Showing papers on "Photoexcitation published in 2015"

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics

Abstract: We report on reversible, light-induced transformations in (CH3NH3)Pb(BrxI1−x)3. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

Population inversion and giant bandgap renormalization in atomically thin WS2 layers

Abstract: Atomically thin layers of transition metal dichalcogenides are shown to exhibit a disappearance of strong excitonic absorption along with population inversion at the direct gap over a spectral range of hundreds of meV after pulsed photoexcitation.

Distinguishing between plasmon-induced and photoexcited carriers in a device geometry

Abstract: The use of surface plasmons, charge density oscillations of conduction electrons of metallic nanostructures, to boost the efficiency of light-harvesting devices through increased light-matter interactions could drastically alter how sunlight is converted into electricity or fuels. These excitations can decay directly into energetic electron-hole pairs, useful for photocurrent generation or photocatalysis. However, the mechanisms behind plasmonic carrier generation remain poorly understood. Here we use nanowire-based hot-carrier devices on a wide-bandgap semiconductor to show that plasmonic carrier generation is proportional to internal field-intensity enhancement and occurs independently of bulk absorption. We also show that plasmon-induced hot electrons have higher energies than carriers generated by direct excitation and that reducing the barrier height allows for the collection of carriers from plasmons and direct photoexcitation. Our results provide a route to increasing the efficiency of plasmonic hot-carrier devices, which could lead to more efficient devices for converting sunlight into usable energy.

Tuning of Magnetic Optical Response in a Dielectric Nanoparticle by Ultrafast Photoexcitation of Dense Electron-Hole Plasma.

Abstract: We propose a novel approach for efficient tuning of optical properties of a high refractive index subwavelength nanoparticle with a magnetic Mie-type resonance by means of femtosecond laser irradiation. This concept is based on ultrafast photoinjection of dense (>1020 cm–3) electron–hole plasma within such nanoparticle, drastically changing its transient dielectric permittivity. This allows manipulation by both electric and magnetic nanoparticle responses, resulting in dramatic changes of its scattering diagram and scattering cross section. We experimentally demonstrate 20% tuning of reflectance of a single silicon nanoparticle by femtosecond laser pulses with wavelength in the vicinity of the magnetic dipole resonance. Such a single-particle nanodevice enables designing of fast and ultracompact optical switchers and modulators.

Dynamical Evolution of Anisotropic Response in Black Phosphorus under Ultrafast Photoexcitation

Abstract: Black phosphorus has recently emerged as a promising material for high-performance electronic and optoelectronic device for its high mobility, tunable mid-infrared bandgap, and anisotropic electronic properties. Dynamical evolution of photoexcited carriers and the induced transient change of electronic properties are critical for materials’ high-field performance but remain to be explored for black phosphorus. In this work, we perform angle-resolved transient reflection spectroscopy to study the dynamical evolution of anisotropic properties of black phosphorus under photoexcitation. We find that the anisotropy of reflectivity is enhanced in the pump-induced quasi-equilibrium state, suggesting an extraordinary enhancement of the anisotropy in dynamical conductivity in hot carrier dominated regime. These results raise attractive possibilities of creating high-field, angle-sensitive electronic, optoelectronic, and remote sensing devices exploiting the dynamical electronic anisotropy with black phosphorus.

Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides

Abstract: Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of π-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar π-π stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple π-stacked dimer, the photoexcitation energy in the columnar π-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process.

On the mechanism of vibrational control of light-induced charge transfer in donor–bridge–acceptor assemblies

Abstract: Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.

Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles.

Abstract: We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI+•–PDI–• in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron–nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI+•–PDI–• to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Semiconductor interfacial carrier dynamics via photoinduced electric fields

Abstract: Solar photoconversion in semiconductors is driven by charge separation at the interface of the semiconductor and contacting layers. Here we demonstrate that time-resolved photoinduced reflectance from a semiconductor captures interfacial carrier dynamics. We applied this transient photoreflectance method to study charge transfer at p-type gallium-indium phosphide (p-GaInP2) interfaces critically important to solar-driven water splitting. We monitored the formation and decay of transient electric fields that form upon photoexcitation within bare p-GaInP2, p-GaInP2/platinum (Pt), and p-GaInP2/amorphous titania (TiO2) interfaces. The data show that a field at both the p-GaInP2/Pt and p-GaInP2/TiO2 interfaces drives charge separation. Additionally, the charge recombination rate at the p-GaInP2/TiO2 interface is greatly reduced owing to its p-n nature, compared with the Schottky nature of the p-GaInP2/Pt interface.

Efficient near-infrared up-conversion photoluminescence in carbon nanotubes

Abstract: Photoluminescence phenomena normally obey Stokes' law of luminescence according to which the emitted photon energy is typically lower than its excitation counterparts. Here we show that carbon nanotubes break this rule under one-photon excitation conditions. We found that the carbon nanotubes exhibit efficient near-infrared photoluminescence upon photoexcitation even at an energy lying >100-200 meV below that of the emission at room temperature. This apparently anomalous phenomenon is attributed to efficient one-phonon-assisted up-conversion processes resulting from unique excited-state dynamics emerging in an individual carbon nanotube with accidentally or intentionally embedded localized states. These findings may open new doors for energy harvesting, optoelectronics and deep-tissue photoluminescence imaging in the near-infrared optical range.

Ultrafast Singlet Fission in a Push-Pull Low-Bandgap Polymer Film.

Abstract: Excited-state dynamics in poly[4,6-(dodecyl-thieno[3,4-b]thiophene-2-carboxylate)-alt-2,6-(4,8-dioctoxylbenzo[1,2-b:4,5-b]dithiophene)] (PTB1) was studied by transient absorption spectroscopy. Upon photoexcitation at 400 nm, an additional transient species is promptly generated along with singlet excitons and survives up to nanoseconds, while singlet excitons disappear completely. In order to assign the long-lived species, we measured transient absorption spectra over the wide spectral range from 900 to 2500 nm. As a result, we found that the long-lived species is ascribed not to polarons but to triplet excitons, which is formed through the ultrafast singlet fission (SF). We discuss the ultrafast SF mechanism in push–pull low-bandgap polymer PTB1 films on the basis of the excited-state dynamics under various excitation wavelengths and intensities.

Charge Photogeneration in Few-Layer MoS2

Abstract: The 2D semiconductor MoS2 in its mono- and few-layer form is expected to have a significant exciton binding energy of several 100 meV, suggesting excitons as the primary photoexcited species. Nevertheless, even single layers show a strong photovoltaic effect and work as the active material in high sensitivity photodetectors, thus indicating efficient charge carrier photogeneration. Here, modulation spectroscopy in the sub-ps and ms time scales is used to study the photoexcitation dynamics in few-layer MoS2. The results suggest that the primary photoexcitations are excitons that efficiently dissociate into charges with a characteristic time of 700 fs. Based on these findings, simple suggestions for the design of efficient MoS2 photovoltaic and photodetector devices are made.

Probing Photoexcited Carriers in a Few-Layer MoS2 Laminate by Time-Resolved Optical Pump-Terahertz Probe Spectroscopy

Abstract: We report the dynamics of photoinduced carriers in a free-standing MoS2 laminate consisting of a few layers (1-6 layers) using time-resolved optical pump-terahertz probe spectroscopy. Upon photoexcitation with the 800 nm pump pulse, the terahertz conductivity increases due to absorption by the photoinduced charge carriers. The relaxation of the non-equilibrium carriers shows fast as well as slow decay channels, analyzed using a rate equation model incorporating defect-assisted Auger scattering of photoexcited electrons, holes, and excitons. The fast relaxation time occurs due to the capture of electrons and holes by defects via Auger processes, resulting in nonradiative recombination. The slower relaxation arises since the excitons are bound to the defects, preventing the defect-assisted Auger recombination of the electrons and the holes. Our results provide a comprehensive understanding of the non-equilibrium carrier kinetics in a system of unscreened Coulomb interactions, where defect-assisted Auger processes dominate and should be applicable to other 2D systems.

Determination of Exciton Diffusion Length by Transient Photoluminescence Quenching and Its Application to Quantum Dot Films

Abstract: We present a framework for analyzing transient photoluminescence interfacial quenching experiments to extract exciton diffusivity and diffusion length. Through analytical solutions and finite element simulations at the continuum level, we derive spatiotemporal exciton distributions in films with arbitrary optical thickness and under noninstantaneous photoexcitation, paying particular attention to the effects of imperfect quenching and time-dependent diffusivity (i.e., subdiffusive transport). We demonstrate the utility of our model by applying it to a colloidal quantum dot (QD) thin film interface found in a recently reported record-efficiency QD light-emitting device. We find the exciton diffusion length in these CdSe/CdS core/shell QD films to be in the range 19–24 nm, in agreement with recent measurements of similar materials. We discuss limitations of the continuum-level analysis due to the finite size of individual QDs and an apparent subpopulation of “stationary” excitons that do not diffuse.

An intermediate band dye-sensitised solar cell using triplet–triplet annihilation

Abstract: A new mechanism of charge photogeneration is demonstrated for the first time, based on organic molecular structures This intermediate band approach, integrated into a dye-sensitised solar cell configuration is shown to generate charges upon illumination with low energy photons Specifically 610 nm photoexcitation of Pt porphyrins, through a series of energy transfer steps and triplet–triplet annihilation, excites a higher energy absorption onset molecule, which is then capable of charge injection into TiO2 Transient absorption measurements reveal further detail of the processes involved

Observation of Ground- and Excited-State Charge Transfer at the C60/Graphene Interface

Abstract: We examine charge transfer interactions in the hybrid system of a film of C60 molecules deposited on single-layer graphene using Raman spectroscopy and Terahertz (THz) time-domain spectroscopy. In the absence of photoexcitation, we find that the C60 molecules in the deposited film act as electron acceptors for graphene, yielding increased hole doping in the graphene layer. Hole doping of the graphene film by a uniform C60 film at a level of 5.6 × 1012/cm2 or 0.04 holes per interfacial C60 molecule was determined by the use of both Raman and THz spectroscopy. We also investigate transient charge transfer occurring upon photoexcitation by femtosecond laser pulses with a photon energy of 3.1 eV. The C60/graphene hybrid exhibits a short-lived (ps) decrease in THz conductivity, followed by a long-lived increase in conductivity. The initial negative photoconductivity transient, which decays within 2 ps, reflects the intrinsic photoresponse of graphene. The longer-lived positive conductivity transient, with a li...

Hot-carrier photocurrent effects at graphene–metal interfaces

Abstract: Photoexcitation of graphene leads to an interesting sequence of phenomena, some of which can be exploited in optoelectronic devices based on graphene. In particular, the efficient and ultrafast generation of an electron distribution with an elevated electron temperature and the concomitant generation of a photo-thermoelectric voltage at symmetry-breaking interfaces is of interest for photosensing and light harvesting. Here, we experimentally study the generated photocurrent at the graphene–metal interface, focusing on the time-resolved photocurrent, the effects of photon energy, Fermi energy and light polarization. We show that a single framework based on photo-thermoelectric photocurrent generation explains all experimental results.

Modeling photoionization of aqueous DNA and its components.

Abstract: Radiation damage to DNA is usually considered in terms of UVA and UVB radiation. These ultraviolet rays, which are part of the solar spectrum, can indeed cause chemical lesions in DNA, triggered by photoexcitation particularly in the UVB range. Damage can, however, be also caused by higher energy radiation, which can ionize directly the DNA or its immediate surroundings, leading to indirect damage. Thanks to absorption in the atmosphere, the intensity of such ionizing radiation is negligible in the solar spectrum at the surface of Earth. Nevertheless, such an ionizing scenario can become dangerously plausible for astronauts or flight personnel, as well as for persons present at nuclear power plant accidents. On the beneficial side, ionizing radiation is employed as means for destroying the DNA of cancer cells during radiation therapy. Quantitative information about ionization of DNA and its components is important not only for DNA radiation damage, but also for understanding redox properties of DNA in redox sensing or labeling, as well as charge migration along the double helix in nanoelectronics applications. Until recently, the vast majority of experimental and computational data on DNA ionization was pertinent to its components in the gas phase, which is far from its native aqueous environment. The situation has, however, changed for the better due to the advent of photoelectron spectroscopy in liquid microjets and its most recent application to photoionization of aqueous nucleosides, nucleotides, and larger DNA fragments. Here, we present a consistent and efficient computational methodology, which allows to accurately evaluate ionization energies and model photoelectron spectra of aqueous DNA and its individual components. After careful benchmarking, the method based on density functional theory and its time-dependent variant with properly chosen hybrid functionals and polarizable continuum solvent model provides ionization energies with accuracy of 0.2-0.3 eV, allowing for faithful modeling and interpretation of DNA photoionization. The key finding is that the aqueous medium is remarkably efficient in screening the interactions within DNA such that, unlike in the gas phase, ionization of a base, nucleoside, or nucleotide depends only very weakly on the particular DNA context. An exception is the electronic interaction between neighboring bases which can lead to sequence-specific effects, such as a partial delocalization of the cationic hole upon ionization enabled by presence of adjacent bases of the same type.

Time-resolved terahertz dynamics in thin films of the topological insulator Bi2Se3

Abstract: We use optical pump–THz probe spectroscopy at low temperatures to study the hot carrier response in thin Bi2Se3 films of several thicknesses, allowing us to separate the bulk from the surface transient response. We find that for thinner films the photoexcitation changes the transport scattering rate and reduces the THz conductivity, which relaxes within 10 picoseconds (ps). For thicker films, the conductivity increases upon photoexcitation and scales with increasing both the film thickness and the optical fluence, with a decay time of approximately 5 ps as well as a much higher scattering rate. These different dynamics are attributed to the surface and bulk electrons, respectively, and demonstrate that long-lived mobile surface photo-carriers can be accessed independently below certain film thicknesses for possible optoelectronic applications.

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

Abstract: The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ∼6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, upon CH2Cl2 vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ∼4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.

Ultrafast optical tuning of ferromagnetism via the carrier density

Abstract: The control of the magnetic order by optical pulses is of practical relevance for information storage as well as of fundamental interest to understand magnetic processes. Here, the authors demonstrate the control of magnetic order by changing the carrier density in Eu1−x Gd x O via resonant photoexcitation.

Nonlinear terahertz field-induced carrier dynamics in photoexcited epitaxial monolayer graphene

Abstract: Optical measurements on highly doped single-layer epitaxial graphene reveal that the photoexcitation of charge carriers leads to an enhancement of the THz transmission. In this paper, the results are explained in terms of the change in the carrier scattering rate due to the optical pump fluence and the THz electric field.

Photogenerated Intrinsic Free Carriers in Small-molecule Organic Semiconductors Visualized by Ultrafast Spectroscopy.

Abstract: Confirmation of direct photogeneration of intrinsic delocalized free carriers in small-molecule organic semiconductors has been a long-sought but unsolved issue, which is of fundamental significance to its application in photo-electric devices. Although the excitonic description of photoexcitation in these materials has been widely accepted, this concept is challenged by recently reported phenomena. Here we report observation of direct delocalized free carrier generation upon interband photoexcitation in highly crystalline zinc phthalocyanine films prepared by the weak epitaxy growth method using ultrafast spectroscopy. Transient absorption spectra spanning the visible to mid-infrared region revealed the existence of short-lived free electrons and holes with a diffusion length estimated to cross at least 11 molecules along the π-π stacking direction that subsequently localize to form charge transfer excitons. The interband transition was evidenced by ultraviolet-visible absorption, photoluminescence and electroluminescence spectroscopy. Our results suggest that delocalized free carriers photogeneration can also be achieved in organic semiconductors when the molecules are packed properly.

Photoinduced spontaneous free-carrier generation in semiconducting single-walled carbon nanotubes

Abstract: Strong quantum confinement and low dielectric screening impart single-walled carbon nanotubes with exciton-binding energies substantially exceeding kBT at room temperature. Despite these large binding energies, reported photoluminescence quantum yields are typically low and some studies suggest that photoexcitation of carbon nanotube excitonic transitions can produce free charge carriers. Here we report the direct measurement of long-lived free-carrier generation in chirality-pure, single-walled carbon nanotubes in a low dielectric solvent. Time-resolved microwave conductivity enables contactless and quantitative measurement of the real and imaginary photoconductance of individually suspended nanotubes. The conditions of the microwave conductivity measurement allow us to avoid the complications of most previous measurements of nanotube free-carrier generation, including tube-tube/tube-electrode contact, dielectric screening by nearby excitons and many-body interactions. Even at low photon fluence (approximately 0.05 excitons per μm length of tubes), we directly observe free carriers on excitation of the first and second carbon nanotube exciton transitions.

Direct Observation of Ground-State Product Formation in a 1,3-Cyclohexadiene Ring-Opening Reaction

Abstract: Ultrafast photoelectron imaging using a 90 nm vacuum-UV probe pulse is applied to the ring-opening reaction of 1,3-cyclohexadiene (CHD) in the gas phase, and formation of 1,3,5-hexatriene (HT) and CHD in their electronic ground states is observed in real time. The analysis of the transient photoelectron kinetic energy spectra reveals the branching ratio into HT and CHD as 3:7 upon 270 nm photoexcitation. The ratio is in reasonable agreement with the experimental values reported for the liquid phase and theoretical values for the gas phase, resolving the discrepancy.

Ultrafast electron and hole relaxation pathways in few-layer MoS2

Abstract: Femtosecond optical pump–probe spectroscopy is employed to elucidate the band-selective ultrafast carrier dynamics of few-layer MoS2. Following narrowband resonant photoexcitation of the exciton A transition, the subpicosecond to picosecond relaxation dynamics of the electron and the hole at the K valley are separately interrogated by a broadband probe pulse. The temporal evolution of the spectral first moment reveals nonexponential intravalley relaxation dynamics in the conduction band. Fluence dependence measurements suggest that this relaxation process is predominantly mediated by acoustic phonon emission. Intervalley scattering of carriers from the K valley to the extrema of the conduction and valence bands is also observed via the decay of the spectral zeroth moment. In addition, second-order Raman scattering leads to the emergence of sidebands in the normalized differential transmission spectra. The observed two-phonon energies and the fluence-dependent time constants suggest that the E1g longitudinal optical (LO) phonon and the LA phonon participate in intervalley scattering in the conduction and valence bands, respectively. Ab initio nonadiabatic molecular dynamics simulations yield time constants of 0.80 and 0.72 ps for intra- and intervalley electronic relaxation, respectively; the latter agrees well with experiment. Finally, the normalized differential transmission spectra reveal a two-electron shake-up satellite that originates from band-edge radiative recombination and the simultaneous excitation of a hole from Kv1 to Kv2. From its spectral position, a Kv1–Kv2 spin–orbit splitting of 1166 ± 1 cm–1 is deduced. The observation of the two-electron transition points to the existence of strong electron correlation in photoexcited few-layer MoS2.

Broadband Transient Absorption and Two-Dimensional Electronic Spectroscopy of Methylene Blue

Abstract: Broadband transient absorption and two-dimensional electronic spectroscopy (2DES) studies of methylene blue in aqueous solution are reported. By isolating the coherent oscillations of the nonlinear signal amplitude and Fourier transforming with respect to the population time, we analyzed a significant number of coherences in the frequency domain and compared them with predictions of the vibronic spectrum from density function theory (DFT) calculations. We show here that such a comparison enables reliable assignments of vibrational coherences to particular vibrational modes, with their constituent combination bands and overtones also being identified via Franck–Condon analysis aided by DFT. Evaluation of the Fourier transform (FT) spectrum of transient absorption recorded to picosecond population times, in coincidence with 2D oscillation maps that disperse the FT spectrum into the additional excitation axis, is shown to be a complementary approach toward detailed coherence determination. Using the Franck–Condon overlap integrals determined from DFT calculations, we modeled 2D oscillation maps up to two vibrational quanta in the ground and excited state (six-level model), showing agreement with experiment. This semiquantitative analysis is used to interpret the geometry change upon photoexcitation as an expansion of the central sulfur/nitrogen containing ring due to the increased antibonding character in the excited state.