotionally meaningful textile design within a ‘craft futures’ scenario. Functional, utilitarian and decorative, quilts mark the commonplace rituals and universal emotions of bed, and the momentous and miniscule events and significations of life. Those quilts are embedded with human experience, an interface where a human subject performatively meets and merges with a designed object. Conventionally, the future for textile design is described as hi-tech / ‘smart’ (wearable computers, bio-mimetic fibres, electronic and digital fabrics, geo-textiles, engineering textile composites...) and ‘eco’ (sustainable, biodegradable, recyclable processes and products). Where does emotional design fit in? My paper advocates a fresh examination of the very particular traditions, characteristics, processes and outcomes of hand-crafted, fabric-salvaged, highly-functional, labour-intensive, emotionally-invested, collectively-stitched, pre-industrial, domestic quilts both in the US and in my family. I will indicate how those aesthetics and materialities might allow a redefinition of ‘textile design futures’. I will disclose one practical aspect of my vision of how technological textile innovations and advances might allow emotionally-rich, quality-measurable, poetically-valuable designed future living.

Despite being widely used in reporter technologies, bioluminescent systems are largely understudied. Of at least forty different bioluminescent systems thought to exist in nature, molecular components of only seven light-emitting reactions are known, and the full biochemical pathway leading to light emission is only understood for two of them. Here, we provide a succinct overview of currently known bioluminescent systems highlighting available tools for research and discussing future applications.

Four new 1,8-naphthalimide based compounds, 4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-ylmethyl)-benzoic acid (LH), 4(1,3-dioxo-1H,3H-benzo [de]isoquinolin-2-ylmethyp-benzoic acid methyl ester (LMe), 4-(1,3-dioxo-1H,3H-benzo[de]isoquinolin-2-ylmethyl)-benzoyl chloride (LCl), and 4-(1,3-dioxo-1H,3H-benzo [de]isoquinolin-2-ylmethyl)benzoic acid hydrazide (LN) are synthesized and characterized using spectral data and X-ray crystallography. They form nanoaggregates in aqueous-DMF solution and exhibited aggregation enhanced emission. The nano aggregates are characterized using their scanning electron and atomic force microscopy images. The emission intensity follows the order as LH > LMe > LCl > LN. Their photophysical properties are recorded both in solution and in the solid-state and are correlated with the nature of benzoic acid derivatives owing to the combinatorial effect of pi-pi stacking and intermolecular and intramolecular interactions. The density functional theory calculations empower the understanding of their molecular and cumulative electronic behaviors. Antiparallel dimeric interactions in the solid-state extend a herringbone arrangement to LH and 2D channel and stair-like arrangement for LCl and LN, respectively.

Precise knowledge of the local density of optical states (LDOS) is fundamental to understanding nanophotonic systems and devices. Complete LDOS mapping requires resolution in energy, momentum, and space, and hence a versatile measurement approach capable of providing simultaneous access to the LDOS components is highly desirable. Here, we explore a modality of cathodoluminescence spectroscopy able to resolve, in single acquisitions, the dispersion in energy and momentum of the radiative LDOS. We perform measurements on a titanium nitride diffraction grating, bulk molybdenum disulfide, and silicon to demonstrate that the technique can probe and disentangle the dispersion of coherent and incoherent cathodoluminescence signals. The approach presented raises cathodoluminescence spectroscopy to a versatile tool for subwavelength design and optimization of nanophotonic devices in the reciprocal space.

In this work a novel process allowing for the production of nanoporous Ge thin films is presented. This process uses the combination of two techniques: Ge sputtering on SiO2 and dopant ion implantation. The process entails four successive steps: (i) Ge sputtering on SiO2, (ii) implantation preannealing, (iii) high-dose dopant implantation, and (iv) implantation postannealing. Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of the Ge film at different process steps under different postannealing conditions. For the same postannealing conditions, the Ge film topology was shown to be similar for different implantation doses and different dopants. However, the film topology can be controlled by adjusting the postannealing conditions.

Electromechanical coupling through piezoelectric polymer chains allows the emission of organic molecules in active nanowires to be tuned. This effect is evidenced by highly bendable arrays of counter-ion dye-doped nanowires made of a poly(vinylidenefluoride) copolymer. A reversible redshift of the dye emission is found upon the application of dynamic stress during highly accurate bending experiments. By density functional theory calculations it is found that these photophysical properties are associated with mechanical stresses applied to electrostatically interacting molecular systems, namely to counterion-mediated states that involve light-emitting molecules as well as charged regions of piezoelectric polymer chains. These systems are an electrostatic class of supramolecular functional stress-sensitive units, which might impart new functionalities in hybrid molecular nanosystems and anisotropic nanostructures for sensing devices and soft robotics., Comment: 32 pages, 18 figures

Ca(2+)-regulated photoproteins are responsible for the bioluminescence of a variety of marine organisms, mostly coelenterates. The photoproteins consist of a single polypeptide chain to which an imidazopyrazinone derivative (2-hydroperoxycoelenterazine) is tightly bound. According to photoprotein spatial structures the side chains of His175, Trp179, and Tyr190 in obelin and His169, Trp173, Tyr184 in aequorin are at distances that allow hydrogen bonding with the peroxide and carbonyl groups of the 2-hydroperoxycoelenterazine ligand. We replaced these amino acids in both photoproteins by residues with different hydrogen bond donor-acceptor capacity. All mutants exhibited luciferase-like bioluminescence activity, hardly present in the wild-type photoproteins, and showed low or no photoprotein activity, except for aeqH169Q (24% of wild-type activity), obeW179Y (23%), obeW179F (67%), obeY190F (14%), and aeqY184F (22%). The results clearly support the supposition made from photoprotein spatial structures that the hydrogen bond network formed by His-Trp-Tyr triad participates in stabilizing the 2-hydroperoxy adduct of coelenterazine. These residues are also essential for the positioning of the 2-hydroperoxycoelenterazine intermediate, light emitting reaction, and for the formation of active photoprotein. In addition, we demonstrate that although the positions of His-Trp-Tyr residues in aequorin and obelin spatial structures are almost identical the substitution effects might be noticeably different.

International audience; Adding Tin (Sn) to Germanium (Ge) can turn it into a direct bandgap group IV semiconductor emitting in the mid-infrared wavelength range. Several approaches are currently being investigated to improve the GeSn devices. It has been theoretically predicted that the strain can improve their optical properties. However, the impact of strain on band parameters has not yet been measured for really high Sn contents (i.e., above 11%). In this work, we have used the photocurrent and photoluminescence spectroscopy to measure the gamma bandgap in compressively strained GeSn layers grown on Ge buffers. A good agreement is found with the modeling and the literature. We show here that the conventional GeSn deformation potentials used in the literature for smaller Sn contents can be applied up to 15% Sn. This gives a better understanding of strained-GeSn for future laser designs. Published by AIP Publishing.

Silicon-nanocrystals (Si-NCs) realized by SiOx8 MV/cm; independent of temperature), while for lower electric fields (5-8 MV/cm) at higher temperatures, the trap-related Generalized Poole-Frenkel (GPF) is dominant. This signified the role of traps in modifying the conduction in bulk ICPCVD SiO2 films. We then present the conduction in ML samples. For multilayer samples with SiO2 sublayer thickness of 1.5 nm and 2.5 nm, Direct Tunneling (DT) is observed to be dominant, while for SiO2 sublayer thickness of 3.5 nm, Space Charge Limited Conduction (SCLC) with exponential trap distribution is found to be the dominant conduction mechanism. This signifies the role of traps in modifying the conduction in Si-NC multilayer samples and SiO2 sublayer thickness dependence. (C) 2016 Elsevier B.V. All rights reserved.

Strong and directionally specific forward scattering from optical nanoantennas is of utmost importance for various applications in the broader context of photovoltaics and integrated light sources. Here, we outline a simple yet powerful design principle to perceive a nanoantenna that provides directional scattering into a higher index substrate based on the interference of multiple electric dipoles. A structural implementation of the electric dipole distribution is possible using plasmonic nanoparticles with a fairly simple geometry, i.e. two coupled rectangular nanoparticles, forming a dimer, on top of a substrate. The key to achieve directionality is to choose a sufficiently large size for the nanoparticles. This promotes the excitation of vertical electric dipole moments due to the bi-anisotropy of the nanoantenna. In turn, asymmetric scattering is obtained by ensuring the appropriate phase relation between the vertical electric dipole moments. The scattering strength and angular spread for an optimized nanoantenna can be shown to be broadband and robust against changes in the incidence angle. The scattering directionality is maintained even for an array configuration of the dimer. It only requires the preferred scattering direction of the isolated nanoantenna not to be prohibited by interference. (C) 2016 Optical Society of America

Many proteins require a non-covalently bound ligand to be functional. How ligand binding affects protein conformation is often unknown. Here we address thermal unfolding of the free and ligand-bound forms of photoprotein obelin. Fluorescence and far-UV circular dichroism (CD) data show that the various ligand-dependent conformational states of obelin differ significantly in stability against thermal unfolding. Binding of coelenterazine and calcium considerably stabilizes obelin. In solution, all obelin structures are similar, except for apo-obelin without calcium. This latter protein is an ensemble of conformational states, the populations of which alter upon increasing temperature.

The microscopic origin of the bright nanosecond blue-green photoluminescence (PL), frequently reported for synthesized organically terminated Si quantum dots (Si-QDs), has not been fully resolved, hampering potential applications of this interesting material. Here a comprehensive study of the PL from alkyl-terminated Si-QDs of 2-3 nm size, prepared by wet chemical synthesis is reported. Results obtained on the ensemble and those from the single nano-object level are compared, and they provide conclusive evidence that efficient and tunable emission arises due to radiative recombination of electron-hole pairs confined in the Si-QDs. This understanding paves the way towards applications of chemical synthesis for the development of Si-QDs with tunable sizes and bandgaps.

We report on an experimental study with UV and visible ultrafast time-gated emission and transient absorption of the early photodynamics of horse heart Cytochrome c in both ferric and ferrous redox states. A clear separation in time and energy of tryptophan and haem emission is observed. Excitation of the haem via resonant energy transfer from the tryptophan residue is observed in the subsequent haem electronic relaxation. Different Trp-haem energy transfer time constants of the ferrous and ferric forms are obtained. An almost instantaneous relaxation to the lowest singlet excited state (corresponding to the so-called Q band) characterizes the earliest electronic dynamics of the haem, independent of excitation energy, while dark intermediate states govern the ground-state recovery. The information gathered in these two experiments and in the literature allows us to propose a simple scheme for the electronic relaxation leading to ligand dissociation.

The photophysical properties are described of silicon nanoparticles protected with a shell of n-butyl chains, and with an asymmetric size distribution with a peak between 2 and 3 nm, and a tail extending up to 7 nm. The excited nanoparticles decay via multiexponential luminescence on a time scale of a few nanoseconds. Longer-lived nonluminescent dark states were observed by nanosecond transient absorption spectroscopy. The average lifetime of the luminescent excited states increased somewhat with increasing wavelengths of excitation and emission. The nanosecond transient absorption spectra shifted to longer wavelengths with time. Probably, these observations are related to the size distribution of the particles: larger particles are excited at longer wavelength, emit at longer wavelength, and have longer-lived and red-shifted nanosecond transient absorption spectra. Two-photon excited luminescence showed broader emission spectra than one-photon excited luminescence at the same excitation energies. The two-photon cross-sections were found to be surprisingly small.

Herein, we report the synthesis, separation and characterisation of the E- and Z-isomers of dipyrrolyldiphenylethene to study their emission behaviour in the aggregation state and solid state. The E-isomer showed pronounced aggregation induced emission (AIE) whereas the Z-isomer showed crystallization induced emission (CIE). The present study explains that the emission behaviour (AIE/CIE) is dependent on the inter/intra molecular interactions between the molecules. The study also confirms that restriction of intramolecular rotation (RIR) is the main cause of AIE/CIE in olefinic luminogens Tetraphenylethylene (TPE) type systems rather than E/Z isomerisation.

International audience; Applying tensile strain in a single germanium crystal is a very promising way to tune its bandstructure and turn it into a direct band gap semiconductor. In this work, we stress vapor-liquid-solid grown germanium nanowires along their [111] axis thanks to the strain tranfer from a silicon nitride thin film by a microfabrication process. We measure the Gamma-LH direct band gap transition by photocurrent spectrometry and quantify associated strain by X-ray Laue microdiffraction on beamline BM32 at the European Synchrotron Radiation Facility. Nanowires exhibit up to 1.48% strain and an absorption threshold down to 0.73 eV, which is in good agreement with theoretical computations for the Gamma-LH transition, showing that the nanowire geometry is an efficient way of applying tensile uniaxial stress along the [111] axis of a germanium crystal.

Transparent monoliths and films of urea cross-linked tripodal siloxane-based hybrids (named tri-ureasils) were prepared by the sol-gel process, under controlled atmosphere (inside a glove box) and ambient conditions and their structure and optical features were compared. X-ray diffraction data point out that all the materials are essentially amorphous and Si-29 NMR reveal an increase in the condensation degree (0.97) for the hybrids prepared under controlled atmosphere relatively to that found for those prepared under ambient conditions (0.84-0.91). The tri-ureasils are white light emitters under UV/Visible excitation (from 250 to 453 nm) being observed for the composites prepared inside the glove box a significant enhancement (60-80 %) of the absorption coefficient and higher emission quantum yield values (similar to 0.27 and similar to 0.20 for monoliths and films, respectively) relatively to those synthesized under ambient condition.

Porous silicon, which is being obtained by electrochemical etching of silicon wafers in electrolytes on the base of hydrofluoric acid, recently attracted the attention of specialists in photovoltaics even more due to a number of its unique properties. However, at present, acceptable results are obtained for the use of porous silicon as antireflecting coating for silicon solar cells only. In the present paper, previous experience of the use of per-Si in the silicon solar cells has been reviewed. an the base of examination of the porous silicon properties, a number of new directions of improvement of photoconversion efficiency of structures with optimized layers of porous silicon are proposed. The results of numerical calculations carried, confirm perspectiveness of use of porous silicon for efficiency improvement for different types of silicon solar cells. These can be increased of their internal quantum efficiency, expansions of operating spectral range toward ultra-violet and infrared spectrum range, decrease of losses of photogenerated power due to the influence of bulk and surface recombination. (C) 1999 Elsevier Science Ltd. All rights reserved.