Photoinduced coherent acoustic phonon dynamics inside Mott insulator Sr2IrO4 films observed by femtosecond X-ray pulses

NASA Astrophysics Data System (ADS)

Zhang, Bing-Bing; Liu, Jian; Wei, Xu; Sun, Da-Rui; Jia, Quan-Jie; Li, Yuelin; Tao, Ye

2017-04-01

We investigate the transient photoexcited lattice dynamics in a layered perovskite Mott insulator Sr2IrO4 film by femtosecond X-ray diffraction using a laser plasma-based X-ray source. The ultrafast structural dynamics of Sr2IrO4 thin films are determined by observing the shift and broadening of (0012) Bragg diffraction after excitation by 1.5 eV and 3.0 eV pump photons for films with different thicknesses. The observed transient lattice response can be well interpreted as a distinct three-step dynamics due to the propagation of coherent acoustic phonons generated by photoinduced quasiparticles (QPs). Employing a normalized phonon propagation model, we found that the photoinduced angular shifts of the Bragg peak collapse into a universal curve after introducing normalized coordinates to account for different thicknesses and pump photon energies, pinpointing the origin of the lattice distortion and its early evolution. In addition, a transient photocurrent measurement indicates that the photoinduced QPs are charge neutral excitons. Mapping the phonon propagation and correlating its dynamics with the QP by ultrafast X-ray diffraction (UXRD) establish a powerful way to study electron-phonon coupling and uncover the exotic physics in strongly correlated systems under nonequilibrium conditions.

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz, Michael; Cho, Sung; Niklas, Jens

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (T ET ≤ 0.4 ps) and very slow charge recombination (T CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cmmore » -1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70@COP-5 complex.« less

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

DOE PAGES

Ortiz, Michael; Cho, Sung; Niklas, Jens; ...

2017-03-13

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (T ET ≤ 0.4 ps) and very slow charge recombination (T CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cmmore » -1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70@COP-5 complex.« less

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium.

PubMed

Ortiz, Michael; Cho, Sung; Niklas, Jens; Kim, Seonah; Poluektov, Oleg G; Zhang, Wei; Rumbles, Garry; Park, Jaehong

2017-03-29

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70 -encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70 @COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τ ET ≤ 0.4 ps) and very slow charge recombination (τ CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm -1 ) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70 @COP-5 complex.

Photophysics and morphology of poly (3-dodecylthienylenevinylene)-[6,6]-phenyl-C{sub 61}-butyric acid methyl ester composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lafalce, E.; Toglia, P.; Jiang, X.

2012-05-21

A series of low band gap poly(3-dodecylthienylenevinylene) (PTV) with controlled morphological order have been synthesized and blended with the electron acceptor [6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) for organic photovoltaic devices. Two polymers with the most and least side chain regioregularity were chosen in this work, namely the PTV010 and PTV55, respectively. Using photoluminescence, photo-induced absorption spectroscopy, and atomic force microscopy, we find no direct evidence of photoinduced charge transfer between the two constituents, independent of the bulk-heterojunction morphology of the film, although the possibility of formation of P{sup +}/C{sub 60}{sup -} charge transfer complex was not completely ruled out.more » The large exciton binding energy (E{sub b} = 0.6 eV) in PTV inhibits the photoinduced electron transfer from PTV to PCBM. In addition, excitons formed on polymer chains suffer ultrafast (« less

Reduced Charge Transfer Exciton Recombination in Organic Semiconductor Heterojunctions by Molecular Doping

NASA Astrophysics Data System (ADS)

Deschler, Felix; da Como, Enrico; Limmer, Thomas; Tautz, Raphael; Godde, Tillmann; Bayer, Manfred; von Hauff, Elizabeth; Yilmaz, Seyfullah; Allard, Sybille; Scherf, Ullrich; Feldmann, Jochen

2011-09-01

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer-fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and results in a favored formation of separated carriers. This is observed by the ultrafast quenching of photoluminescence from charge transfer excitons and the increase in photoinduced polaron density by ˜70%. The results are consistent with a reduced formation of emissive charge transfer excitons, induced by state filling of tail states.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bing-Bing; Liu, Jian; Wei, Xu

We investigate the transient photoexcited lattice dynamics in a layered perovskite Mott insulator Sr2IrO4 film by femtosecond X-ray diffraction using a laser plasma-based X-ray source. The ultrafast structural dynamics of Sr2IrO4 thin films are determined by observing the shift and broadening of (0012) Bragg diffraction after excitation by 1.5 eV and 3.0 eV pump photons for films with different thicknesses. The observed transient lattice response can be well interpreted as a distinct three-step dynamics due to the propagation of coherent acoustic phonons generated by photoinduced quasiparticles (QPs). Employing a normalized phonon propagation model, we found that the photoinduced angular shiftsmore » of the Bragg peak collapse into a universal curve after introducing normalizedn coordinates to account for different thicknesses and pump photon energies, pinpointing the origin of the lattice distortion and its early evolution. In addition, a transient photocurrent measurement indicates that the photoinduced QPs are charge neutral excitons. Mapping the phonon propagation and correlating its dynamics with the QP by ultrafast X-ray diffraction (UXRD) establish a powerful way to study electron-phonon coupling and uncover the exotic physics in strongly correlated systems under nonequilibrium conditions.« less

Photoinduced piezooptics effect in TeO2-Ga2O3 glasses

NASA Astrophysics Data System (ADS)

Ozga, K.; Fedorchuk, A. O.; Armand, P.

2015-08-01

We have found that during the bicolor illumination by two boicolor coherent wavelengths 1540 nm/770 nm there occurred substantial changes of the elastooptical non-diagonal coefficients at 1150 nm cw laser wavelength. They are maximal at power densities 400 … 500 MW/cm2. The studies have shown that the maximal effect exists for ultra-fast quenching glasses and occurs after the 1-2 min of the treatment. The switching off of the optical treatment leads to the disappearance of the photoinduced piezooptics at about 100 ms. The observed changes are explained within the photoinduced changes of the charge density distribution for the principal structural clusters within a framework of the DFT approach. The studies were done both for diagonal as well as off-diagonal piezooptical effect (POE) tensor components.

Excited-State Dynamics of Biological Molecules in Solution: Photoinduced Charge Transfer in Oxidatively Damaged DNA and Deactivation of Violacein in Viscous Solvents

NASA Astrophysics Data System (ADS)

Beckstead, Ashley Ann

UV radiation from the sun is strongly absorbed by DNA, and the resulting electronic excited states can lead to the formation of mutagenic photoproducts. Decades of research have brought to light the excited-state dynamics of single RNA and DNA nucleobases, but questions remain about the nature of excited states accessed in DNA strands. In this thesis, I present ultrafast spectroscopic observations of photoinduced electron transfer from the oxidatively damaged bases, 8-oxo-7,8-dihydro-2'-deoxyguanosine, 5-hydroxy-2'-deoxycytidine and 5-hydroxy-2'-deoxyuridine, to adenine in three dinucleotides. The results reveal that charge transfer states are formed on a timescale faster than our instrumental resolution (<0.5 ps), and back electron transfer efficiently returns the excited-state population to the ground state on timescales from tens to hundreds of ps. In addition to recent spectroscopic observations of charge transfer state species in DNA by other groups, our results have augmented understanding of the long-lived transient signals observed in DNA strands. The observation of photoinduced electron transfer in these oxidatively damaged nucleobases also supports a recent proposal regarding the role of oxidative products in pre-RNA catalysis. I discuss these observations in the contexts of fundamental DNA excited-state dynamics and prebiotic chemical evolution. In this thesis, I also present the first ultrafast spectroscopic investigation of violacein, a pigment isolated from Antarctic bacteria. Despite claims for the photoprotective role of this pigment, there has never been a spectroscopic analysis of excited-state deactivation in violacein. Emission spectra, fluorescence quantum yields and excited-state lifetimes of violacein in various solvents were measured for the first time. Both the fluorescence quantum yield and excited-state lifetime of violacein increase in increasingly viscous solvents, suggesting a large-scale motion mediates excited-state deactivation. I compare these results to similar observations of viscosity-dependent excited-state decay rates in other molecules. I also consider the relevance of violacein's excited-state properties to the hypothesized sunscreening role of violacein. Overall, the studies presented in this dissertation illustrate how ultrafast spectroscopic techniques can be used to unravel complex biomolecular excited-state dynamics in solution.

Dynamics and mechanisms of interfacial photoinduced electron transfer processes of third generation photovoltaics and photocatalysis.

PubMed

Bauer, Christophe; Teuscher, Joël; Brauer, Jan C; Punzi, Angela; Marchioro, Arianna; Ghadiri, Elham; De Jonghe, Jelissa; Wielopolski, Mateusz; Banerji, Natalie; Moser, Jacques E

2011-01-01

Photoinduced electron transfer (PET) across molecular/bulk interfaces has gained attention only recently and is still poorly understood. These interfaces offer an excellent case study, pertinent to a variety of photovoltaic systems, photo- and electrochemistry, molecular electronics, analytical detection, photography, and quantum confinement devices. They play in particular a key role in the emerging fields of third-generation photovoltaic energy converters and artificial photosynthetic systems aimed at the production of solar fuels, creating a need for a better understanding and theoretical treatment of the dynamics and mechanisms of interfacial PET processes. We aim to achieve a fundamental understanding of these phenomena by designing experiments that can be used to test and alter modern theory and computational modeling. One example illustrating recent investigations into the details of the ultrafast processes that form the basis for photoinduced charge separation at a molecular/bulk interface relevant to dye-sensitized solar cells is briefly presented here: Kinetics of interfacial PET and charge recombination processes were measured by fs and ns transient spectroscopy in a heterogeneous donor-bridge-acceptor (D-B-A) system, where D is a Ru(II)(terpyridyl-PO3)(NCS)3 complex, B an oligo-p-phenylene bridge, and A nanocrystalline TiO2. The forward ET reaction was found to be faster than vibrational relaxation of the vibronic excited state of the donor. Instead, the back ET occurred on the micros time scale and involved fully thermalized species. The D-A distance dependence of the electron transfer rate was studied by varying the number of p-phenylene units contained in the bridge moiety. The remarkably low damping factor beta = 0.16 angstroms(-1) observed for the ultrafast charge injection from the dye excited state into the conduction band of TiO2 is attributed to the coupling of electron tunneling with nonequilibrium vibrations redistributed on the bridge, giving rise to polaronic transport of charges from the donor ligand to the acceptor solid oxide surface.

Ultrafast Photoinduced Multimode Antiferromagnetic Spin Dynamics in Exchange-Coupled Fe/RFeO3 (R = Er or Dy) Heterostructures.

PubMed

Tang, Jin; Ke, Yajiao; He, Wei; Zhang, Xiangqun; Zhang, Wei; Li, Na; Zhang, Yongsheng; Li, Yan; Cheng, Zhaohua

2018-05-25

Antiferromagnetic spin dynamics is important for both fundamental and applied antiferromagnetic spintronic devices; however, it is rarely explored by external fields because of the strong exchange interaction in antiferromagnetic materials. Here, the photoinduced excitation of ultrafast antiferromagnetic spin dynamics is achieved by capping antiferromagnetic RFeO 3 (R = Er or Dy) with an exchange-coupled ferromagnetic Fe film. Compared with antiferromagnetic spin dynamics of bare RFeO 3 orthoferrite single crystals, which can be triggered effectively by ultrafast laser heating just below the phase transition temperature, the ultrafast photoinduced multimode antiferromagnetic spin dynamic modes, for exchange-coupled Fe/RFeO 3 heterostructures, including quasiferromagnetic resonance, impurity, coherent phonon, and quasiantiferromagnetic modes, are observed in a temperature range of 10-300 K. These experimental results not only offer an effective means to trigger ultrafast antiferromagnetic spin dynamics of rare-earth orthoferrites, but also shed light on the ultrafast manipulation of antiferromagnetic magnetization in Fe/RFeO 3 heterostructures. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in Novel Donor-Acceptor Core-Shell Nanostructures for Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Strain, Jacob; Jamhawi, Abdelqader; Abeywickrama, Thulitha M.; Loomis, Wendy; Rathnayake, Hemali; Liu, Jinjun

2016-06-01

Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

Cooperative photoinduced metastable phase control in strained manganite films

NASA Astrophysics Data System (ADS)

Zhang, Jingdi; Tan, Xuelian; Liu, Mengkun; Teitelbaum, S. W.; Post, K. W.; Jin, Feng; Nelson, K. A.; Basov, D. N.; Wu, Wenbin; Averitt, R. D.

2016-09-01

A major challenge in condensed-matter physics is active control of quantum phases. Dynamic control with pulsed electromagnetic fields can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. Here we demonstrate strain-engineered tuning of La2/3Ca1/3MnO3 into an emergent charge-ordered insulating phase with extreme photo-susceptibility, where even a single optical pulse can initiate a transition to a long-lived metastable hidden metallic phase. Comprehensive single-shot pulsed excitation measurements demonstrate that the transition is cooperative and ultrafast, requiring a critical absorbed photon density to activate local charge excitations that mediate magnetic-lattice coupling that, in turn, stabilize the metallic phase. These results reveal that strain engineering can tune emergent functionality towards proximal macroscopic states to enable dynamic ultrafast optical phase switching and control.

Nonadiabatic excited-state molecular dynamics modeling of photoinduced dynamics in conjugated molecules.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir; Roitberg, Adrian E; Tretiak, Sergei

2011-05-12

Nonadiabatic dynamics generally defines the entire evolution of electronic excitations in optically active molecular materials. It is commonly associated with a number of fundamental and complex processes such as intraband relaxation, energy transfer, and light harvesting influenced by the spatial evolution of excitations and transformation of photoexcitation energy into electrical energy via charge separation (e.g., charge injection at interfaces). To treat ultrafast excited-state dynamics and exciton/charge transport we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework incorporating quantum transitions. Our calculations rely on the use of the Collective Electronic Oscillator (CEO) package accounting for many-body effects and actual potential energy surfaces of the excited states combined with Tully's fewest switches algorithm for surface hopping for probing nonadiabatic processes. This method is applied to model the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene, PPV). Our analysis shows intricate details of photoinduced vibronic relaxation and identifies specific slow and fast nuclear motions that are strongly coupled to the electronic degrees of freedom, namely, torsion and bond length alternation, respectively. Nonadiabatic relaxation of the highly excited mA(g) state is predicted to occur on a femtosecond time scale at room temperature and on a picosecond time scale at low temperature.

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

PubMed

Wu, Yilei; Young, Ryan M; Frasconi, Marco; Schneebeli, Severin T; Spenst, Peter; Gardner, Daniel M; Brown, Kristen E; Würthner, Frank; Stoddart, J Fraser; Wasielewski, Michael R

2015-10-21

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.

Photoinduced Electron Transfer in the Strong Coupling Regime: Waveguide-Plasmon Polaritons.

PubMed

Zeng, Peng; Cadusch, Jasper; Chakraborty, Debadi; Smith, Trevor A; Roberts, Ann; Sader, John E; Davis, Timothy J; Gómez, Daniel E

2016-04-13

Reversible exchange of photons between a material and an optical cavity can lead to the formation of hybrid light-matter states where material properties such as the work function [ Hutchison et al. Adv. Mater. 2013 , 25 , 2481 - 2485 ], chemical reactivity [ Hutchison et al. Angew. Chem., Int. Ed. 2012 , 51 , 1592 - 1596 ], ultrafast energy relaxation [ Salomon et al. Angew. Chem., Int. Ed. 2009 , 48 , 8748 - 8751 ; Gomez et al. J. Phys. Chem. B 2013 , 117 , 4340 - 4346 ], and electrical conductivity [ Orgiu et al. Nat. Mater. 2015 , 14 , 1123 - 1129 ] of matter differ significantly to those of the same material in the absence of strong interactions with the electromagnetic fields. Here we show that strong light-matter coupling between confined photons on a semiconductor waveguide and localized plasmon resonances on metal nanowires modifies the efficiency of the photoinduced charge-transfer rate of plasmonic derived (hot) electrons into accepting states in the semiconductor material. Ultrafast spectroscopy measurements reveal a strong correlation between the amplitude of the transient signals, attributed to electrons residing in the semiconductor and the hybridization of waveguide and plasmon excitations.

Ultrafast Spin Crossover in [FeII (bpy)3 ]2+ : Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy.

PubMed

Moguilevski, Alexandre; Wilke, Martin; Grell, Gilbert; Bokarev, Sergey I; Aziz, Saadullah G; Engel, Nicholas; Raheem, Azhr A; Kühn, Oliver; Kiyan, Igor Yu; Aziz, Emad F

2017-03-03

Photoinduced spin-flip in Fe II complexes is an ultrafast phenomenon that has the potential to become an alternative to conventional processing and magnetic storage of information. Following the initial excitation by visible light into the singlet metal-to-ligand charge-transfer state, the electronic transition to the high-spin quintet state may undergo different pathways. Here we apply ultrafast XUV (extreme ultraviolet) photoemission spectroscopy to track the low-to-high spin dynamics in the aqueous iron tris-bipyridine complex, [Fe(bpy) 3 ] 2+ , by monitoring the transient electron density distribution among excited states with femtosecond time resolution. Aided by first-principles calculations, this approach enables us to reveal unambiguously both the sequential and direct de-excitation pathways from singlet to quintet state, with a branching ratio of 4.5:1. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-amplified photo-induced gap quenching in a correlated electron material

PubMed Central

Mathias, S.; Eich, S.; Urbancic, J.; Michael, S.; Carr, A. V.; Emmerich, S.; Stange, A.; Popmintchev, T.; Rohwer, T.; Wiesenmayer, M.; Ruffing, A.; Jakobs, S.; Hellmann, S.; Matyba, P.; Chen, C.; Kipp, L.; Bauer, M.; Kapteyn, H. C.; Schneider, H. C.; Rossnagel, K.; Murnane, M. M.; Aeschlimann, M.

2016-01-01

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. We show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically depends on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation. PMID:27698341

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

Covalent Linking Greatly Enhances Photoinduced Electron Transfer in Fullerene-Quantum Dot Nanocomposites: Time-Domain Ab Initio Study.

PubMed

Chaban, Vitaly V; Prezhdo, Victor V; Prezhdo, Oleg V

2013-01-03

Nonadiabatic molecular dynamics combined with time-domain density functional theory are used to study electron transfer (ET) from a CdSe quantum dot (QD) to the C60 fullerene, occurring in several types of hybrid organic/inorganic nanocomposites. By unveiling the time dependence of the ET process, we show that covalent bonding between the QD and C60 is particularly important to ensure ultrafast transmission of the excited electron from the QD photon-harvester to the C60 electron acceptor. Despite the close proximity of the donor and acceptor species provided by direct van der Waals contact, it leads to a notably weaker QD-C60 interaction than a lengthy molecular bridge. We show that the ET rate in a nonbonded mixture of QDs and C60 can be enhanced by doping. The photoinduced ET is promoted primarily by mid- and low-frequency vibrations. The study establishes the basic design principles for enhancing photoinduced charge separation in nanoscale light harvesting materials.

Photoinduced ultrafast charge-order melting: Charge-order inversion and nonthermal effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Veenendaal, Michel

2016-09-01

The effect of photoexcitation is studied for a system with checkerboard charge order induced by displacements of ligands around a metal site. The motion of the ligands is treated classically and the electronic charges are simplified to two-level molecular bond charges. The calculations are done for a checkerboard charge-ordered system with about 100 000 ligand oscillators coupled to a fixed-temperature bath. The initial photoexcitation is followed by a rapid decrease in the charge-order parameter within 50–100 femtoseconds while leaving the correlation length almost unchanged. Depending on the fluence, a complete melting of the charge order occurs in less than amore » picosecond. While for low fluences, the system returns to its original state, for full melting, it recovers to its broken-symmetry state leading to an inversion of the charge order. For small long-range interactions, recovery can be slow due to domain formation.« less

Photoinduced ultrafast charge-order melting: Charge-order inversion and nonthermal effects

DOE PAGES

van Veenendaal, Michel

2016-09-01

The effect of photoexcitation is studied for a system with checkerboard charge order induced by displacements of ligands around a metal site. The motion of the ligands is treated classically and the electronic charges are simplified to two-level molecular bond charges. The calculations are done for a checkerboard charge-ordered system with about 100 000 ligand oscillators coupled to a fixed-temperature bath. The initial photoexcitation is followed by a rapid decrease in the charge-order parameter within 50–100 femtoseconds while leaving the correlation length almost unchanged. Depending on the fluence, a complete melting of the charge order occurs in less than amore » picosecond. While for low fluences, the system returns to its original state, for full melting, it recovers to its broken-symmetry state leading to an inversion of the charge order. Finally, for small long-range interactions, recovery can be slow due to domain formation.« less

Ultrafast dynamics during the photoinduced phase transition in VO2

NASA Astrophysics Data System (ADS)

Wegkamp, Daniel; Stähler, Julia

2015-12-01

The phase transition of VO2 from a monoclinic insulator to a rutile metal, which occurs thermally at TC = 340 K, can also be driven by strong photoexcitation. The ultrafast dynamics during this photoinduced phase transition (PIPT) have attracted great scientific attention for decades, as this approach promises to answer the question of whether the insulator-to-metal (IMT) transition is caused by electronic or crystallographic processes through disentanglement of the different contributions in the time domain. We review our recent results achieved by femtosecond time-resolved photoelectron, optical, and coherent phonon spectroscopy and discuss them within the framework of a selection of latest, complementary studies of the ultrafast PIPT in VO2. We show that the population change of electrons and holes caused by photoexcitation launches a highly non-equilibrium plasma phase characterized by enhanced screening due to quasi-free carriers and followed by two branches of non-equilibrium dynamics: (i) an instantaneous (within the time resolution) collapse of the insulating gap that precedes charge carrier relaxation and significant ionic motion and (ii) an instantaneous lattice potential symmetry change that represents the onset of the crystallographic phase transition through ionic motion on longer timescales. We discuss the interconnection between these two non-thermal pathways with particular focus on the meaning of the critical fluence of the PIPT in different types of experiments. Based on this, we conclude that the PIPT threshold identified in optical experiments is most probably determined by the excitation density required to drive the lattice potential change rather than the IMT. These considerations suggest that the IMT can be driven by weaker excitation, predicting a transiently metallic, monoclinic state of VO2 that is not stabilized by the non-thermal structural transition and, thus, decays on ultrafast timescales.

Probing Photoinduced Structural Phase Transitions by Fast or Ultra-Fast Time-Resolved X-Ray Diffraction

NASA Astrophysics Data System (ADS)

Cailleau, Hervé Collet, Eric; Buron-Le Cointe, Marylise; Lemée-Cailleau, Marie-Hélène Koshihara, Shin-Ya

A new frontier in the field of structural science is the emergence of the fast and ultra-fast X-ray science. Recent developments in time-resolved X-ray diffraction promise direct access to the dynamics of electronic, atomic and molecular motions in condensed matter triggered by a pulsed laser irradiation, i.e. to record "molecular movies" during the transformation of matter initiated by light pulse. These laser pump and X-ray probe techniques now provide an outstanding opportunity for the direct observation of a photoinduced structural phase transition as it takes place. The use of X-ray short-pulse of about 100ps around third-generation synchrotron sources allows structural investigations of fast photoinduced processes. Other new X-ray sources, such as laser-produced plasma ones, generate ultra-short pulses down to 100 fs. This opens the way to femtosecond X-ray crystallography, but with rather low X-ray intensities and more limited experimental possibilities at present. However this new ultra-fast science rapidly progresses around these sources and new large-scale projects exist. It is the aim of this contribution to overview the state of art and the perspectives of fast and ultra-fast X-ray scattering techniques to study photoinduced phase transitions (here, the word ultra-fast is used for sub-picosecond time resolution). In particular we would like to largely present the contribution of crystallographic methods in comparison with optical methods, such as pump-probe reflectivity measurements, the reader being not necessary familiar with X-ray scattering. Thus we want to present which type of physical information can be obtained from the positions of the Bragg peaks, their intensity and their shape, as well as from the diffuse scattering beyond Bragg peaks. An important physical feature is to take into consideration the difference in nature between a photoinduced phase transition and conventional homogeneous photoinduced chemical or biochemical processes where molecules transform in an independent way each other. Actually the photoinduced phase transition with the establishment of the new electronic and structural oscopic order is preceded by precursor co-operative phenomena due to the formation of nano-scale correlated objects. These are the counterpart of pre-transitional fluctuations at thermal equilibrium which take place above the transition temperature (short range order preceding long range one). Moreover ultra-fast X-ray scattering will play a central role within the fascinating field of manipulating coherence, for instance to directly observe coherent atomic motions induced by a light pulse, such as optical phonons. In the first part of this contribution we present what experimental features are accessible by X-ray scattering to describe the physical picture for a photoinduced structural phase transition. The second part shows how a time-resolved X-ray scattering experiment can be performed with regards to the different pulsed X-ray sources. The first time-resolved X-ray diffraction experiments on photoinduced phase transitions are described and discussed in the third part. Finally some challenges for future are briefly indicated in the conclusion.

Observation of Internal Photoinduced Electron and Hole Separation in Hybrid Two-Dimentional Perovskite Films.

PubMed

Liu, Junxue; Leng, Jing; Wu, Kaifeng; Zhang, Jun; Jin, Shengye

2017-02-01

Two-dimensional (2D) organolead halide perovskites are promising for various optoelectronic applications. Here we report a unique spontaneous charge (electron/hole) separation property in multilayered (BA) 2 (MA) n-1 Pb n I 3n+1 (BA = CH 3 (CH 2 ) 3 NH 3 + , MA = CH 3 NH 3 + ) 2D perovskite films by studying the charge carrier dynamics using ultrafast transient absorption and photoluminescence spectroscopy. Surprisingly, the 2D perovskite films, although nominally prepared as "n = 4", are found to be mixture of multiple perovskite phases, with n = 2, 3, 4 and ≈ ∞, that naturally align in the order of n along the direction perpendicular to the substrate. Driven by the band alignment between 2D perovskites phases, we observe consecutive photoinduced electron transfer from small-n to large-n phases and hole transfer in the opposite direction on hundreds of picoseconds inside the 2D film of ∼358 nm thickness. This internal charge transfer efficiently separates electrons and holes to the upper and bottom surfaces of the films, which is a unique property beneficial for applications in photovoltaics and other optoelectronics devices.

Self-amplified photo-induced gap quenching in a correlated electron material

DOE PAGES

Mathias, S.; Eich, S.; Urbancic, J.; ...

2016-10-04

Capturing the dynamic electronic band structure of a correlated material presents a powerful capability for uncovering the complex couplings between the electronic and structural degrees of freedom. When combined with ultrafast laser excitation, new phases of matter can result, since far-from-equilibrium excited states are instantaneously populated. Here, we elucidate a general relation between ultrafast non-equilibrium electron dynamics and the size of the characteristic energy gap in a correlated electron material. Here, we show that carrier multiplication via impact ionization can be one of the most important processes in a gapped material, and that the speed of carrier multiplication critically dependsmore » on the size of the energy gap. In the case of the charge-density wave material 1T-TiSe 2, our data indicate that carrier multiplication and gap dynamics mutually amplify each other, which explains—on a microscopic level—the extremely fast response of this material to ultrafast optical excitation.« less

Ultrafast Nanoimaging of the Photoinduced Phase Transition Dynamics in VO2.

PubMed

Dönges, Sven A; Khatib, Omar; O'Callahan, Brian T; Atkin, Joanna M; Park, Jae Hyung; Cobden, David; Raschke, Markus B

2016-05-11

Many phase transitions in correlated matter exhibit spatial inhomogeneities with expected yet unexplored effects on the associated ultrafast dynamics. Here we demonstrate the combination of ultrafast nondegenerate pump-probe spectroscopy with far from equilibrium excitation, and scattering scanning near-field optical microscopy (s-SNOM) for ultrafast nanoimaging. In a femtosecond near-field near-IR (NIR) pump and mid-IR (MIR) probe study, we investigate the photoinduced insulator-to-metal (IMT) transition in nominally homogeneous VO2 microcrystals. With pump fluences as high as 5 mJ/cm(2), we can reach three distinct excitation regimes. We observe a spatial heterogeneity on ∼50-100 nm length scales in the fluence-dependent IMT dynamics ranging from <100 fs to ∼1 ps. These results suggest a high sensitivity of the IMT with respect to small local variations in strain, doping, or defects that are difficult to discern microscopically. We provide a perspective with the distinct requirements and considerations of ultrafast spatiotemporal nanoimaging of phase transitions in quantum materials.

Time-domain ab initio modeling of photoinduced dynamics at nanoscale interfaces.

PubMed

Wang, Linjun; Long, Run; Prezhdo, Oleg V

2015-04-01

Nonequilibrium processes involving electronic and vibrational degrees of freedom in nanoscale materials are under active experimental investigation. Corresponding theoretical studies are much scarcer. The review starts with the basics of time-dependent density functional theory, recent developments in nonadiabatic molecular dynamics, and the fusion of the two techniques. Ab initio simulations of this kind allow us to directly mimic a great variety of time-resolved experiments performed with pump-probe laser spectroscopies. The focus is on the ultrafast photoinduced charge and exciton dynamics at interfaces formed by two complementary materials. We consider purely inorganic materials, inorganic-organic hybrids, and all organic interfaces, involving bulk semiconductors, metallic and semiconducting nanoclusters, graphene, carbon nanotubes, fullerenes, polymers, molecular crystals, molecules, and solvent. The detailed atomistic insights available from time-domain ab initio studies provide a unique description and a comprehensive understanding of the competition between electron transfer, thermal relaxation, energy transfer, and charge recombination processes. These advances now make it possible to directly guide the development of organic and hybrid solar cells, as well as photocatalytic, electronic, spintronic, and other devices relying on complex interfacial dynamics.

Direct experimental evidence for photoinduced strong-coupling polarons in organolead halide perovskite nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Kaibo; Qatar Univ., Doha; Abdellah, Mohamed

Echoing the roaring success of their bulk coun-terparts, nano-objects built from organolead halide perov-skites (OLHP) present bright prospects for surpassing the performances of their conventional organic and inorganic analogues in photodriven technologies. Unraveling the pho-toinduced charge dynamics is essential for optimizing OLHP optoelectronic functionalities. However, mapping the carri-er-lattice interactions remains challenging, owing to their manifestations on multiple length scales and time scales. By correlating ultrafast time-resolved optical and X-ray absorp-tion measurements, this work reveals the photoinduced formation of strong-coupling polarons in CH 3NH 3PbBr 3 nanoparticles. Such polarons originate from the self-trapping of electrons in the net Coulombic field causedmore » by the dis-placed inorganic nuclei and the oriented organic cations. The transient structural change detected at the Pb L 3 X-ray ab-sorption edge is well captured by a distortion with average bond elongation in the [PbBr 6] 2- motif. As a result, general implications for designing novel OLHP nanomaterials targeting the active utilization of these quasi-particles are outlined.« less

Direct experimental evidence for photoinduced strong-coupling polarons in organolead halide perovskite nanoparticles

DOE PAGES

Zheng, Kaibo; Qatar Univ., Doha; Abdellah, Mohamed; ...

2016-10-28

Echoing the roaring success of their bulk coun-terparts, nano-objects built from organolead halide perov-skites (OLHP) present bright prospects for surpassing the performances of their conventional organic and inorganic analogues in photodriven technologies. Unraveling the pho-toinduced charge dynamics is essential for optimizing OLHP optoelectronic functionalities. However, mapping the carri-er-lattice interactions remains challenging, owing to their manifestations on multiple length scales and time scales. By correlating ultrafast time-resolved optical and X-ray absorp-tion measurements, this work reveals the photoinduced formation of strong-coupling polarons in CH 3NH 3PbBr 3 nanoparticles. Such polarons originate from the self-trapping of electrons in the net Coulombic field causedmore » by the dis-placed inorganic nuclei and the oriented organic cations. The transient structural change detected at the Pb L 3 X-ray ab-sorption edge is well captured by a distortion with average bond elongation in the [PbBr 6] 2- motif. As a result, general implications for designing novel OLHP nanomaterials targeting the active utilization of these quasi-particles are outlined.« less

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2

NASA Astrophysics Data System (ADS)

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-02-01

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO2) via the observation of a positive absorption signal (at λ pr  >  610 nm) at later delay times. An electron transfer rate of 7  ×  1010 s-1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO2.

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2.

PubMed

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-01-05

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO 2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO 2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO 2 ) via the observation of a positive absorption signal (at λ pr   >  610 nm) at later delay times. An electron transfer rate of 7  ×  10 10 s -1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO 2 .

A time-dependent order parameter for ultrafast photoinduced phase transitions.

PubMed

Beaud, P; Caviezel, A; Mariager, S O; Rettig, L; Ingold, G; Dornes, C; Huang, S-W; Johnson, J A; Radovic, M; Huber, T; Kubacka, T; Ferrer, A; Lemke, H T; Chollet, M; Zhu, D; Glownia, J M; Sikorski, M; Robert, A; Wadati, H; Nakamura, M; Kawasaki, M; Tokura, Y; Johnson, S L; Staub, U

2014-10-01

Strongly correlated electron systems often exhibit very strong interactions between structural and electronic degrees of freedom that lead to complex and interesting phase diagrams. For technological applications of these materials it is important to learn how to drive transitions from one phase to another. A key question here is the ultimate speed of such phase transitions, and to understand how a phase transition evolves in the time domain. Here we apply time-resolved X-ray diffraction to directly measure the changes in long-range order during ultrafast melting of the charge and orbitally ordered phase in a perovskite manganite. We find that although the actual change in crystal symmetry associated with this transition occurs over different timescales characteristic of the many electronic and vibrational coordinates of the system, the dynamics of the phase transformation can be well described using a single time-dependent 'order parameter' that depends exclusively on the electronic excitation.

Photoinduced Ultrafast Intramolecular Excited-State Energy Transfer in the Silylene-Bridged Biphenyl and Stilbene (SBS) System: A Nonadiabatic Dynamics Point of View.

PubMed

Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang

2015-07-09

The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.

Laser pulse control of ultrafast heterogeneous electron transfer: a computational study.

PubMed

Wang, Luxia; May, Volkhard

2004-10-22

Laser pulse control of the photoinduced 90 fs charge injection from perylene into the conduction band of TiO2 is studied theoretically. The approach accounts for the electronic-ground state of the dye, the first excited state, the ionized state formed after charge injection, and the continuum of the electronic states in the conduction band, all defined vs a single reaction coordinate. To address different control tasks optimal control theory is combined with a full quantum dynamical description of the electron-vibrational motion accompanying the charge injection process. First it is proved in which way the charge injection time can be changed by tailored laser pulses. In a second step a pump-dump scheme from the perylene ground state to the first excited electronic state and back to the ground state is discussed. Because of the strong coupling of the excited perylene state to the band continuum of TiO2 this control task is more suited to an experimental test than the direct control of the charge injection.

Evidence of Photo-induced Dynamic Competition of Metallic and Insulating Phase in a Layered Manganite.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuelin; Walko, Donald A.; Li, Qing'an

2015-12-16

We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr2Mn2O7, can be manipulated using ultrafast optical excitation. The time- dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the lasermore » excitation modulates the local competition between the metallic and the insulating phases.« less

Evidence of photo-induced dynamic competition of metallic and insulating phase in a layered manganite

DOE PAGES

Li, Yuelin; Walko, Daonld A.; Li, Qing'an; ...

2015-11-17

We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr 2Mn 2O 7, can be manipulated using ultrafast optical excitation. The time-dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario wherebymore » the laser excitation modulates the local competition between the metallic and the insulating phases.« less

What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

PubMed

Jakowetz, Andreas C; Böhm, Marcus L; Zhang, Jiangbin; Sadhanala, Aditya; Huettner, Sven; Bakulin, Artem A; Rao, Akshay; Friend, Richard H

2016-09-14

In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

DOE PAGES

Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud; ...

2016-10-18

We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS 2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud

We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS 2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer Processes

DTIC Science & Technology

devices and photoelectrochemical cells. Theoretical methodology for simulating the nonadiabatic dynamics of photoinduced PCET reactions in solution has...tuning and control of the ultrafast dynamics is crucial for designing renewable and sustainable energy sources, such as artificial photosynthesis...describes the solute with a multiconfigurational method in a bath of explicit solvent molecules. The transferring hydrogen nucleus is represented as a

Photoinduced Processes in Cobalt-Complexes: Condensed Phase and Gas Phase

NASA Astrophysics Data System (ADS)

Rupp, F.; Chevalier, K.; Wolf, M. M. N.; Krüger, H.-J.; Wüllen, C. v.; Nosenko, Y.; Niedner-Schatteburg, Y.; Riehn, C.; Diller, R.

2013-03-01

Femtosecond time-resolved, steady-state spectroscopic methods and quantum chemical calculations are employed to study ultrafast photoinduced processes in [Co(III)-(L-N4Me2)(dbc)](BPh4) and [Co(II)-(L-N4tBu2)(dbsq)](B(p-C6H4Cl)4) and to characterise the transient redox- and spin-states in condensed and gas phase.

Structural dynamics of a noncovalent charge transfer complex from femtosecond stimulated Raman spectroscopy.

PubMed

Fujisawa, Tomotsumi; Creelman, Mark; Mathies, Richard A

2012-09-06

Femtosecond stimulated Raman spectroscopy is used to examine the structural dynamics of photoinduced charge transfer within a noncovalent electron acceptor/donor complex of pyromellitic dianhydride (PMDA, electron acceptor) and hexamethylbenzene (HMB, electron donor) in ethylacetate and acetonitrile. The evolution of the vibrational spectrum reveals the ultrafast structural changes that occur during the charge separation (Franck-Condon excited state complex → contact ion pair) and the subsequent charge recombination (contact ion pair → ground state complex). The Franck-Condon excited state is shown to have significant charge-separated character because its vibrational spectrum is similar to that of the ion pair. The charge separation rate (2.5 ps in ethylacetate and ∼0.5 ps in acetonitrile) is comparable to solvation dynamics and is unaffected by the perdeuteration of HMB, supporting the dominant role of solvent rearrangement in charge separation. On the other hand, the charge recombination slows by a factor of ∼1.4 when using perdeuterated HMB, indicating that methyl hydrogen motions of HMB mediate the charge recombination process. Resonance Raman enhancement of the HMB vibrations in the complex reveals that the ring stretches of HMB, and especially the C-CH(3) deformations are the primary acceptor modes promoting charge recombination.

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer.

PubMed

Lynch, Michael S; Slenkamp, Karla M; Khalil, Munira

2012-06-28

Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ∼57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs.

Femtosecond activation of magnetoelectricity

NASA Astrophysics Data System (ADS)

Bossini, D.; Konishi, K.; Toyoda, S.; Arima, T.; Yumoto, J.; Kuwata-Gonokami, M.

2018-04-01

In magnetoelectric and multiferroic materials, the magnetic degree of freedom can be controlled by electric field, and vice versa. A significant amount of research has been devoted to exploiting this effect for magnetoelectric data storage and manipulation devices driven by d.c. electric fields1-4. Aiming at ever-faster schemes of magnetoelectric manipulation, a promising alternative approach offers similar control on a femtosecond timescale, relying on laser pulses4-6 to control both the charge7,8 and the magnetic9,10 order of solids. Here we photo-induce magnetoelectricity and multiferroicity in CuB2O4 on a sub-picosecond timescale. This process is triggered by the resonant optical generation of the highest-energy magnetic excitations—magnons with wavevectors near the edges of the Brillouin zone. The most striking consequence of the photo-excitation is that the absorption of light becomes non-reciprocal, which means that the material exhibits a different transparency for two opposite directions of propagation of light. The photo-induced magnetoelectricity does not show any decay on the picosecond timescale. Our findings uncover a path for ultrafast manipulations of the intrinsic coupling between charges and spins in multiferroics4, which may reveal unexplored magnetic configurations and unravel new functionalities in terms of femtosecond optical control of magnetism.

Direct characterization of photoinduced lattice dynamics in BaFe 2As 2

DOE PAGES

Gerber, S.; Kim, K. W.; Zhang, Y.; ...

2015-06-08

Ultrafast light pulses can modify electronic properties of quantum materials by perturbing the underlying, intertwined degrees of freedom. In particular, iron-based superconductors exhibit a strong coupling among electronic nematic fluctuations, spins and the lattice, serving as a playground for ultrafast manipulation. Here we use time-resolved X-ray scattering to measure the lattice dynamics of photoexcited BaFe 2As 2. On optical excitation, no signature of an ultrafast change of the crystal symmetry is observed, but the lattice oscillates rapidly in time due to the coherent excitation of an A1g mode that modulates the Fe–As–Fe bond angle. We directly quantify the coherent latticemore » dynamics and show that even a small photoinduced lattice distortion can induce notable changes in the electronic and magnetic properties. Our analysis implies that transient structural modification can be an effective tool for manipulating the electronic properties of multi-orbital systems, where electronic instabilities are sensitive to the orbital character of bands.« less

Direct characterization of photoinduced lattice dynamics in BaFe2As2

PubMed Central

Gerber, S.; Kim, K. W.; Zhang, Y.; Zhu, D.; Plonka, N.; Yi, M.; Dakovski, G. L.; Leuenberger, D.; Kirchmann, P.S.; Moore, R. G.; Chollet, M.; Glownia, J. M.; Feng, Y.; Lee, J.-S.; Mehta, A.; Kemper, A. F.; Wolf, T.; Chuang, Y.-D.; Hussain, Z.; Kao, C.-C.; Moritz, B.; Shen, Z.-X.; Devereaux, T. P.; Lee, W.-S.

2015-01-01

Ultrafast light pulses can modify electronic properties of quantum materials by perturbing the underlying, intertwined degrees of freedom. In particular, iron-based superconductors exhibit a strong coupling among electronic nematic fluctuations, spins and the lattice, serving as a playground for ultrafast manipulation. Here we use time-resolved X-ray scattering to measure the lattice dynamics of photoexcited BaFe2As2. On optical excitation, no signature of an ultrafast change of the crystal symmetry is observed, but the lattice oscillates rapidly in time due to the coherent excitation of an A1g mode that modulates the Fe–As–Fe bond angle. We directly quantify the coherent lattice dynamics and show that even a small photoinduced lattice distortion can induce notable changes in the electronic and magnetic properties. Our analysis implies that transient structural modification can be an effective tool for manipulating the electronic properties of multi-orbital systems, where electronic instabilities are sensitive to the orbital character of bands. PMID:26051704

Nonequilibrium Phase Precursors during a Photoexcited Insulator-to-Metal Transition in V2O3

NASA Astrophysics Data System (ADS)

Singer, Andrej; Ramirez, Juan Gabriel; Valmianski, Ilya; Cela, Devin; Hua, Nelson; Kukreja, Roopali; Wingert, James; Kovalchuk, Olesya; Glownia, James M.; Sikorski, Marcin; Chollet, Matthieu; Holt, Martin; Schuller, Ivan K.; Shpyrko, Oleg G.

2018-05-01

Here, we photoinduce and directly observe with x-ray scattering an ultrafast enhancement of the structural long-range order in the archetypal Mott system V2O3 . Despite the ultrafast increase in crystal symmetry, the change of unit cell volume occurs an order of magnitude slower and coincides with the insulator-to-metal transition. The decoupling between the two structural responses in the time domain highlights the existence of a transient photoinduced precursor phase, which is distinct from the two structural phases present in equilibrium. X-ray nanoscopy reveals that acoustic phonons trapped in nanoscale twin domains govern the dynamics of the ultrafast transition into the precursor phase, while nucleation and growth of metallic domains dictate the duration of the slower transition into the metallic phase. The enhancement of the long-range order before completion of the electronic transition demonstrates the critical role the nonequilibrium structural phases play during electronic phase transitions in correlated electrons systems.

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in POLY(3-HEXYLTHIOPHENE)-BLOCK-OLIGO(ANTHRACENE-9,10-DIYL)

NASA Astrophysics Data System (ADS)

Strain, Jacob; Rathnayake, Hemali; Liu, Jinjun

2017-06-01

Semiconducting polymer nanostructures featuring bulk heterojunction (BHJ) architecture are promising light harvesters in photovoltaic (PV) devices because they allow control of individual domain sizes, internal structure and ordering, as well as well-defined contact between the electron donor and acceptor. Power conversion efficiency (PCE) of PV devices strongly depends on photoinduced dynamics. Understanding and optimizing photoinduced charge transfer processes in BHJ's hence help improve the performance of PV devices and increase their PCE in particular. We have investigated the photoinduced dynamics of a block polymer containing moieties of poly-3-hexylthiophene (P3HT) and polyanthracene (PANT) in solution and in solid state with femtosecond transient absorption (TA) spectroscopy. The dynamics of the polymer PANT alone are also studied as a control. The TA spectra of PANT includes a strong excited state absorption centered at 610 (nm) along with a stimulated emission signal stretching past the detection limit into the UV region which is absent in the monomer's spectra in the detection window. The block polymer's TA spectra strongly resembles that of P3HT but a noticeable positive pull on P3HT's stimulated emission signal residing at 575-620 (nm) is indicative of the excited state absorption of PANT in the adjacent spectral region. The doubling of the lifetime exciton delocalization on the block polymer versus P3HT alone have alluded that the lifetime of P3HT is extended by the covalent addition of PANT. The current spectroscopic investigation represents an interesting example of photoinduced processes in systems with complex energy level structure. Studies of dependence of change generation and separation on composition, dimension, and morphology of the heterojunctions are in process.

Revealing Extremely Low Energy Amplitude Modes in the Charge-Density-Wave Compound LaAgSb_{2}.

PubMed

Chen, R Y; Zhang, S J; Zhang, M Y; Dong, T; Wang, N L

2017-03-10

Using infrared spectroscopy and ultrafast pump probe measurement, we have studied the two charge-density-wave (CDW) instabilities in the layered compound LaAgSb_{2}. The development of CDW energy gaps was clearly observed by optical spectroscopy, which removed most of the free carrier spectral weight. More interestingly, our time-resolved measurements revealed two coherent oscillations that softened by approaching the two phase transition temperatures, respectively. We addressed that these two oscillations come from the amplitude modes of CDW collective excitations, the surprisingly low energies (0.12 THz and 0.34 THz for the higher and lower temperature ones, respectively) of which are associated with the extremely small nesting wave vectors. Additionally, the amplitude and relaxation time of photoinduced reflectivity of LaAgSb_{2} single crystals stayed unchanged across the CDW phase transitions, which is quite rare and deserves further investigation.

Photoinduced charge-transfer materials for nonlinear optical applications

DOEpatents

McBranch, Duncan W.

2006-10-24

A method using polyelectrolyte self-assembly for preparing multi-layered organic molecular materials having individual layers which exhibit ultrafast electron and/or energy transfer in a controlled direction occurring over the entire structure. Using a high molecular weight, water-soluble, anionic form of poly-phenylene vinylene, self-assembled films can be formed which show high photoluminescence quantum efficiency (QE). The highest emission QE is achieved using poly(propylene-imine) (PPI) dendrimers as cationic binders. Self-quenching of the luminescence is observed as the solid polymer film thickness is increased and can be reversed by inserting additional spacer layers of transparent polyelectrolytes between each active conjugated layer, such that the QE grows with thickness. A red shift of the luminescence is also observed as additional PPV layers are added. This effect persists as self-quenching is eliminated. Charge transfer superlattices can be formed by additionally incorporating C.sub.60 acceptor layers.

Ultrafast structural and electronic dynamics of the metallic phase in a layered manganite

PubMed Central

Piazza, L.; Ma, C.; Yang, H. X.; Mann, A.; Zhu, Y.; Li, J. Q.; Carbone, F.

2013-01-01

The transition between different states in manganites can be driven by various external stimuli. Controlling these transitions with light opens the possibility to investigate the microscopic path through which they evolve. We performed femtosecond (fs) transmission electron microscopy on a bi-layered manganite to study its response to ultrafast photoexcitation. We show that a photoinduced temperature jump launches a pressure wave that provokes coherent oscillations of the lattice parameters, detected via ultrafast electron diffraction. Their impact on the electronic structure are monitored via ultrafast electron energy loss spectroscopy, revealing the dynamics of the different orbitals in response to specific structural distortions. PMID:26913564

Ultrafast photo-induced hidden phases in strained manganite thin films

NASA Astrophysics Data System (ADS)

Zhang, Jingdi; McLeod, A. S.; Zhang, Gu-Feng; Stoica, Vladimir; Jin, Feng; Gu, Mingqiang; Gopalan, Venkatraman; Freeland, John W.; Wu, Wenbin; Rondinelli, James; Wen, Haidan; Basov, D. N.; Averitt, R. D.

Correlated transition metal oxides (TMOs) are particularly sensitive to external control because of energy degeneracy in a complex energy landscape that promote a plethora of metastable states. However, it remains a grand challenge to actively control and fully explore the rich landscape of TMOs. Dynamic control with pulsed photons can overcome energetic barriers, enabling access to transient or metastable states that are not thermally accessible. In the past, we have demonstrated that mode-selective single-laser-pulse excitation of a strained manganite thin film La2/3Ca1/3MnO3 initiates a persistent phase transition from an emergent antiferromagnetic insulating ground state to a ferromagnetic metallic metastable state. Beyond the photo-induced insulator to metal transition, we recently discovered a new peculiar photo-induced hidden phase, identified by an experimental approach that combines ultrafast pump-probe spectroscopy, THz spectroscopy, X-ray diffraction, cryogenic near-field spectroscopy and SHG probe. This work is funded by the DOE, Office of Science, Office of Basic Energy Science under Award Numbers DE-SC0012375 and DE-SC0012592.

Triphenylamine-Based Push–Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics

PubMed Central

2017-01-01

Small push–pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs. PMID:28413568

Ultrafast Electron Transfer across a Nanocapsular Wall: Coumarins as Donors, Viologen as Acceptor, and Octa Acid Capsule as the Mediator.

PubMed

Chuang, Chi-Hung; Porel, Mintu; Choudhury, Rajib; Burda, Clemens; Ramamurthy, V

2018-01-11

Results of our study on ultrafast electron transfer (eT) dynamics from coumarins (coumarin-1, coumarin-480, and coumarin-153) incarcerated within octa acid (OA) capsules as electron donors to methyl viologen dissolved in water as acceptor are presented. Upon photoexcitation, coumarin inside the OA capsule transfers an electron to the acceptor electrostatically attached to the capsule leading to a long-lived radical-ion pair separated by the OA capsular wall. This charge-separated state returns to the neutral ground state via back electron transfer on the nanosecond time scale. This system allows for ultrafast electron transfer processes through a molecular wall from the apolar capsular interior to the highly polar (aqueous) environment on the femtosecond time scale. Employing femtosecond transient absorption spectroscopy, distinct rates of both forward (1-25 ps) and backward eT (700-1200 ps) processes were measured. Further understanding of the energetics is provided using Rehm-Weller analysis for the investigated photoinduced eT reactions. The results provide the rates of the eT across a molecular wall, akin to an isotropic solution, depending on the standard free energy of the reaction. The insights from this work could be utilized in the future design of efficient electron transfer processes across interfaces separating apolar and polar environments.

Ultrafast photoinduced electron transfer in the micelle and the gel phase of a PEO-PPO-PEO triblock copolymer

NASA Astrophysics Data System (ADS)

Mandal, Ujjwal; Ghosh, Subhadip; Dey, Shantanu; Adhikari, Aniruddha; Bhattacharyya, Kankan

2008-04-01

Ultrafast photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to coumarin dyes is studied in the micelle and the gel phase of a triblock copolymer, (PEO)20-(PPO)70-(PEO)20 (Pluronic P123) by picosecond and femtosecond emission spectroscopies. The rate of PET in a P123 micelle and gel is found to be nonexponential and faster than the slow components of solvation dynamics. In a P123 micelle and gel, PET occurs on multiple time scales ranging from a subpicosecond time scale to a few nanoseconds. In the gel phase, the highest rate constant (9.3×109M-1s-1) of ET for C152 is about two times higher than that (3.8×109M-1s-1) observed in micelle phase. The ultrafast components of electron transfer (ET) exhibits a bell shaped dependence with the free energy change which is similar to the Marcus inversion. Possible reasons for slower PET in P123 micelle compared to other micelles and relative to P123 gel are discussed.

Elucidating the Ultrafast Dynamics of Photoinduced Charge Separation in Metalloporphyrin-Fullerene Dyads Across the Electromagnetic Spectrum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, J.; Pápai, M.; Hirsch, A.

Metalloporphyrins are prominent building blocks in the synthetic toolbox of advanced photodriven molecular devices. When the central ion is paramagnetic, the relaxation pathways within the manifold of excited states are highly intricate so that unravelling the intramolecular energy and electron transfer processes is usually a very complex task. This fact is critically hampering the development of applications based on the enhanced coupling offered by the electronic exchange interaction. In this work, the dynamics of charge separation in a copper porphyrin-fullerene are studied with several complementary spectroscopic tools across the electromagnetic spectrum (from near infra-red to X-ray wavelengths), each of themmore » providing specific diagnostics. Correlating the various rates clearly demonstrates that the lifetime of the photoinduced charge-separated state exceeds by about 10 fold that of the isolated photoexcited CuII porphyrin. As revealed by the spectral modifications in the XANES region, this stabilization is accompanied by a transient change in covalency around the CuII center, which is induced by an enhanced interaction with the C60 moiety. This experimental finding is further confirmed by state-of-the art calculations using DFT and TD-DFT including dispersion effects that explain the electrostatic and structural origins of this interaction, as the CuIIP cation becomes ruffled and approaches closer to the fullerene in the charge-separated state. From a methodological point of view, these results exemplify the potential of multielectron excitation features in transient X-ray spectra as future diagnostics of sub-femtosecond electronic dynamics. From a practical point of view, this work is paving the way for elucidating out-of-equilibrium electron transfer events coupled to magnetic interaction processes on their intrinsic time-scales.« less

Ultrafast Electron Dynamics in Solar Energy Conversion.

PubMed

Ponseca, Carlito S; Chábera, Pavel; Uhlig, Jens; Persson, Petter; Sundström, Villy

2017-08-23

Electrons are the workhorses of solar energy conversion. Conversion of the energy of light to electricity in photovoltaics, or to energy-rich molecules (solar fuel) through photocatalytic processes, invariably starts with photoinduced generation of energy-rich electrons. The harvesting of these electrons in practical devices rests on a series of electron transfer processes whose dynamics and efficiencies determine the function of materials and devices. To capture the energy of a photogenerated electron-hole pair in a solar cell material, charges of opposite sign have to be separated against electrostatic attractions, prevented from recombining and being transported through the active material to electrodes where they can be extracted. In photocatalytic solar fuel production, these electron processes are coupled to chemical reactions leading to storage of the energy of light in chemical bonds. With the focus on the ultrafast time scale, we here discuss the light-induced electron processes underlying the function of several molecular and hybrid materials currently under development for solar energy applications in dye or quantum dot-sensitized solar cells, polymer-fullerene polymer solar cells, organometal halide perovskite solar cells, and finally some photocatalytic systems.

Structure and Dynamics with Ultrafast Electron Microscopes

NASA Astrophysics Data System (ADS)

Siwick, Bradley

In this talk I will describe how combining ultrafast lasers and electron microscopes in novel ways makes it possible to directly `watch' the time-evolving structure of condensed matter, both at the level of atomic-scale structural rearrangements in the unit cell and at the level of a material's nano- microstructure. First, I will briefly describe my group's efforts to develop ultrafast electron diffraction using radio- frequency compressed electron pulses in the 100keV range, a system that rivals the capabilities of xray free electron lasers for diffraction experiments. I will give several examples of the new kinds of information that can be gleaned from such experiments. In vanadium dioxide we have mapped the detailed reorganization of the unit cell during the much debated insulator-metal transition. In particular, we have been able to identify and separate lattice structural changes from valence charge density redistribution in the material on the ultrafast timescale. In doing so we uncovered a previously unreported optically accessible phase/state of vanadium dioxide that has monoclinic crystallography like the insulator, but electronic structure and properties that are more like the rutile metal. We have also combined these dynamic structural measurements with broadband ultrafast spectroscopy to make detailed connections between structure and properties for the photoinduced insulator to metal transition. Second, I will show how dynamic transmission electron microscopy (DTEM) can be used to make direct, real space images of nano-microstructural evolution during laser-induced crystallization of amorphous semiconductors at unprecedented spatio-temporal resolution. This is a remarkably complex process that involves several distinct modes of crystal growth and the development of intricate microstructural patterns on the nanosecond to ten microsecond timescales all of which can be imaged directly with DTEM.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies

NASA Astrophysics Data System (ADS)

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-01

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ˜130 cm-1 low-frequency phenyl torsional mode. Two vibrational marker bands, Cet=Cet stretching (˜1512 cm-1) and Cph=Cph stretching (˜1584 cm-1) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the Cph=Cph stretching mode with a time constant of ˜400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the Cet=Cet stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central Cet=Cet twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Femtosecond coherent nuclear dynamics of excited tetraphenylethylene: Ultrafast transient absorption and ultrafast Raman loss spectroscopic studies.

PubMed

Kayal, Surajit; Roy, Khokan; Umapathy, Siva

2018-01-14

Ultrafast torsional dynamics plays an important role in the photoinduced excited state dynamics. Tetraphenylethylene (TPE), a model system for the molecular motor, executes interesting torsional dynamics upon photoexcitation. The photoreaction of TPE involves ultrafast internal conversion via a nearly planar intermediate state (relaxed state) that further leads to a twisted zwitterionic state. Here, we report the photoinduced structural dynamics of excited TPE during the course of photoisomerization in the condensed phase by ultrafast Raman loss (URLS) and femtosecond transient absorption (TA) spectroscopy. TA measurements on the S 1 state reveal step-wise population relaxation from the Franck-Condon (FC) state → relaxed state → twisted state, while the URLS study provides insights on the vibrational dynamics during the course of the reaction. The TA spectral dynamics and vibrational Raman amplitudes within 1 ps reveal vibrational wave packet propagating from the FC state to the relaxed state. Fourier transformation of this oscillation leads to a ∼130 cm -1 low-frequency phenyl torsional mode. Two vibrational marker bands, C et =C et stretching (∼1512 cm -1 ) and C ph =C ph stretching (∼1584 cm -1 ) modes, appear immediately after photoexcitation in the URLS spectra. The initial red-shift of the C ph =C ph stretching mode with a time constant of ∼400 fs (in butyronitrile) is assigned to the rate of planarization of excited TPE. In addition, the C et =C et stretching mode shows initial blue-shift within 1 ps followed by frequency red-shift, suggesting that on the sub-picosecond time scale, structural relaxation is dominated by phenyl torsion rather than the central C et =C et twist. Furthermore, the effect of the solvent on the structural dynamics is discussed in the context of ultrafast nuclear dynamics and solute-solvent coupling.

Universal ultrafast signatures of photoexcitations in conjugated polymers: excitons and charge-transfer polarons

NASA Astrophysics Data System (ADS)

McBranch, Duncan W.; Kraabel, Brett; Xu, Su; Wang, Hsing-Lin; Klimov, Victor I.

1999-12-01

Using subpicosecond transient absorption spectroscopy, we have investigated the primary photoexcitations in thin films and solution of several phenylene-based conjugated polymers and an oligomer. We identify two features in the transient absorption spectra and dynamics that are common to all of the materials which we have studied from this family. The first spectral feature is a photoinduced absorption (PA) band peaking near 1 eV which has intensity-dependent dynamics which match the stimulated emission dynamics exactly over two orders of magnitude in excitation density. This band is associated with singlet intrachain excitons. The second spectral feature (observed only in thin films and aggregated solutions) is a PA band peaking near 1.8 eV, which is longer-lived than the 1 eV exciton PA band, and which has dynamics that are independent (or weakly-dependent) on excitation density. This feature is attributed to charge separated (interchain) excitations. These excitations are generated through a bimolecular process. By comparing to samples in which charged excitations are created deliberately by doping with C6O, we assign these secondary species as bound polarons.

Spectroscopic Analysis of a Biomimetic Model of Tyr(Z) Function in PSII.

PubMed

Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; Kodis, Gerdenis; Megiatto, Jackson D; Méndez-Hernández, Dalvin D; Frese, Raoul N; van Grondelle, Rienk; Moore, Thomas A; Moore, Ana L; Gust, Devens; Kennis, John T M

2015-09-17

Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the TyrZ-D1His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

Condensation of collective charge ordering in chromium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singer, A.; Marsh, M. J.; Dietze, S. H.

2015-03-01

We report on the dynamics of the structural order parameter in a chromium film using synchrotron radiation in response to photoinduced ultrafast excitations. Following transient optical excitations the effective lattice temperature of the film rises close to the Neel temperature and the charge-density wave (CDW) amplitude is reduced but does not appear to ever be fully destroyed. The persistence of the CDW diffraction signal demonstrates that the CDW, if destroyed by the laser pulse, must be reestablished within the 100-ps time resolution of the synchrotron x-ray pulses. Furthermore, at all times after photoexcitation, the CDW retains its low-temperature periodicity, rathermore » than regenerating with its high-temperature period shortly after photoexcitation. The long-term evolution shows that the CDW reverts to its ground state on a time scale of 370 +/- 40 ps. We attribute the apparent persistence of the CDW to the long-lived periodic lattice displacement in chromium. This study highlights the fundamental role of the lattice distortion and its impact on the recondensation dynamics of the charge ordered state in strongly correlated materials.« less

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization

PubMed Central

Amini, Kasra; Savelyev, Evgeny; Brauße, Felix; Berrah, Nora; Bomme, Cédric; Brouard, Mark; Burt, Michael; Christensen, Lauge; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Kierspel, Thomas; Krecinic, Faruk; Lauer, Alexandra; Lee, Jason W. L.; Müller, Maria; Müller, Erland; Mullins, Terence; Redlin, Harald; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Vallance, Claire; Wiese, Joss; Johnsson, Per; Küpper, Jochen; Rudenko, Artem; Rouzée, Arnaud; Stapelfeldt, Henrik; Rolles, Daniel; Boll, Rebecca

2018-01-01

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon–iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules. PMID:29430482

Photodissociation of aligned CH3I and C6H3F2I molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

PubMed

Amini, Kasra; Savelyev, Evgeny; Brauße, Felix; Berrah, Nora; Bomme, Cédric; Brouard, Mark; Burt, Michael; Christensen, Lauge; Düsterer, Stefan; Erk, Benjamin; Höppner, Hauke; Kierspel, Thomas; Krecinic, Faruk; Lauer, Alexandra; Lee, Jason W L; Müller, Maria; Müller, Erland; Mullins, Terence; Redlin, Harald; Schirmel, Nora; Thøgersen, Jan; Techert, Simone; Toleikis, Sven; Treusch, Rolf; Trippel, Sebastian; Ulmer, Anatoli; Vallance, Claire; Wiese, Joss; Johnsson, Per; Küpper, Jochen; Rudenko, Artem; Rouzée, Arnaud; Stapelfeldt, Henrik; Rolles, Daniel; Boll, Rebecca

2018-01-01

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon-iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Ultrafast non-radiative dynamics of atomically thin MoSe 2

DOE PAGES

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind; ...

2017-10-17

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy transfer between the electronic system and the lattice.« less

Ultrafast non-radiative dynamics of atomically thin MoSe 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Ming -Fu; Kochat, Vidya; Krishnamoorthy, Aravind

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2. Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the highmore » electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy transfer between the electronic system and the lattice.« less

QM/MM nonadiabatic dynamics simulations on photoinduced Wolff rearrangements of 1,2,3-thiadiazole

NASA Astrophysics Data System (ADS)

Liu, Xiang-Yang; Fang, Ye-Guang; Xie, Bin-Bin; Fang, Wei-Hai; Cui, Ganglong

2017-06-01

The photoinduced rearrangement reaction mechanism of 1,2,3-thiadiazole remains experimentally elusive. Two possible mechanisms have been proposed to date. The first is a stepwise mechanism via a thiocarbene intermediate; the second is an excited-state concerted rearrangement mechanism. Herein we have adopted both the electronic structure calculations and nonadiabatic dynamics simulations to study the photoinduced rearrangement reactions of 1,2,3-thiadiazole in the S2, S1, and S0 states in solution. On the basis of QM(CASPT2)/MM [quantum mechanics(complete active space self-consistent field second-order perturbation theory)/molecular mechanics] calculations, we have found that (1) the thiocarbene intermediate is not stable; thus, the stepwise mechanism should be unfavorable; (2) the excited-state decay from the S2 via S1 to S0 state is ultrafast and completed within ca. 200 fs; therefore, both the S2 and S1 states should not have a long enough time for the excited-state rearrangements. Instead, we have computationally proposed a modified photoinduced rearrangement mechanism. Upon irradiation, the S2 state is first populated (114.0 kcal/mol), followed by an ultrafast S2 → S1 → S0 excited-state decay along the S-N bond fission, which eventually leads to a very "hot" intermediate with the S-N bond broken (18.3 kcal/mol). Then, thermal rearrangements to thioketene, thiirene, and ethynethiol occur in a concerted asynchronous way. This mechanistic scenario has been verified by full-dimensional trajectory-based nonadiabatic dynamics simulations at the QM(CASPT2)/MM level. Finally, our present computational work provides experimentally interesting mechanistic insights into the photoinduced rearrangement reactions of cyclic and acyclic diazo compounds.

Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

PubMed

Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

2008-01-01

The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical impact of the attachment position of the spacer on the porphyrin on the electron transfer rate, and this strategy can represent a useful approach to develop molecular photonic devices for long-range charge separations.

Ultrafast photodynamics of the indoline dye D149 adsorbed to porous ZnO in dye-sensitized solar cells.

PubMed

Rohwer, Egmont; Richter, Christoph; Heming, Nadine; Strauch, Kerstin; Litwinski, Christian; Nyokong, Tebello; Schlettwein, Derck; Schwoerer, Heinrich

2013-01-14

We investigate the ultrafast dynamics of the photoinduced electron transfer between surface-adsorbed indoline D149 dye and porous ZnO as used in the working electrodes of dye-sensitized solar cells. Transient absorption spectroscopy was conducted on the dye in solution, on solid state samples and for the latter in contact to a I(-)/I(3)(-) redox electrolyte typical for dye-sensitized solar cells to elucidate the effect of each component in the observed dynamics. D149 in a solution of 1:1 acetonitrile and tert-butyl alcohol shows excited-state lifetimes of 300±50 ps. This signature is severely quenched when D149 is adsorbed to ZnO, with the fastest component of the decay trace measured at 150±20 fs due to the charge-transfer mechanism. Absorption bands of the oxidized dye molecule were investigated to determine regeneration times which are in excess of 1 ns. The addition of the redox electrolyte to the system results in faster regeneration times, of the order of 1 ns. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast carrier dynamics in band edge and broad deep defect emission ZnSe nanowires

NASA Astrophysics Data System (ADS)

Othonos, Andreas; Lioudakis, Emmanouil; Philipose, U.; Ruda, Harry E.

2007-12-01

Ultrafast carrier dynamics of ZnSe nanowires grown under different growth conditions have been studied. Transient absorption measurements reveal the dependence of the competing effects of state filling and photoinduced absorption on the probed energy states. The relaxation of the photogenerated carriers occupying defect states in the stoichiometric and Se-rich samples are single exponentials with time constants of 3-4ps. State filling is the main contribution for probe energies below 1.85eV in the Zn-rich grown sample. This ultrafast carrier dynamics study provides an important insight into the role that intrinsic point defects play in the observed photoluminescence from ZnSe nanowires.

Photoinduced surface plasmon switching at VO2/Au interface.

PubMed

Kumar, Nardeep; Rúa, Armando; Aldama, Jennifer; Echeverría, Karla; Fernández, Félix E; Lysenko, Sergiy

2018-05-28

Angle-resolved reflection, light scattering and ultrafast pump-probe spectroscopy combined with a surface plasmon-polariton (SPP) resonance technique in attenuated total reflection geometry was used to investigate the light-induced plasmonic switching in a photorefractive VO 2 /Au hybrid structure. Measurements of SPP scattering and reflection shows that the optically-induced formation of metallic state in a vanadium dioxide layer deposited on a gold film significantly alters the electromagnetic field enhancement and SPP propagation length at the VO 2 /Au interface. The ultrafast optical manipulation of SPP resonance is shown on a picosecond timescale. Obtained results demonstrate high potential of photorefractive vanadium oxides as efficient plasmonic modulating materials for ultrafast optoelectronic devices.

Spatially confined low-power optically pumped ultrafast synchrotron x-ray nanodiffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Joonkyu; Zhang, Qingteng; Chen, Pice

2015-08-27

The combination of ultrafast optical excitation and time-resolved synchrotron x-ray nanodiffraction provides unique insight into the photoinduced dynamics of materials, with the spatial resolution required to probe individual nanostructures or small volumes within heterogeneous materials. Optically excited x-ray nanobeam experiments are challenging because the high total optical power required for experimentally relevant optical fluences leads to mechanical instability due to heating. For a given fluence, tightly focusing the optical excitation reduces the average optical power by more than three orders of magnitude and thus ensures sufficient thermal stability for x-ray nanobeam studies. Delivering optical pulses via a scannable fiber-coupled opticalmore » objective provides a well-defined excitation geometry during rotation and translation of the sample and allows the selective excitation of isolated areas within the sample. Finally, experimental studies of the photoinduced lattice dynamics of a 35 nm BiFeO 3 thin film on a SrTiO 3 substrate demonstrate the potential to excite and probe nanoscale volumes.« less

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy

NASA Astrophysics Data System (ADS)

Hall, James P.; Poynton, Fergus E.; Keane, Páraic M.; Gurung, Sarah P.; Brazier, John A.; Cardin, David J.; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V.; Towrie, Michael; Cardin, Christine J.; Kelly, John M.; Quinn, Susan J.

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

PubMed Central

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin-ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

2015-01-01

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined. PMID:25727920

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

DOE PAGES

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; ...

2015-03-02

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

Discrete Chromatic Aberrations Arising from Photoinduced Electron-Photon Interactions in Ultrafast Electron Microscopy.

PubMed

Plemmons, Dayne A; Flannigan, David J

2016-05-26

In femtosecond ultrafast electron microscopy (UEM) experiments, the initial excitation period is composed of spatiotemporal overlap of the temporally commensurate pump photon pulse and probe photoelectron packet. Generation of evanescent near-fields at the nanostructure specimens produces a dispersion relation that enables coupling of the photons (ℏω = 2.4 eV, for example) and freely propagating electrons (200 keV, for example) in the near-field. Typically, this manifests as discrete peaks occurring at integer multiples (n) of the photon energy in the low-loss/gain region of electron-energy spectra (i.e., at 200 keV ± nℏω eV). Here, we examine the UEM imaging resolution implications of the strong inelastic near-field interactions between the photons employed in optical excitation and the probe photoelectrons. We find that the additional photoinduced energy dispersion occurring when swift electrons pass through intense evanescent near-fields results in a discrete chromatic aberration that limits the spatial resolving power to several angstroms during the excitation period.

Monitoring one-electron photo-oxidation of guanine in DNA crystals using ultrafast infrared spectroscopy.

PubMed

Hall, James P; Poynton, Fergus E; Keane, Páraic M; Gurung, Sarah P; Brazier, John A; Cardin, David J; Winter, Graeme; Gunnlaugsson, Thorfinnur; Sazanovich, Igor V; Towrie, Michael; Cardin, Christine J; Kelly, John M; Quinn, Susan J

2015-12-01

To understand the molecular origins of diseases caused by ultraviolet and visible light, and also to develop photodynamic therapy, it is important to resolve the mechanism of photoinduced DNA damage. Damage to DNA bound to a photosensitizer molecule frequently proceeds by one-electron photo-oxidation of guanine, but the precise dynamics of this process are sensitive to the location and the orientation of the photosensitizer, which are very difficult to define in solution. To overcome this, ultrafast time-resolved infrared (TRIR) spectroscopy was performed on photoexcited ruthenium polypyridyl-DNA crystals, the atomic structure of which was determined by X-ray crystallography. By combining the X-ray and TRIR data we are able to define both the geometry of the reaction site and the rates of individual steps in a reversible photoinduced electron-transfer process. This allows us to propose an individual guanine as the reaction site and, intriguingly, reveals that the dynamics in the crystal state are quite similar to those observed in the solvent medium.

Final Technical Report for SISGR: Ultrafast Molecular Scale Chemical Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hersam, Mark C.; Guest, Jeffrey R.; Guisinger, Nathan P.

2017-04-10

The Northwestern-Argonne SISGR program utilized newly developed instrumentation and techniques including integrated ultra-high vacuum tip-enhanced Raman spectroscopy/scanning tunneling microscopy (UHV-TERS/STM) and surface-enhanced femtosecond stimulated Raman scattering (SE-FSRS) to advance the spatial and temporal resolution of chemical imaging for the study of photoinduced dynamics of molecules on plasmonically active surfaces. An accompanying theory program addressed modeling of charge transfer processes using constrained density functional theory (DFT) in addition to modeling of SE-FSRS, thereby providing a detailed description of the excited state dynamics. This interdisciplinary and highly collaborative research resulted in 62 publications with ~ 48% of them being co-authored by multiplemore » SISGR team members. A summary of the scientific accomplishments from this SISGR program is provided in this final technical report.« less

Ultrafast photoinduced charge transport in Pt(II) donor-acceptor assembly bearing naphthalimide electron acceptor and phenothiazine electron donor.

PubMed

Sazanovich, Igor V; Best, Jonathan; Scattergood, Paul A; Towrie, Michael; Tikhomirov, Sergei A; Bouganov, Oleg V; Meijer, Anthony J H M; Weinstein, Julia A

2014-12-21

Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor-chromophore-donor, (NDI-phen)Pt(II)(-C≡C-Ph-CH2-PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(-C≡C-Ph-)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a (3)MLCT/LL'CT, with {Pt(II)-acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI(-)-phen-[Pt-(C≡C)2](+)-PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of ∼15 ps during which the hole migrates from the [Pt-(C≡C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C≡C-Ph-CH2-PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C≡C-Ph-C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering

DOE PAGES

Eckert, Sebastian; Norell, Jesper; Miedema, Piter S.; ...

2017-04-04

Here, the femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort timescale.

Identification of the dominant photochemical pathways and mechanistic insights to the ultrafast ligand exchange of Fe(CO) 5 to Fe(CO) 4EtOH

DOE PAGES

Kunnus, K.; Josefsson, I.; Rajkovic, I.; ...

2016-02-09

We utilized femtosecond time-resolved resonant inelastic X-ray scattering and ab initio theory to study the transient electronic structure and the photoinduced molecular dynamics of a model metal carbonyl photocatalyst Fe(CO) 5 in ethanol solution. We propose mechanistic explanation for the parallel ultrafast intra-molecular spin crossover and ligation of the Fe(CO) 4 which are observed following a charge transfer photoexcitation of Fe(CO) 5 as reported in our previous study [Wernet et al., Nature 520, 78 (2015)]. We find that branching of the reaction pathway likely happens in the 1A 1 state of Fe(CO) 4. A sub-picosecond time constant of themore » spin crossover from 1B 2 to 3B 2 is rationalized by the proposed 1B 2 → 1A 1 → 3B 2 mechanism. Ultrafast ligation of the 1B 2 Fe(CO) 4 state is significantly faster than the spin-forbidden and diffusion limited ligation process occurring from the 3B 2 Fe(CO) 4 ground state that has been observed in the previous studies. We propose that the ultrafast ligation occurs via 1B 2 → 1A 1 → 1A' Fe(CO) 4EtOH pathway and the time scale of the 1A 1 Fe(CO) 4 state ligation is governed by the solute-solvent collision frequency. In conclusion, our study emphasizes the importance of understanding the interaction of molecular excited states with the surrounding environment to explain the relaxation pathways of photoexcited metal carbonyls in solution.« less

Generation Dependent Ultrafast Charge Separation and Recombination in a Pyrene-Viologen Family of Dendrons.

PubMed

Gong, Zheng; Bao, Jianhua; Nagai, Keiji; Iyoda, Tomokazu; Kawauchi, Takehiro; Piotrowiak, Piotr

2016-05-12

The ability of a dendritic network to intercept electrons and extend the lifetime of a short-lived photoinduced charge separated (CS) state was investigated in a homologous family of methyl viologen (MV(2+)) dendrons spanning four generations, G0 through G3. The CS state in the parent pyrene-methylene-viologen G0 system with a single acceptor exhibits an extremely short lifetime of τ = 0.72 ps. The expansion of the viologen network introduces slower components to the recombination kinetics by allowing the injected electron to migrate further away from the donor. The long-lived fraction of the population increases monotonically in the order G3 > G2 > G1 > G0, while the respective recombination rates decrease. In the highest generation of the dendron ∼14% of the CS state population experiences a 10-fold or greater lifetime extension. Long range tunneling across multiple viologen units and sequential site-to-site hopping both contribute to the overall effect. The large excess energy deposited in the apical viologen upon charge separation and the presence of an extended network of low lying π-orbitals likely facilitate shuttling the electron further down the dendron.

Ultrafast electron transfer in all-carbon-based SWCNT-C60 donor-acceptor nanoensembles connected by poly(phenylene-ethynylene) spacers

NASA Astrophysics Data System (ADS)

Barrejón, Myriam; Gobeze, Habtom B.; Gómez-Escalonilla, María J.; Fierro, José Luis G.; Zhang, Minfang; Yudasaka, Masako; Iijima, Sumio; D'Souza, Francis; Langa, Fernando

2016-08-01

Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices.Building all-carbon based functional materials for light energy harvesting applications could be a solution to tackle and reduce environmental carbon output. However, development of such all-carbon based donor-acceptor hybrids and demonstration of photoinduced charge separation in such nanohybrids is a challenge since in these hybrids part of the carbon material should act as an electron donating or accepting photosensitizer while the second part should fulfil the role of an electron acceptor or donor. In the present work, we have successfully addressed this issue by synthesizing covalently linked all-carbon-based donor-acceptor nanoensembles using single-walled carbon nanotubes (SWCNTs) as the donor and C60 as the acceptor. The donor-acceptor entities in the nanoensembles were connected by phenylene-ethynylene spacer units to achieve better electronic communication and to vary the distance between the components. These novel SWCNT-C60 nanoensembles have been characterized by a number of techniques, including TGA, FT-IR, Raman, AFM, absorbance and electrochemical methods. The moderate number of fullerene addends present on the side-walls of the nanotubes largely preserved the electronic structure of the nanotubes. The thermodynamic feasibility of charge separation in these nanoensembles was established using spectral and electrochemical data. Finally, occurrence of ultrafast electron transfer from the excited nanotubes in these donor-acceptor nanohybrids has been established by femtosecond transient absorption studies, signifying their utility in building light energy harvesting devices. Electronic supplementary information (ESI) available: Synthesis, TGA, FTIR, AFM and XPS data, UV-vis and transient absorption spectra (Fig. S1-S15 and Tables S1 and S2). See DOI: 10.1039/c6nr02829b

Excited state dynamics can be used to probe donor-acceptor distances for H-tunneling reactions catalyzed by flavoproteins.

PubMed

Hardman, Samantha J O; Pudney, Christopher R; Hay, Sam; Scrutton, Nigel S

2013-12-03

In enzyme systems where fast motions are thought to contribute to H-transfer efficiency, the distance between hydrogen donor and acceptor is a very important factor. Sub-ångstrom changes in donor-acceptor distance can have a large effect on the rate of reaction, so a sensitive probe of these changes is a vital tool in our understanding of enzyme function. In this study we use ultrafast transient absorption spectroscopy to investigate the photoinduced electron transfer rates, which are also very sensitive to small changes in distance, between coenzyme analog, NAD(P)H4, and the isoalloxazine center in the model flavoenzymes morphinone reductase (wild-type and selected variants) and pentaerythritol tetranitrate reductase (wild-type). It is shown that upon addition of coenzyme to the protein the rate of photoinduced electron transfer is increased. By comparing the magnitude of this increase with existing values for NAD(P)H4-FMN distances, based on charge-transfer complex absorbance and experimental kinetic isotope effect reaction data, we show that this method can be used as a sensitive probe of donor-acceptor distance in a range of enzyme systems. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

A Saturn-Like Complex Composed of Macrocyclic Oligothiophene and C60 Fullerene: Structure, Stability, and Photophysical Properties in Solution and the Solid State.

PubMed

Shimizu, Hideyuki; Park, Kyu Hyung; Otani, Hiroyuki; Aoyagi, Shinobu; Nishinaga, Tohru; Aso, Yoshio; Kim, Dongho; Iyoda, Masahiko

2018-03-12

A Saturn-like 1:1 complex composed of macrocyclic oligothiophene E-8T7A and C 60 fullerene (C 60 ) was synthesized to investigate the interaction between macrocyclic oligothiophenes and C 60 in solution and the solid state. Because the Saturn-like 1:1 complex E-8T7A⋅C 60 is mainly stabilized by van der Waals interactions between C 60 and the sulfur atoms of the E-8T7A macrocycle, C 60 is rather weakly incorporated inside the macro-ring in solution. However, in the solid state the Saturn-like 1:1 complex preferentially formed single crystals or nanostructured polymorphs. Interestingly, X-ray analysis and theoretical calculations exhibited hindered rotation of C 60 in the Saturn-like complex due to interactions between C 60 and the sulfur atoms. Furthermore, the photoinduced charge transfer (CT) interaction between E-8T7A and C 60 in solution was investigated by using femtosecond transient absorption (TA) spectroscopy. The ultrafast TA spectral changes in the photoinduced absorption bands were attributed to the CT process in the Saturn-like structure. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Time-resolved spectroscopic characterization of photo-induced valence tautomerism for a cobalt dioxolene complex

NASA Astrophysics Data System (ADS)

Gentili, Pier Luigi; Bussotti, Laura; Righini, Roberto; Beni, Alessandra; Bogani, Lapo; Dei, Andrea

2005-07-01

The valence tautomerism of low-spin Co III(Cat-N-BQ)(Cat-N-SQ) (where Cat-N-BQ is 2-(2-hydroxy-3,5-di- tert-butylphenylimino)-4,6-di- tert-butylcyclohexa-3,5-dienone and Cat-N-SQ is the dianionic radical analogue) was investigated by means of UV-vis pump-probe transient absorption spectroscopy and 1H NMR technique in chloroform and dichloromethane. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin Co II(Cat-N-BQ) 2 that, secondly, reaches the chemical equilibrium with the reactant species. The rate constant of back valence tautomerization estimated by measuring the lifetime of high-spin Co II(Cat-N-BQ) 2 species and the equilibrium constant for the Co III(Cat-N-BQ)(Cat-N-SQ) ⇄ Co II(Cat-N-BQ) 2 interconversion, is significantly large (on the order of 10 9 s -1). It is interpreted under the point of view of the theory formulated by Jortner and Buhks et al. for non-adiabatic radiationless processes.

The nature of photoinduced phase transition and metastable states in vanadium dioxide

DOE PAGES

Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; ...

2016-12-16

Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO 2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M 2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picosecondsmore » at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.« less

The nature of photoinduced phase transition and metastable states in vanadium dioxide

PubMed Central

Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

2016-01-01

Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium. PMID:27982066

The nature of photoinduced phase transition and metastable states in vanadium dioxide

NASA Astrophysics Data System (ADS)

Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.; Torres, David; Wang, Tongyu; Sepulveda, Nelson; Chang, Kiseok; Young, Margaret; Lunt, Richard R.; Ruan, Chong-Yu

2016-12-01

Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picoseconds at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.

Mechanistic insights into the photoinduced charge carrier dynamics of BiOBr/CdS nanosheet heterojunctions for photovoltaic application.

PubMed

Jia, Huimin; Zhang, Beibei; He, Weiwei; Xiang, Yong; Zheng, Zhi

2017-03-02

The rational design of high performance hetero-structure photovoltaic devices requires a full understanding of the photoinduced charge transfer mechanism and kinetics at the interface of heterojunctions. In this paper, we intelligently fabricated p-BiOBr/n-CdS heterojunctions with perfect nanosheet arrays by using a facile successive ionic layer adsorption and reaction and chemical bath deposition methods at low temperature. A BiOBr/CdS heterojunction based solar cell has been fabricated which exhibited enhanced photovoltaic responses. Assisted by the surface photovoltage (SPV), transient photovoltage (TPV) and Kelvin probe technique, the photoinduced charge transfer dynamics on the BiOBr nanosheet and p-BiOBr/n-CdS interface were systematically investigated. It was found that the BiOBr/CdS nanosheet array heterojunctions were more efficient in facilitating charge carrier separation than both bare BiOBr and CdS films. The mechanism underlying the photoinduced charge carrier transfer behaviour was unravelled by allying the energy band of BiOBr/CdS p-n junctions from both the interfacial electric field and surface electric field. In addition, the CdS loading thickness in the p-BiOBr/n-CdS heterojunction and the incident wavelength affected greatly the transfer behavior of photoinduced charges, which was of great value for design of photovoltaic devices.

Nonadiabatic excited-state molecular dynamics: modeling photophysics in organic conjugated materials.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E; Tretiak, Sergei

2014-04-15

To design functional photoactive materials for a variety of technological applications, researchers need to understand their electronic properties in detail and have ways to control their photoinduced pathways. When excited by photons of light, organic conjugated materials (OCMs) show dynamics that are often characterized by large nonadiabatic (NA) couplings between multiple excited states through a breakdown of the Born-Oppenheimer (BO) approximation. Following photoexcitation, various nonradiative intraband relaxation pathways can lead to a number of complex processes. Therefore, computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons. Over the years, we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework that efficiently and accurately describes photoinduced phenomena in extended conjugated molecular systems. We use the fewest-switches surface hopping (FSSH) algorithm to treat quantum transitions among multiple adiabatic excited state potential energy surfaces (PESs). Extended molecular systems often contain hundreds of atoms and involve large densities of excited states that participate in the photoinduced dynamics. We can achieve an accurate description of the multiple excited states using the configuration interaction single (CIS) formalism with a semiempirical model Hamiltonian. Analytical techniques allow the trajectory to be propagated "on the fly" using the complete set of NA coupling terms and remove computational bottlenecks in the evaluation of excited-state gradients and NA couplings. Furthermore, the use of state-specific gradients for propagation of nuclei on the native excited-state PES eliminates the need for simplifications such as the classical path approximation (CPA), which only uses ground-state gradients. Thus, the NA-ESMD methodology offers a computationally tractable route for simulating hundreds of atoms on ~10 ps time scales where multiple coupled excited states are involved. In this Account, we review recent developments in the NA-ESMD modeling of photoinduced dynamics in extended conjugated molecules involving multiple coupled electronic states. We have successfully applied the outlined NA-ESMD framework to study ultrafast conformational planarization in polyfluorenes where the rate of torsional relaxation can be controlled based on the initial excitation. With the addition of the state reassignment algorithm to identify instances of unavoided crossings between noninteracting PESs, NA-ESMD can now be used to study systems in which these so-called trivial unavoided crossings are expected to predominate. We employ this technique to analyze the energy transfer between poly(phenylene vinylene) (PPV) segments where conformational fluctuations give rise to numerous instances of unavoided crossings leading to multiple pathways and complex energy transfer dynamics that cannot be described using a simple Förster model. In addition, we have investigated the mechanism of ultrafast unidirectional energy transfer in dendrimers composed of poly(phenylene ethynylene) (PPE) chromophores and have demonstrated that differential nuclear motion favors downhill energy transfer in dendrimers. The use of native excited-state gradients allows us to observe this feature.

Photo-reactive charge trapping memory based on lanthanide complex.

PubMed

Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V A L

2015-10-09

Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 10(4) s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

Photo-reactive charge trapping memory based on lanthanide complex

NASA Astrophysics Data System (ADS)

Zhuang, Jiaqing; Lo, Wai-Sum; Zhou, Li; Sun, Qi-Jun; Chan, Chi-Fai; Zhou, Ye; Han, Su-Ting; Yan, Yan; Wong, Wing-Tak; Wong, Ka-Leung; Roy, V. A. L.

2015-10-01

Traditional utilization of photo-induced excitons is popularly but restricted in the fields of photovoltaic devices as well as photodetectors, and efforts on broadening its function have always been attempted. However, rare reports are available on organic field effect transistor (OFET) memory employing photo-induced charges. Here, we demonstrate an OFET memory containing a novel organic lanthanide complex Eu(tta)3ppta (Eu(tta)3 = Europium(III) thenoyltrifluoroacetonate, ppta = 2-phenyl-4,6-bis(pyrazol-1-yl)-1,3,5-triazine), in which the photo-induced charges can be successfully trapped and detrapped. The luminescent complex emits intense red emission upon ultraviolet (UV) light excitation and serves as a trapping element of holes injected from the pentacene semiconductor layer. Memory window can be significantly enlarged by light-assisted programming and erasing procedures, during which the photo-induced excitons in the semiconductor layer are separated by voltage bias. The enhancement of memory window is attributed to the increasing number of photo-induced excitons by the UV light. The charges are stored in this luminescent complex for at least 104 s after withdrawing voltage bias. The present study on photo-assisted novel memory may motivate the research on a new type of light tunable charge trapping photo-reactive memory devices.

A transferable model for singlet-fission kinetics.

PubMed

Yost, Shane R; Lee, Jiye; Wilson, Mark W B; Wu, Tony; McMahon, David P; Parkhurst, Rebecca R; Thompson, Nicholas J; Congreve, Daniel N; Rao, Akshay; Johnson, Kerr; Sfeir, Matthew Y; Bawendi, Moungi G; Swager, Timothy M; Friend, Richard H; Baldo, Marc A; Van Voorhis, Troy

2014-06-01

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications.

Local Intermolecular Order Controls Photoinduced Charge Separation at Donor/Acceptor Interfaces in Organic Semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feier, Hilary M.; Reid, Obadiah G.; Pace, Natalie A.

2016-03-23

How free charge is generated at organic donor-acceptor interfaces is an important question, as the binding energy of the lowest energy (localized) charge transfer states should be too high for the electron and hole to escape each other. Recently, it has been proposed that delocalization of the electronic states participating in charge transfer is crucial, and aggregated or otherwise locally ordered structures of the donor or the acceptor are the precondition for this electronic characteristic. The effect of intermolecular aggregation of both the polymer donor and fullerene acceptor on charge separation is studied. In the first case, the dilute electronmore » acceptor triethylsilylhydroxy-1,4,8,11,15,18,22,25-octabutoxyphthalocyaninatosilicon(IV) (SiPc) is used to eliminate the influence of acceptor aggregation, and control polymer order through side-chain regioregularity, comparing charge generation in 96% regioregular (RR-) poly(3-hexylthiophene) (P3HT) with its regiorandom (RRa-) counterpart. In the second case, ordered phases in the polymer are eliminated by using RRa-P3HT, and phenyl-C61-butyric acid methyl ester (PC61BM) is used as the acceptor, varying its concentration to control aggregation. Time-resolved microwave conductivity, time-resolved photoluminescence, and transient absorption spectroscopy measurements show that while ultrafast charge transfer occurs in all samples, long-lived charge carriers are only produced in films with intermolecular aggregates of either RR-P3HT or PC61BM, and that polymer aggregates are just as effective in this regard as those of fullerenes.« less

Monitoring Ultrafast Chemical Dynamics by Time-Domain X-ray Photo- and Auger-Electron Spectroscopy.

PubMed

Gessner, Oliver; Gühr, Markus

2016-01-19

The directed flow of charge and energy is at the heart of all chemical processes. Extraordinary efforts are underway to monitor and understand the concerted motion of electrons and nuclei with ever increasing spatial and temporal sensitivity. The element specificity, chemical sensitivity, and temporal resolution of ultrafast X-ray spectroscopy techniques hold great promise to provide new insight into the fundamental interactions underlying chemical dynamics in systems ranging from isolated molecules to application-like devices. Here, we focus on the potential of ultrafast X-ray spectroscopy techniques based on the detection of photo- and Auger electrons to provide new fundamental insight into photochemical processes of systems with various degrees of complexity. Isolated nucleobases provide an excellent testing ground for our most fundamental understanding of intramolecular coupling between electrons and nuclei beyond the traditionally applied Born-Oppenheimer approximation. Ultrafast electronic relaxation dynamics enabled by the breakdown of this approximation is the major component of the nucleobase photoprotection mechanisms. Transient X-ray induced Auger electron spectroscopy on photoexcited thymine molecules provides atomic-site specific details of the extremely efficient coupling that converts potentially bond changing ultraviolet photon energy into benign heat. In particular, the time-dependent spectral shift of a specific Auger band is sensitive to the length of a single bond within the molecule. The X-ray induced Auger transients show evidence for an electronic transition out of the initially excited state within only ∼200 fs in contrast to theoretically predicted picosecond population trapping behind a reaction barrier. Photoinduced charge transfer dynamics between transition metal complexes and semiconductor nanostructures are of central importance for many emerging energy and climate relevant technologies. Numerous demonstrations of photovoltaic and photocatalytic activity have been performed based on the combination of strong light absorption in dye molecules with charge separation and transport in adjacent semiconductor nanostructures. However, a fundamental understanding of the enabling and limiting dynamics on critical atomic length- and time scales is often still lacking. Femtosecond time-resolved X-ray photoelectron spectroscopy is employed to gain a better understanding of a short-lived intermediate that may be linked to the unexpectedly limited performance of ZnO based dye-sensitized solar cells by delaying the generation of free charge carriers. The transient spectra strongly suggest that photoexcited dye molecules attached to ZnO nanocrystals inject their charges into the substrate within less than 1 ps but the electrons are then temporarily trapped at the surface of the semiconductor in direct vicinity of the injecting molecules. The experiments are extended to monitor the electronic response of the semiconductor substrate to the collective injection from a monolayer of dye molecules and the subsequent electron-ion recombination dynamics. The results indicate some qualitative similarities but quantitative differences between the recombination dynamics at molecule-semiconductor interfaces and previously studied bulk-surface electron-hole recombination dynamics in photoexcited semiconductors.

Molecular control of pentacene/ZnO photoinduced charge transfer

NASA Astrophysics Data System (ADS)

Spalenka, Josef W.; Paoprasert, Peerasak; Franking, Ryan; Hamers, Robert J.; Gopalan, Padma; Evans, Paul G.

2011-03-01

Photoinduced charge transfer modifies the device properties of illuminated pentacene field effect transistors (FETs) incorporating ZnO quantum dots at the gate insulator/pentacene interface. The transferred charge is trapped on electronic states associated with the ZnO quantum dots, with a steady state population approximately proportional to the rate of organic-inorganic charge transfer. Trapped charge shifts the threshold voltage of the FETs, providing the means to evaluate the rate of organic/inorganic charge transfer and the effects of interface modification. Monolayers of the wide-gap alkane stearic acid and the conjugated oligomer terthiophene attached to the ZnO suppress or permit charge transfer, respectively.

Space charge effects in ultrafast electron diffraction and imaging

NASA Astrophysics Data System (ADS)

Tao, Zhensheng; Zhang, He; Duxbury, P. M.; Berz, Martin; Ruan, Chong-Yu

2012-02-01

Understanding space charge effects is central for the development of high-brightness ultrafast electron diffraction and microscopy techniques for imaging material transformation with atomic scale detail at the fs to ps timescales. We present methods and results for direct ultrafast photoelectron beam characterization employing a shadow projection imaging technique to investigate the generation of ultrafast, non-uniform, intense photoelectron pulses in a dc photo-gun geometry. Combined with N-particle simulations and an analytical Gaussian model, we elucidate three essential space-charge-led features: the pulse lengthening following a power-law scaling, the broadening of the initial energy distribution, and the virtual cathode threshold. The impacts of these space charge effects on the performance of the next generation high-brightness ultrafast electron diffraction and imaging systems are evaluated.

Engineering interfacial photo-induced charge transfer based on nanobamboo array architecture for efficient solar-to-chemical energy conversion.

PubMed

Wang, Xiaotian; Liow, Chihao; Bisht, Ankit; Liu, Xinfeng; Sum, Tze Chien; Chen, Xiaodong; Li, Shuzhou

2015-04-01

Engineering interfacial photo-induced charge transfer for highly synergistic photocatalysis is successfully realized based on nanobamboo array architecture. Programmable assemblies of various components and heterogeneous interfaces, and, in turn, engineering of the energy band structure along the charge transport pathways, play a critical role in generating excellent synergistic effects of multiple components for promoting photocatalytic efficiency. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exciplex formation in bimolecular photoinduced electron-transfer investigated by ultrafast time-resolved infrared spectroscopy.

PubMed

Koch, Marius; Letrun, Romain; Vauthey, Eric

2014-03-12

The dynamics of bimolecular photoinduced electron-transfer reactions has been investigated with three donor/acceptor (D/A) pairs in tetrahydrofuran (THF) and acetonitrile (ACN) using a combination of ultrafast spectroscopic techniques, including time-resolved infrared absorption. For the D/A pairs with the highest driving force of electron transfer, all transient spectroscopic features can be unambiguously assigned to the excited reactant and the ionic products. For the pair with the lowest driving force, three additional transient infrared bands, more intense in THF than in ACN, with a time dependence that differs from those of the other bands are observed. From their frequency and solvent dependence, these bands can be assigned to an exciplex. Moreover, polarization-resolved measurements point to a relatively well-defined mutual orientation of the constituents and to a slower reorientational time compared to those of the individual reactants. Thanks to the minimal overlap of the infrared signature of all transient species in THF, a detailed reaction scheme including the relevant kinetic and thermodynamic parameters could be deduced for this pair. This analysis reveals that the formation and recombination of the ion pair occur almost exclusively via the exciplex.

Multistate photo-induced relaxation and photoisomerization ability of fumaramide threads: a computational and experimental study.

PubMed

Altoè, Piero; Haraszkiewicz, Natalia; Gatti, Francesco G; Wiering, Piet G; Frochot, Céline; Brouwer, Albert M; Balkowski, Grzegorz; Shaw, Daniel; Woutersen, Sander; Buma, Wybren Jan; Zerbetto, Francesco; Orlandi, Giorgio; Leigh, David A; Garavelli, Marco

2009-01-14

Fumaric and maleic amides are the photoactive units of an important and widely investigated class of photocontrollable rotaxanes as they trigger ring shuttling via a cis-trans photoisomerization. Here, ultrafast decay and photoinduced isomerization in isolated fumaramide and solvated nitrogen-substituted fumaramides (that are employed as threads in those rotaxanes) have been investigated by means of CASPT2//CASSCF computational and time-resolved spectroscopic techniques, respectively. A complex multistate network of competitive deactivation channels, involving both internal conversion and intersystem crossing (ISC) processes, has been detected and characterized that accounts for the picosecond decay and photochemical/photophysical properties observed in the singlet as well as triplet (photosensitized) photochemistry of fumaramides threads. Interestingly, singlet photochemistry appears to follow a non-Kasha rule model, where nonequilibrium dynamical factors control the outcome of the photochemical process: accessible high energy portions of extended crossing seams turn out to drive the deactivation process and ground-state recovery. Concurrently, extended singlet/triplet degenerate regions of twisted molecular structures with significant spin-orbit-coupling values account for ultrafast (picosecond time scale) ISC processes that lead to higher photoisomerization efficiencies. This model discloses the principles behind the intrinsic photochemical reactivity of fumaramide and its control.

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy.

PubMed

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G; Zhang, Xiaoyi; Liu, Cunming; Mulfort, Karen L; Chen, Lin X

2018-01-28

The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)-Ru(ii) analogs of the homodinuclear Cu(i)-Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.

Photoinduced Bulk Polarization and Its Effects on Photovoltaic Actions in Perovskite Solar Cells.

PubMed

Wu, Ting; Collins, Liam; Zhang, Jia; Lin, Pei-Ying; Ahmadi, Mahshid; Jesse, Stephen; Hu, Bin

2017-11-28

This article reports an experimental demonstration of photoinduced bulk polarization in hysteresis-free methylammonium (MA) lead-halide perovskite solar cells [ITO/PEDOT:PSS/perovskite/PCBM/PEI/Ag]. An anomalous capacitance-voltage (CV) signal is observed as a broad "shoulder" in the depletion region from -0.5 to +0.5 V under photoexcitation based on CV measurements where a dc bias is gradually scanned to continuously drift mobile ions in order to detect local polarization under a low alternating bias (50 mV, 5 kHz). Essentially, gradually scanning the dc bias and applying a low alternating bias can separately generate continuously drifting ions and a bulk CV signal from local polarization under photoexcitation. Particularly, when the device efficiency is improved from 12.41% to 18.19% upon chlorine incorporation, this anomalous CV signal can be enhanced by a factor of 3. This anomalous CV signal can be assigned as the signature of photoinduced bulk polarization by distinguishing from surface polarization associated with interfacial charge accumulation. Meanwhile, replacing easy-rotational MA + with difficult-rotational formamidinium (FA + ) cations largely minimizes such anomalous CV signal, suggesting that photoinduced bulk polarization relies on the orientational freedom of dipolar organic cations. Furthermore, a Kelvin probe force microscopy study shows that chlorine incorporation can suppress the density of charged defects and thus enhances photoinduced bulk polarization due to the reduced screening effect from charged defects. A bias-dependent photoluminescence study indicates that increasing bulk polarization can suppress carrier recombination by decreasing charge capture probability through the Coulombic screening effect. Clearly, our studies provide an insightful understanding of photoinduced bulk polarization and its effects on photovoltaic actions in perovskite solar cells.

Initial photoinduced dynamics of the photoactive yellow protein.

PubMed

Larsen, Delmar S; van Grondelle, Rienk

2005-05-01

The photoactive yellow protein (PYP) is the photoreceptor protein responsible for initiating the blue-light repellent response of the Halorhodospira halophila bacterium. Optical excitation of the intrinsic chromophore in PYP, p-coumaric acid, leads to the initiation of a photocycle that comprises several distinct intermediates. The dynamical processes responsible for the initiation of the PYP photocycle have been explored with several time-resolved techniques, which include ultrafast electronic and vibrational spectroscopies. Ultrafast electronic spectroscopies, such as pump-visible probe, pump-dump-visible probe, and fluorescence upconversion, are useful in identifying the timescales and connectivity of the transient intermediates, while ultrafast vibrational spectroscopies link these intermediates to dynamic structures. Herein, we present the use of these techniques for exploring the initial dynamics of PYP, and show how these techniques provide the basis for understanding the complex relationship between protein and chromophore, which ultimately results in biological function.

Probing ultrafast spin dynamics through a magnon resonance in the antiferromagnetic multiferroic HoMnO 3

DOE PAGES

Bowlan, P.; Trugman, S. A.; Bowlan, J.; ...

2016-09-26

Here, we demonstrate an approach for directly tracking antiferromagnetic (AFM) spin dynamics by measuring ultrafast changes in a magnon resonance. We also test this idea on the multiferroic HoMnO 3 by optically photoexciting electrons, after which changes in the spin order are probed with a THz pulse tuned to a magnon resonance. This reveals a photoinduced change in the magnon line shape that builds up over 5–12 picoseconds, which we show to be the spin-lattice thermalization time, indicating that electrons heat the spins via phonons. We compare our results to previous studies of spin-lattice thermalization in ferromagnetic manganites, giving insightmore » into fundamental differences between the two systems. Finally, our work sheds light on the microscopic mechanism governing spin-phonon interactions in AFMs and demonstrates a powerful approach for directly monitoring ultrafast spin dynamics.« less

Probing ultrafast spin dynamics through a magnon resonance in the antiferromagnetic multiferroic HoMnO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowlan, P.; Trugman, S. A.; Bowlan, J.

Here, we demonstrate an approach for directly tracking antiferromagnetic (AFM) spin dynamics by measuring ultrafast changes in a magnon resonance. We also test this idea on the multiferroic HoMnO 3 by optically photoexciting electrons, after which changes in the spin order are probed with a THz pulse tuned to a magnon resonance. This reveals a photoinduced change in the magnon line shape that builds up over 5–12 picoseconds, which we show to be the spin-lattice thermalization time, indicating that electrons heat the spins via phonons. We compare our results to previous studies of spin-lattice thermalization in ferromagnetic manganites, giving insightmore » into fundamental differences between the two systems. Finally, our work sheds light on the microscopic mechanism governing spin-phonon interactions in AFMs and demonstrates a powerful approach for directly monitoring ultrafast spin dynamics.« less

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches.

PubMed

Antipov, Sergey V; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2017-11-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research "Molecular Ultrafast Science and Technology," are presented: These include Bohmian dynamics description of the collision of H with H 2 , local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase.

Ultrafast dynamics induced by the interaction of molecules with electromagnetic fields: Several quantum, semiclassical, and classical approaches

PubMed Central

Antipov, Sergey V.; Bhattacharyya, Swarnendu; El Hage, Krystel; Xu, Zhen-Hao; Meuwly, Markus; Rothlisberger, Ursula; Vaníček, Jiří

2018-01-01

Several strategies for simulating the ultrafast dynamics of molecules induced by interactions with electromagnetic fields are presented. After a brief overview of the theory of molecule-field interaction, we present several representative examples of quantum, semiclassical, and classical approaches to describe the ultrafast molecular dynamics, including the multiconfiguration time-dependent Hartree method, Bohmian dynamics, local control theory, semiclassical thawed Gaussian approximation, phase averaging, dephasing representation, molecular mechanics with proton transfer, and multipolar force fields. In addition to the general overview, some focus is given to the description of nuclear quantum effects and to the direct dynamics, in which the ab initio energies and forces acting on the nuclei are evaluated on the fly. Several practical applications, performed within the framework of the Swiss National Center of Competence in Research “Molecular Ultrafast Science and Technology,” are presented: These include Bohmian dynamics description of the collision of H with H2, local control theory applied to the photoinduced ultrafast intramolecular proton transfer, semiclassical evaluation of vibrationally resolved electronic absorption, emission, photoelectron, and time-resolved stimulated emission spectra, infrared spectroscopy of H-bonding systems, and multipolar force fields applications in the condensed phase. PMID:29376107

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Zhensheng; Zhou, Faran; Han, Tzong-Ru T.

Photoinduced threshold switching processes that lead to bistability and the formation of metastable phases in photoinduced phase transition of VO 2 are elucidated through ultrafast electron diffraction and diffusive scattering techniques with varying excitation wavelengths. We uncover two distinct regimes of the dynamical phase change: a nearly instantaneous crossover into an intermediate state and its decay led by lattice instabilities over 10 ps timescales. The structure of this intermediate state is identified to be monoclinic, but more akin to M 2 rather than M1 based on structure refinements. The extinction of all major monoclinic features within just a few picosecondsmore » at the above-threshold-level (~20%) photoexcitations and the distinct dynamics in diffusive scattering that represents medium-range atomic fluctuations at two photon wavelengths strongly suggest a density-driven and nonthermal pathway for the initial process of the photoinduced phase transition. These results highlight the critical roles of electron correlations and lattice instabilities in driving and controlling phase transformations far from equilibrium.« less

Ultrafast Hole Trapping and Relaxation Dynamics in p-Type CuS Nanodisks

DOE PAGES

Ludwig, John; An, Li; Pattengale, Brian; ...

2015-06-22

CuS nanocrystals are potential materials for developing low-cost solar energy conversion devices. Understanding the underlying dynamics of photoinduced carriers in CuS nanocrystals is essential to improve their performance in these devices. In this work, we investigated the photoinduced hole dynamics in CuS nanodisks (NDs) using the combination of transient optical (OTA) and X-ray (XTA) absorption spectroscopy. OTA results show that the broad transient absorption in the visible region is attributed to the photoinduced hot and trapped holes. The hole trapping process occurs on a subpicosecond time scale, followed by carrier recombination (~100 ps). The nature of the hole trapping sites,more » revealed by XTA, is characteristic of S or organic ligands on the surface of CuS NDs. Lastly, these results not only suggest the possibility to control the hole dynamics by tuning the surface chemistry of CuS but also represent the first time observation of hole dynamics in semiconductor nanocrystals using XTA.« less

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

DOE PAGES

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

2017-07-01

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Photoinduced molecular chirality probed by ultrafast resonant X-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rouxel, Jérémy R.; Kowalewski, Markus; Mukamel, Shaul

Recently developed circularly polarized X-ray light sources can probe the ultrafast chiral electronic and nuclear dynamics through spatially localized resonant core transitions. Here, we present simulations of time-resolved circular dichroism signals given by the difference of left and right circularly polarized X-ray probe transmission following an excitation by a circularly polarized optical pump with the variable time delay. Application is made to formamide which is achiral in the ground state and assumes two chiral geometries upon optical excitation to the first valence excited state. Probes resonant with various K-edges (C, N, and O) provide different local windows onto the paritymore » breaking geometry change thus revealing the enantiomer asymmetry.« less

Ultrafast kinetics of linkage isomerism in Na2[Fe(CN)5NO] aqueous solution revealed by time-resolved photoelectron spectroscopy

PubMed Central

Raheem, Azhr A.; Wilke, Martin; Borgwardt, Mario; Engel, Nicholas; Bokarev, Sergey I.; Grell, Gilbert; Aziz, Saadullah G.; Kühn, Oliver; Kiyan, Igor Yu.; Merschjann, Christoph; Aziz, Emad F.

2017-01-01

The kinetics of ultrafast photoinduced structural changes in linkage isomers is investigated using Na2[Fe(CN)5NO] as a model complex. The buildup of the metastable side-on configuration of the NO ligand, as well as the electronic energy levels of ground, excited, and metastable states, has been revealed by means of time-resolved extreme UV (XUV) photoelectron spectroscopy in aqueous solution, aided by theoretical calculations. Evidence of a short-lived intermediate state in the isomerization process and its nature are discussed, finding that the complete isomerization process occurs in less than 240 fs after photoexcitation. PMID:28713840

DOE Office of Scientific and Technical Information (OSTI.GOV)

Samu, Gergely F.; Janaky, Csaba; Kamat, Prashant V.

Photoinduced segregation in mixed halide perovskites has a direct influence on decreasing the solar cell efficiency as segregated I-rich domains serve as charge recombination centers. Here, the changes in the external quantum efficiency mirror the spectral loss in the absorption; however, the time scale of the IPCE recovery in the dark is slower than the absorption recovery, showing the intricate nature of the photoinduced halide segregation and charge collection in solar cell devices.

Femtosecond dynamics and laser control of charge transport in trans-polyacetylene.

PubMed

Franco, Ignacio; Shapiro, Moshe; Brumer, Paul

2008-06-28

The induction of dc electronic transport in rigid and flexible trans-polyacetylene oligomers according to the omega versus 2omega coherent control scenario is investigated using a quantum-classical mean field approximation. The approach involves running a large ensemble of mixed quantum-classical trajectories under the influence of omega+2omega laser fields and choosing the initial conditions by sampling the ground-state Wigner distribution function for the nuclei. The vibronic couplings are shown to change the mean single-particle spectrum, introduce ultrafast decoherence, and enhance intramolecular vibrational and electronic relaxation. Nevertheless, even in the presence of significant couplings, limited coherent control of the electronic dynamics is still viable, the most promising route involving the use of femtosecond pulses with a duration that is comparable to the electronic dephasing time. The simulations offer a realistic description of the behavior of a simple coherent control scenario in a complex system and provide a detailed account of the femtosecond photoinduced vibronic dynamics of a conjugated polymer.

Mapping molecular motions leading to charge delocalization with ultrabright electrons

NASA Astrophysics Data System (ADS)

Sciaini, German

2014-05-01

Ultrafast diffraction has broken the barrier to atomic exploration by combining the atomic spatial resolution of diffraction techniques with the temporal resolution of ultrafast spectroscopy. X-ray free electron lasers, slicing techniques and femtosecond laser-driven X-ray and electron sources have been successfully applied for the study of ultrafast structural dynamics in a variety of samples. Yet, the application of fs-diffraction to the study of rather sensitive organic molecular crystals remains unexplored. Organic crystals are composed by weak scattering centres, often present low melting points, poor heat conductivity and are, typically, radiation sensitive. Low repetition rates (about tens of Hertz) are therefore required to overcome accumulative heating effects from the laser excitation that can degrade the sample and mask the structural dynamics. This imparts tremendous constraints on source brightness to acquire enough diffraction data before adverse photo-degradation effects have played a non-negligible role in the crystalline structure. We implemented ultra-bright femtosecond electron diffraction to obtain a movie of the relevant molecular motions driving the photo-induced insulator-to-metal phase transition in the organic charge-transfer salt (EDO-TTF)2PF6. On the first few picoseconds (0 - 10 ps) the structural evolution, well-described by three main reaction coordinates, reaches a transient intermediate state (TIS). Model structural refinement calculations indicate that fast sliding of flat EDO-TTF molecules with consecutive motion of PF6 counter-ions drive the formation of TS instead of the expected flattening of initially bent EDO-TTF moieties which seems to evolve through a slower thermal pathway that brings the system into a final high temperature-type state. These findings establish the potential of ultrabright femtosecond electron sources for probing the primary processes governing structural dynamics with atomic resolution in labile systems relevant to chemistry and biology. For more information vide-infra Gao et al., Funding for this project was provided by the Natural Sciences and Engineering Research Council of Canada and the Canada Foundation for Innovation and Grant Agencies in Japan, vide infra Nature reference for more details.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

NASA Astrophysics Data System (ADS)

Hong, Sung-Young; Xu, Pan; Camillone, Nina R.; White, Michael G.; Camillone, Nicholas

2016-07-01

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate-adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increases roughly two orders magnitude, and (ii) the adsorbate-substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate-substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, ηel, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of ηel largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Sung-Young; Camillone, Nina R.; Camillone, Nicholas, E-mail: nicholas@bnl.gov

We report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probability increasesmore » roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η{sub el}, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η{sub el} largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Adlayer structure dependent ultrafast desorption dynamics in carbon monoxide adsorbed on Pd (111)

DOE PAGES

Hong, Sung -Young; Xu, Pan; Camillone, Nina R.; ...

2016-07-01

Here, we report our ultrafast photoinduced desorption investigation of the coverage dependence of substrate–adsorbate energy transfer in carbon monoxide adlayers on the (111) surface of palladium. As the CO coverage is increased, the adsorption site population shifts from all threefold hollows (up to 0.33 ML), to bridge and near bridge (>0.5 to 0.6 ML) and finally to mixed threefold hollow plus top site (at saturation at 0.75 ML). We show that between 0.24 and 0.75 ML this progression of binding site motifs is accompanied by two remarkable features in the ultrafast photoinduced desorption of the adsorbates: (i) the desorption probabilitymore » increases roughly two orders magnitude, and (ii) the adsorbate–substrate energy transfer rate observed in two-pulse correlation experiments varies nonmonotonically, having a minimum at intermediate coverages. Simulations using a phenomenological model to describe the adsorbate–substrate energy transfer in terms of frictional coupling indicate that these features are consistent with an adsorption-site dependent electron-mediated energy coupling strength, η el, that decreases with binding site in the order: three-fold hollow > bridge and near bridge > top site. This weakening of η el largely counterbalances the decrease in the desorption activation energy that accompanies this progression of adsorption site motifs, moderating what would otherwise be a rise of several orders of magnitude in the desorption probability. Within this framework, the observed energy transfer rate enhancement at saturation coverage is due to interadsorbate energy transfer from the copopulation of molecules bound in three-fold hollows to their top-site neighbors.« less

Photophysics of detection of explosive vapours via luminescence quenching of thin films: impact of inter-molecular interactions.

PubMed

Shoaee, Safa; Fan, Shengqiang; Burn, Paul L; Shaw, Paul E

2016-09-21

Fluorescence-based detection of explosive analytes requires an understanding of the nature of the excited state responsible for the luminescence response of a sensing material. Many measurements are carried out to elucidate the fundamental photophysical properties of an emissive material in solution. However, simple transfer of the understanding gained from the solution measurements to the solid-state can lead to errors. This is in part due to the absence of inter-molecular interactions of the chromophores in solution, which are present in the solid-state. To understand the role of inter-molecular interactions on the detection of explosive analytes we have chosen dendrimers from two different families, D1 and D2, which allow facile control of the inter-molecular interactions through the choice of dendrons and emissive chromophores. Using ultrafast transient absorption spectroscopy we find that the solution photoinduced absorption (PA) for both materials can be explained in terms of the generation of singlet excitons, which decay to the ground state, or intersystem cross (ISC) to form a triplet exciton. In neat films however, we observe different photophysical behaviours; first, ISC to the triplet state does not occur, and second, depending on the chromophore, charge transfer and charge separated states are formed. Furthermore, we find that when either dendrimer is interfaced with analyte vapour, the singlet state is strongly quenched, generating a charge transfer state that undergoes geminate recombination.

Dynamics of correlation-frozen antinodal quasiparticles in superconducting cuprates

PubMed Central

Cilento, Federico; Manzoni, Giulia; Sterzi, Andrea; Peli, Simone; Ronchi, Andrea; Crepaldi, Alberto; Boschini, Fabio; Cacho, Cephise; Chapman, Richard; Springate, Emma; Eisaki, Hiroshi; Greven, Martin; Berciu, Mona; Kemper, Alexander F.; Damascelli, Andrea; Capone, Massimo; Giannetti, Claudio; Parmigiani, Fulvio

2018-01-01

Many puzzling properties of high–critical temperature (Tc) superconducting (HTSC) copper oxides have deep roots in the nature of the antinodal quasiparticles, the elementary excitations with wave vector parallel to the Cu–O bonds. These electronic states are most affected by the onset of antiferromagnetic correlations and charge instabilities, and they host the maximum of the anisotropic superconducting gap and pseudogap. We use time-resolved extreme-ultraviolet photoemission with proper photon energy (18 eV) and time resolution (50 fs) to disclose the ultrafast dynamics of the antinodal states in a prototypical HTSC cuprate. After photoinducing a nonthermal charge redistribution within the Cu and O orbitals, we reveal a dramatic momentum-space differentiation of the transient electron dynamics. Whereas the nodal quasiparticle distribution is heated up as in a conventional metal, new quasiparticle states transiently emerge at the antinodes, similarly to what is expected for a photoexcited Mott insulator, where the frozen charges can be released by an impulsive excitation. This transient antinodal metallicity is mapped into the dynamics of the O-2p bands, thus directly demonstrating the intertwining between the low- and high-energy scales that is typical of correlated materials. Our results suggest that the correlation-driven freezing of the electrons moving along the Cu–O bonds, analogous to the Mott localization mechanism, constitutes the starting point for any model of high-Tc superconductivity and other exotic phases of HTSC cuprates. PMID:29507885

Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection from a PbSe quantum dot into the TiO2 surface.

PubMed

Long, Run; Prezhdo, Oleg V

2011-11-30

Following recent experiments [Science 2010, 328, 1543; PNAS 2011, 108, 965], we report an ab initio nonadiabatic molecular dynamics (NAMD) simulation of the ultrafast photoinduced electron transfer (ET) from a PbSe quantum dot (QD) into the rutile TiO(2) (110) surface. The system forms the basis for QD-sensitized semiconductor solar cells and demonstrates that ultrafast interfacial ET is instrumental for achieving high efficiencies in solar-to-electrical energy conversion. The simulation supports the observation that the ET successfully competes with energy losses due to electron-phonon relaxation. The ET proceeds by the adiabatic mechanism because of strong donor-acceptor coupling. High frequency polar vibrations of both QD and TiO(2) promote the ET, since these modes can rapidly influence the donor-acceptor state energies and coupling. Low frequency vibrations generate a distribution of initial conditions for ET, which shows a broad variety of scenarios at the single-molecule level. Compared to the molecule-TiO(2) interfaces, the QD-TiO(2) system exhibits pronounced differences that arise due to the larger size and higher rigidity of QDs relative to molecules. Both donor and acceptor states are more delocalized in the QD system, and the ET is promoted by optical phonons, which have relatively low frequencies in the QD materials composed of heavy elements. In contrast, in molecular systems, optical phonons are not thermally accessible under ambient conditions. Meanwhile, TiO(2) acceptor states resemble surface impurities due to the local influence of molecular chromophores. At the same time, the photoinduced ET at both QD-TiO(2) and molecule-TiO(2) interfaces is ultrafast and occurs by the adiabatic mechanism, as a result of strong donor-acceptor coupling. The reported state-of-the-art simulation generates a detailed time-domain atomistic description of the interfacial ET process that is fundamental to a wide variety of applications.

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

PubMed

Zheng, Qijing; Saidi, Wissam A; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V; Petek, Hrvoje; Zhao, Jin

2017-10-11

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

Photoinduced electron transfer in a molecular dyad by nanosecond pump-pump-probe spectroscopy.

PubMed

Ha-Thi, M-H; Pham, V-T; Pino, T; Maslova, V; Quaranta, A; Lefumeux, C; Leibl, W; Aukauloo, A

2018-06-01

The design of robust and inexpensive molecular photocatalysts for the conversion of abundant stable molecules like H2O and CO2 into an energetic carrier is one of the major fundamental questions for scientists nowadays. The outstanding challenge is to couple single photoinduced charge separation events with the sequential accumulation of redox equivalents at the catalytic unit for performing multielectronic catalytic reactions. Herein, double excitation by nanosecond pump-pump-probe experiments was used to interrogate the photoinduced charge transfer and charge accumulation on a molecular dyad composed of a porphyrin chromophore and a ruthenium-based catalyst in the presence of a reversible electron acceptor. An accumulative charge transfer state is unattainable because of rapid reverse electron transfer to the photosensitizer upon the second excitation and the low driving force of the forward photodriven electron transfer reaction. Such a method allows the fundamental understanding of the relaxation mechanism after two sequential photon absorptions, deciphering the undesired electron transfer reactions that limit the charge accumulation efficiency. This study is a step toward the improvement of synthetic strategies of molecular photocatalysts for light-induced charge accumulation and more generally, for solar energy conversion.

Plasmon Enhancement of Photoinduced Resistivity Changes in Bi1-xCaxMnO3 Thin Films

NASA Astrophysics Data System (ADS)

Smolyaninova, Vera; Talanova, E.; Kolagani, Rajeswari; Yong, G.; Kennedy, R.; Steger, M.; Wall, K.

2007-03-01

Doped rare-earth manganese oxides (manganites) exhibit a wide variety of physical phenomena due to complex interplay of electronic, magnetic, orbital, and structural degrees of freedom and their sensitivity to external fields. A photoinduced insulator to conductor transition in charge-ordered manganites is especially interesting from the point of view of creating photonic devices. Thin films of Bi0.4Ca0.6MnO3 exhibit large photoinduced resistivity changes associated with melting of the charge ordering by visible light [1]. We have found a considerable increase of the photoinduced resistivity changes in the Bi0.4Ca0.6MnO3 thin film after depositing metal nanoparticles on the surface. This increase can be explained by enhancement of local electromagnetic field in the vicinity of the gold nanoparticle due to the plasmon resonance. The changes in lifetime of the photoinduced state will be reported, and the possible origin of these effects will be discussed. [1] V. N. Smolyaninova at al., Appl. Phys. Lett. 86, 071922 (2005).

Adapting High Brightness Relativistic Electron Beams for Ultrafast Science

NASA Astrophysics Data System (ADS)

Scoby, Cheyne Matthew

This thesis explores the use of ultrashort bunches generated by a radiofrequency electron photoinjector driven by a femtosecond laser. Rf photoinjector technology has been developed to generate ultra high brightness beams for advanced accelerators and to drive advanced light source applications. The extremely good quality of the beams generated by this source has played a key role in the development of 4th generation light sources such as the Linac Coherent Light Source, thus opening the way to studies of materials science and biological systems with high temporal and spatial resolution. At the Pegasus Photoinjector Lab, we have developed the application of a BNL/SLAC/UCLA 1.6-cell rf photoinjector as a tool for ultrafast science in its own right. It is the aim of this work to explore the generation of ultrashort electron bunches, give descriptions of the novel ultrafast diagnostics developed to be able to characterize the electron bunch and synchronize it with a pump laser, and share some of the scientific results that were obtained with this technology at the UCLA Pegasus laboratory. This dissertation explains the requirements of the drive laser source and describes the principles of rf photoinjector design and operation necessary to produce electron bunches with an rms longitudinal length < 100 femtoseconds containing 107 - 108 electrons per bunch. In this condition, when the laser intensity is sufficiently high, multiphoton photoemission is demonstrated to be more efficient in terms of charge yield than single photon photoemission. When a short laser pulse hits the cathode the resulting beam dynamics are dominated by a strong space charge driven longitudinal expansion which leads to the creation of a nearly ideal uniformly filled ellipsoidal distribution. These beam distributions are characterized by linear space charge forces and hence by high peak brightness and small transverse emittances. This regime of operation of the RF photoinjector is also termed the “blow-out regime.” When the beam charge is maintained low, ultrashort electron bunches can be obtained enabling novel applications such as single shot Femtosecond Relativistic Electron Diffraction (FRED). High precision temporal diagnostic and synchronization techniques are integral to the use of femtosecond electron bunches for ultrafast science. An x-band rf streak camera provides measurements of the longitudinal profiles of sub-ps electron bunches. Spatial encoded electro-optic timestamping is developed to overcome the inherent rf-laser synchronization errors in rf photoinjectors. The ultrafast electron beams generated with the RF photoenjector are employed in pump-probe experiments wherein a target is illuminated with an intense pump laser to induce a transient behavior in the sample. FRED is used to study the melting of gold after heating with an intense femtosecond laser pulse. In a first experiment we study the process by taking different single-shot diffraction patterns at varying delays between the pump an probe beams. In a second experiment a variation of the technique is employed using the rf streak camera to time-stretch the beam after it has diffraction from the sample in order to capture the full melting dynamics in a single shot. Finally, relativistic ultrashort electron bunches are used as a probe of plasma dynamics in electron radiography/shadowgraphy experiments. This technique is used to study photoemission with intense laser pulses and the evolution of electromagnetic fields in a photoinduced dense plasma. This experiment is also performed in two different modes: one where different pictures are acquired at different time delays, and the other where a single streak image is used to obtain visualization of the propagation electromagnetic fields with an unprecedented 35 femtosecond resolution.

Photoinduced transition to charge-ordered phases from dynamical localization in the metallic phase of α -(BEDT-TTF)2I3

NASA Astrophysics Data System (ADS)

Oya, Koudai; Takahashi, Akira

2018-03-01

From theory, we investigate charge localization induced by higher-frequency off-resonance light-pulse excitation in the metallic phase of α -(BEDT-TTF) 2I3 by numerically solving the time-dependent Schrödinger equation in the quarter-filled extended Hubbard model for the material. Around e a A(max )=1 , where e a A(max ) is the maximum amplitude of the dimensionless vector potential of the pump pulse, the charge distribution is significantly changed by photoexcitation, and the light-pulse-induced collective charge oscillations continue after photoexcitation. Furthermore, the charge dynamics depend strongly on the polarization direction of the pump pulse. These results are consistent with experiment. The magnitudes of the effective transfer integrals are reduced by strong photoexcitation, and this precursory phenomenon for dynamical localization is mainly driven by a photoinduced change in the ratio of the effective transfer integrals between the two strongest bonds. For e a A(max )≳2 , the photoinduced transition to the charge-ordered state, which can be regarded as a light-dressed state, occurs because of dynamical localization. Furthermore, the type of photogenerated charge-ordered state can be controlled by choosing e a A(max ) and the polarization direction.

Robust Stacking-Independent Ultrafast Charge Transfer in MoS2/WS2 Bilayers.

PubMed

Ji, Ziheng; Hong, Hao; Zhang, Jin; Zhang, Qi; Huang, Wei; Cao, Ting; Qiao, Ruixi; Liu, Can; Liang, Jing; Jin, Chuanhong; Jiao, Liying; Shi, Kebin; Meng, Sheng; Liu, Kaihui

2017-12-26

Van der Waals-coupled two-dimensional (2D) heterostructures have attracted great attention recently due to their high potential in the next-generation photodetectors and solar cells. The understanding of charge-transfer process between adjacent atomic layers is the key to design optimal devices as it directly determines the fundamental response speed and photon-electron conversion efficiency. However, general belief and theoretical studies have shown that the charge transfer behavior depends sensitively on interlayer configurations, which is difficult to control accurately, bringing great uncertainties in device designing. Here we investigate the ultrafast dynamics of interlayer charge transfer in a prototype heterostructure, the MoS 2 /WS 2 bilayer with various stacking configurations, by optical two-color ultrafast pump-probe spectroscopy. Surprisingly, we found that the charge transfer is robust against varying interlayer twist angles and interlayer coupling strength, in time scale of ∼90 fs. Our observation, together with atomic-resolved transmission electron characterization and time-dependent density functional theory simulations, reveals that the robust ultrafast charge transfer is attributed to the heterogeneous interlayer stretching/sliding, which provides additional channels for efficient charge transfer previously unknown. Our results elucidate the origin of transfer rate robustness against interlayer stacking configurations in optical devices based on 2D heterostructures, facilitating their applications in ultrafast and high-efficient optoelectronic and photovoltaic devices in the near future.

Photoinduced electron transfer and solvation in iodide-doped acetonitrile clusters.

PubMed

Ehrler, Oli T; Griffin, Graham B; Young, Ryan M; Neumark, Daniel M

2009-04-02

We have used ultrafast time-resolved photoelectron imaging to measure charge transfer dynamics in iodide-doped acetonitrile clusters I(-)(CH(3)CN)(n) with n = 5-10. Strong modulations of vertical detachment energies were observed following charge transfer from the halide, allowing interpretation of the ongoing dynamics. We observe a sharp drop in the vertical detachment energy (VDE) within 300-400 fs, followed by a biexponential increase that is complete by approximately 10 ps. Comparison to theory suggests that the iodide is internally solvated and that photodetachment results in formation of a diffuse electron cloud in a confined cavity. We interpret the initial drop in VDE as a combination of expansion of the cavity and localization of the excess electron on one or two solvent molecules. The subsequent increase in VDE is attributed to a combination of the I atom leaving the cavity and rearrangement of the acetonitrile molecules to solvate the electron. The n = 5-8 clusters then show a drop in VDE of around 50 meV on a much longer time scale. The long-time VDEs are consistent with those of (CH(3)CN)(n)(-) clusters with internally solvated electrons. Although the excited-state created by the pump pulse decays by emission of a slow electron, no such decay is seen by 200 ps.

Dynamics of Photoexcited State of Semiconductor Quantum Dots

NASA Astrophysics Data System (ADS)

Trivedi, Dhara J.

In this thesis, non-adiabatic molecular dynamics (NAMD) of excited states in semiconductor quantum dots are investigated. Nanoscale systems provide important opportunities for theory and computation for research because the experimental tools often provide an incomplete picture of the structure and/or function of nanomaterials, and theory can often fill in missing features crucial in understanding what is being measured. The simulation of NAMD is an indispensable tool for understanding complex ultrafast photoinduced processes such as charge and energy transfer, thermal relaxation, and charge recombination. Based on the state-of-the-art ab initio approaches in both the energy and time domains, the thesis presents a comprehensive discussion of the dynamical processes in quantum dots, ranging from the initial photon absorption to the final emission. We investigate the energy relaxation and transfer rates in pure and surface passivated quantum dots of different sizes. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. We develop and implement more accurate and efficient methods for NAMD. These methods are advantageous over the traditional ones when one encounters classically forbidden transitions. We also explore the effect of decoherence and non-adiabatic couplings on the dynamics. The results indicate significant influence on the accuracy and related computational cost of the simulated dynamics.

Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

NASA Astrophysics Data System (ADS)

Ma, X.; Fang, F.; Li, Q.; Zhu, J.; Yang, Y.; Wu, Y. Z.; Zhao, H. B.; Lüpke, G.

2015-10-01

Optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recovery time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

DOE PAGES

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G.; ...

2017-11-28

Here, the kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(I) bis(phenanthroline)/ruthenium(II) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(I)–Ru(II) analogs of the homodinuclear Cu(I)–Cu(I) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These resultsmore » suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.« less

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G.

Here, the kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(I) bis(phenanthroline)/ruthenium(II) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(I)–Ru(II) analogs of the homodinuclear Cu(I)–Cu(I) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These resultsmore » suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE PAGES

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.; ...

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Layer-Dependent Ultrafast Carrier and Coherent Phonon Dynamics in Black Phosphorus.

PubMed

Miao, Xianchong; Zhang, Guowei; Wang, Fanjie; Yan, Hugen; Ji, Minbiao

2018-05-09

Black phosphorus is a layered semiconducting material, demonstrating strong layer-dependent optical and electronic properties. Probing the photophysical properties on ultrafast time scales is of central importance in understanding many-body interactions and nonequilibrium quasiparticle dynamics. Here, we applied temporally, spectrally, and spatially resolved pump-probe microscopy to study the transient optical responses of mechanically exfoliated few-layer black phosphorus, with layer numbers ranging from 2 to 9. We have observed layer-dependent resonant transient absorption spectra with both photobleaching and red-shifted photoinduced absorption features, which could be attributed to band gap renormalization of higher subband transitions. Surprisingly, coherent phonon oscillations with unprecedented intensities were observed when the probe photons were in resonance with the optical transitions, which correspond to the low-frequency layer-breathing mode. Our results reveal strong Coulomb interactions and electron-phonon couplings in photoexcited black phosphorus, providing important insights into the ultrafast optical, nanomechanical, and optoelectronic properties of this novel two-dimensional material.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium.

PubMed

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J; Kraus, Peter M; Cushing, Scott K; Gandman, Andrey; Kaplan, Christopher J; Oh, Myoung Hwan; Prell, James S; Prendergast, David; Pemmaraju, Chaitanya D; Neumark, Daniel M; Leone, Stephen R

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20  cm -3 . Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley-Read-Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.

Alternative Electron-Transfer Channels Ensure Ultrafast Deactivation of Light-Induced Excited States in Riboflavin Binding Protein.

PubMed

Zanetti-Polzi, Laura; Aschi, Massimiliano; Amadei, Andrea; Daidone, Isabella

2017-07-20

Flavoproteins, containing flavin chromophores, are enzymes capable of transferring electrons at very high speeds. The ultrafast photoinduced electron-transfer (ET) kinetics of riboflavin binding protein to the excited riboflavin was studied by femtosecond spectroscopy and found to occur within a few hundred femtoseconds [ Zhong and Zewail, Proc. Natl. Acad. Sci. U.S.A. 2001, 98, 11867-11872 ]. This ultrafast kinetics was attributed to the presence of two aromatic rings that could transfer the electron to riboflavin: the side chains of tryptophan 156 and tyrosine 75. However, the underlying ET mechanism remained unclear. Here, using a hybrid quantum mechanical-molecular dynamics approach, we perform ET dynamics simulations taking into account the motion of the protein and the solvent upon ET. This approach reveals that ET occurs via a major reaction channel involving tyrosine 75 (83%) and a minor one involving tryptophan 156 (17%). We also show that the protein environment is designed to ensure the fast quenching of the riboflavin excited state.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J.; Kraus, Peter M.; Cushing, Scott K.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm−3. Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley–Read–Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions. PMID:28569752

Visualization of a stable intermediate phase in photoinduced metal-to-insulator transition in manganites

NASA Astrophysics Data System (ADS)

Lin, Hanxuan; Liu, Hao; Bai, Yu; Miao, Tian; Yu, Yang; Zhu, Yinyan; Chen, Hongyan; Kou, Yunfang; Niu, Jiebin; Wang, Wenbin; Yin, Lifeng; Shen, Jian

First order metal-insulator transition, accounting for various intriguing phenomena, is one of the most important phase transitions in condensed matter systems. Aside from the initial and final states, i.e. the metallic and insulating phases, no stable intermediate phase has been experimentally identified in such first order phase transition, though some transient phases do exist at the ultrafast time scale. Here, using our unique low-temperature, high-field magnetic force microscopy with photoexcitation, we directly observed a stable intermediate phase emerging and mediating the photoinduced first order metal-insulator transition in manganites. This phase is characteristic of low net magnetization and high resistivity. Our observations unveil the microscopic details of the photoinduced metal-insulator transition in manganites, which may be insightful to study first order metal-insulator transition in other condensed matter systems. This work was supported by National Key Research Program of China (2016YFA0300702), National Basic Research Program of China (973 Program) under the Grant No. 2013CB932901 and 2014CB921104; National Natural Science Foundation of China (11274071, 11504053).

Spectral resolution of states relevant to photoinduced charge transfer in modified pentacene/ZnO field-effect transistors

NASA Astrophysics Data System (ADS)

Spalenka, Josef W.; Mannebach, Ehren M.; Bindl, Dominick J.; Arnold, Michael S.; Evans, Paul G.

2011-11-01

Pentacene field-effect transistors incorporating ZnO quantum dots can be used as a sensitive probe of the optical properties of a buried donor-acceptor interface. Photoinduced charge transfer between pentacene and ZnO in these devices varies with incident photon energy and reveals which energies will contribute most to charge transfer in other structures. A subsequent slow return to the dark state following the end of illumination arises from near-interface traps. Charge transfer has a sharp onset at 1.7 eV and peaks at 1.82 and 2.1 eV due to transitions associated with excitons, features absent in pentacene FETs without ZnO.

Photoinduced currents in pristine and ion irradiated kapton-H polyimide

NASA Astrophysics Data System (ADS)

Sharma, Anu; Sridharbabu, Y.; Quamara, J. K.

2014-10-01

The photoinduced currents in pristine and ion irradiated kapton-H polyimide have been investigated for different applied electric fields at 200°C. Particularly the effect of illumination intensity on the maximum current obtained as a result of photoinduced polarization has been studied. Samples were irradiated by using PELLETRON facility, IUAC, New Delhi. The photo-carrier charge generation depends directly on intensity of illumination. The samples irradiated at higher fluence show a decrease in the peak current with intensity of illumination. The secondary radiation induced crystallinity (SRIC) is responsible for the increase in maximum photoinduced currents generated with intensity of illumination.

Photoinduced currents in pristine and ion irradiated kapton-H polyimide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Anu, E-mail: sharmaanu81@gmail.com; Sridharbabu, Y., E-mail: sharmaanu81@gmail.com; Quamara, J. K., E-mail: sharmaanu81@gmail.com

2014-10-15

The photoinduced currents in pristine and ion irradiated kapton-H polyimide have been investigated for different applied electric fields at 200°C. Particularly the effect of illumination intensity on the maximum current obtained as a result of photoinduced polarization has been studied. Samples were irradiated by using PELLETRON facility, IUAC, New Delhi. The photo-carrier charge generation depends directly on intensity of illumination. The samples irradiated at higher fluence show a decrease in the peak current with intensity of illumination. The secondary radiation induced crystallinity (SRIC) is responsible for the increase in maximum photoinduced currents generated with intensity of illumination.

Photoinduced doping in heterostructures of graphene and boron nitride.

PubMed

Ju, L; Velasco, J; Huang, E; Kahn, S; Nosiglia, C; Tsai, Hsin-Zon; Yang, W; Taniguchi, T; Watanabe, K; Zhang, Y; Zhang, G; Crommie, M; Zettl, A; Wang, F

2014-05-01

The design of stacks of layered materials in which adjacent layers interact by van der Waals forces has enabled the combination of various two-dimensional crystals with different electrical, optical and mechanical properties as well as the emergence of novel physical phenomena and device functionality. Here, we report photoinduced doping in van der Waals heterostructures consisting of graphene and boron nitride layers. It enables flexible and repeatable writing and erasing of charge doping in graphene with visible light. We demonstrate that this photoinduced doping maintains the high carrier mobility of the graphene/boron nitride heterostructure, thus resembling the modulation doping technique used in semiconductor heterojunctions, and can be used to generate spatially varying doping profiles such as p-n junctions. We show that this photoinduced doping arises from microscopically coupled optical and electrical responses of graphene/boron nitride heterostructures, including optical excitation of defect transitions in boron nitride, electrical transport in graphene, and charge transfer between boron nitride and graphene.

A Victim of Halide Ion Segregation. How Light Soaking Affects Solar Cell Performance of Mixed Halide Lead Perovskites

DOE PAGES

Samu, Gergely F.; Janaky, Csaba; Kamat, Prashant V.

2017-07-24

Photoinduced segregation in mixed halide perovskites has a direct influence on decreasing the solar cell efficiency as segregated I-rich domains serve as charge recombination centers. Here, the changes in the external quantum efficiency mirror the spectral loss in the absorption; however, the time scale of the IPCE recovery in the dark is slower than the absorption recovery, showing the intricate nature of the photoinduced halide segregation and charge collection in solar cell devices.

Dynamic Optoelectronic Properties in Perovskite Oxide Thin Films Measured with Ultrafast Transient Absorption & Reflectance Spectroscopy

NASA Astrophysics Data System (ADS)

Smolin, Sergey Y.

Ultrafast transient absorption and reflectance spectroscopy are foundational techniques for studying photoexcited carrier recombination mechanisms, lifetimes, and charge transfer rates. Because quantifying photoexcited carrier dynamics is central to the intelligent design and improvement of many solid state devices, these transient optical techniques have been applied to a wide range of semiconductors. However, despite their promise, interpretation of transient absorption and reflectance data is not always straightforward and often relies on assumptions of physical processes, especially with respect to the influence of heating. Studying the material space of perovskite oxides, the careful collection, interpretation, and analysis of ultrafast data is presented here as a guide for future research into novel semiconductors. Perovskite oxides are a class of transition metal oxides with the chemical structure ABO3. Although traditionally studied for their diverse physical, electronic, and magnetic properties, perovskite oxides have gained recent research attention as novel candidates for light harvesting applications. Indeed, strong tunable absorption, unique interfacial properties, and vast chemical flexibility make perovskite oxides a promising photoactive material system. However, there is limited research characterizing dynamic optoelectronic properties, such as recombination lifetimes, which are critical to know in the design of any light-harvesting device. In this thesis, ultrafast transient absorption and reflectance spectroscopy was used to understand these dynamic optoelectronic properties in highquality, thin (<50 nm) perovskite oxide films grown by molecular beam epitaxy. Starting with epitaxial LaFeO3 (LFO) grown on (LaAlO 3)0.3(Sr2AlTaO6)0.7 (LSAT), transient absorption spectroscopy reveals two photoinduced absorption features at the band gap of LFO at 2.4 eV and at the higher energy absorption edge at 3.5 eV. Using a combination of temperature-dependent, variable-angle spectroscopic ellipsometry and time-resolved ultrafast optical spectroscopy on a type I heterostructure, we clarify thermal and electronic contributions to spectral transients in LaFeO3. Upon comparison to thermally-derived static spectra of LaFeO3, we find that thermal contributions dominate the transient absorption and reflectance spectra above the band gap. A transient photoinduced absorption feature below the band gap at 1.9 eV is not reproduced in the thermally derived spectra and has significantly longer decay kinetics from the thermallyinduced features; therefore, this long lived photoinduced absorption is likely derived, at least partially, from photoexcited carriers with lifetimes much longer than 3 nanoseconds. LaFeO3 has a wide band gap of 2.4 eV but its absorption can be decreased with chemical substitution of Sr for Fe to make it more suitable for various applications. This type of A-site substitution is a common route to change static optical absorption in perovskite oxides, but there are no systematic studies looking at how A-site substitution changes dynamic optoelectronic properties. To understand the relationship between composition and static and dynamic optical properties we worked with the model system of La1-xSrxFeO 3-delta epitaxial films grown on LSAT, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy with broadband visible (1.6 eV to 4 eV) and near-infrared (0.9 eV to 1.5 eV) probes. The sign of the reflectance change in the near-infrared region in LSFO is indicative of carrier bandfilling of newly created electronic states by photoexcited carriers. Moreover, we find that similar transient spectral trends can be induced with A-site substitution or through oxygen vacancies, which is a surprising result. Probing the near-infrared region reveals similar nanosecond (1-3 ns) photoexcited carrier lifetimes for oxygen deficient and stoichiometric films. These results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in long lived recombination kinetics. Although this thesis represents one of the first comprehensive studies using broad band transient absorption and reflectance spectroscopy to study dynamic optoelectronic phenomena in perovskite oxides, it can also serve as a guide for the implementation and interpretation of ultrafast spectroscopy in other material systems. Moreover, the ultrafast work on perovskite oxides indicates that these materials have long nanosecond lifetimes required for light harvesting devices and should be investigated further.

Charge transport and recombination in bulk heterojunction solar cells studied by the photoinduced charge extraction in linearly increasing voltage technique

NASA Astrophysics Data System (ADS)

Mozer, A. J.; Sariciftci, N. S.; Lutsen, L.; Vanderzande, D.; Österbacka, R.; Westerling, M.; Juška, G.

2005-03-01

Charge carrier mobility and recombination in a bulk heterojunction solar cell based on the mixture of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-phenylene vinylene] (MDMO-PPV) and 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)-C61 (PCBM) has been studied using the novel technique of photoinduced charge carrier extraction in a linearly increasing voltage (Photo-CELIV). In this technique, charge carriers are photogenerated by a short laser flash, and extracted under a reverse bias voltage ramp after an adjustable delay time (tdel). The Photo-CELIV mobility at room temperature is found to be μ =2×10-4cm2V-1s-1, which is almost independent on charge carrier density, but slightly dependent on tdel. Furthermore, determination of charge carrier lifetime and demonstration of an electric field dependent mobility is presented.

Optoelectronic properties and depth profile of charge transport in nanocrystal films

NASA Astrophysics Data System (ADS)

Aigner, Willi; Bienek, Oliver; Desta, Derese; Wiggers, Hartmut; Stutzmann, Martin; Pereira, Rui N.

2017-07-01

We investigate the charge transport in nanocrystal (NC) films using field effect transistors (FETs) of silicon NCs. By studying films with various thicknesses in the dark and under illumination with photons with different penetration depths (UV and red light), we are able to predictably change the spatial distribution of charge carriers across the films' profile. The experimental data are compared with photoinduced charge carrier generation rates computed using finite-difference time-domain (FDTD) simulations complemented with optical measurements. This enables us to understand the optoelectronic properties of NC films and the depth profile dependence of the charge transport properties. From electrical measurements, we extract the total (bulk) photoinduced charge carrier densities (nphoto) and the photoinduced charge carrier densities in the FETs channel (nphoto*). We observe that the values of nphoto and their dependence on film thickness are similar for UV and red light illumination, whereas a significant difference is observed for the values of nphoto*. The dependencies of nphoto and nphoto* on film thickness and illumination wavelength are compared with data from FDTD simulations. Combining experimental data and simulation results, we find that charge carriers in the top rough surface of the films cannot contribute to the macroscopic charge transport. Moreover, we conclude that below the top rough surface of NC films, the efficiency of charge transport, including the charge carrier mobility, is homogeneous across the film thickness. Our work shows that the use of NC films as photoactive layers in applications requiring harvesting of strongly absorbed photons such as photodetectors and photovoltaics demands a very rigorous control over the films' roughness.

Enhanced emission and photoconductivity due to photo-induced charge transfer from Au nanoislands to ZnO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Shang-Hsuan; Chan, Ching-Hsiang; Liang, Ching-Tarng

2016-01-25

We report systematic studies based on photoluminescence, Hall, and photoconductivity measurements together with theoretical modeling in order to identify mechanisms for the photo-induced charge transfer effects in ZnO thin film incorporated with the Au nano-islands (AuNIs). Significant enhancement of near band edge emission and improvement in conductivity of ZnO/AuNIs samples after illumination are observed, which are attributed to the photo-induced hot electrons in Au which are then transferred into the conduction band of ZnO as long as the excitation energy is higher than the offset between the ZnO conduction-band minimum and Au Fermi level. Our experimental results are consistent withmore » the general features predicted by first principles calculations.« less

Photoinduced charge carriers' accumulation and its impact on random lasing in Nd3+ doped (Pb,La)(Zr,Ti)O3 ceramics

NASA Astrophysics Data System (ADS)

Xu, Caixia; Zhang, Jingwen; Xu, Long; Ma, Xinyan; Zhao, Hua

2017-06-01

To pinpoint the driving forces behind the random lasing in Nd3+ doped lanthanum lead zirconate titanate (Nd:PLZT) ceramic plates, a combinatorial cavity with two gain media (Nd:YVO4 and Nd:PLZT) was used to study the switching feature between conventional lasing and random lasing oscillations. The complex laser output dynamics observed hinted that the photo-induced charge accumulation on the plate surface and the grain boundaries of Nd:PLZT is responsible for the lasing action switching, which was confirmed by a series of experiments, including strong electro-induced scattering, remarkable photoinduced currents, and light transmission reduction, along with measured single-pass-gain over the theoretical limit. It was found that the charge accumulation results in optical energy storage and nonuniform refractive index and hence strong scattering, which give rise to the random walks and weak localization of photons and long lasting lasing action and mode switching.

Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

DOE PAGES

Ma, X.; Fang, F.; Li, Q.; ...

2015-10-28

In this study, optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recoverymore » time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.« less

Rational material design for ultrafast rechargeable lithium-ion batteries.

PubMed

Tang, Yuxin; Zhang, Yanyan; Li, Wenlong; Ma, Bing; Chen, Xiaodong

2015-10-07

Rechargeable lithium-ion batteries (LIBs) are important electrochemical energy storage devices for consumer electronics and emerging electrical/hybrid vehicles. However, one of the formidable challenges is to develop ultrafast charging LIBs with the rate capability at least one order of magnitude (>10 C) higher than that of the currently commercialized LIBs. This tutorial review presents the state-of-the-art developments in ultrafast charging LIBs by the rational design of materials. First of all, fundamental electrochemistry and related ionic/electronic conduction theories identify that the rate capability of LIBs is kinetically limited by the sluggish solid-state diffusion process in electrode materials. Then, several aspects of the intrinsic materials, materials engineering and processing, and electrode materials architecture design towards maximizing both ionic and electronic conductivity in the electrode with a short diffusion length are deliberated. Finally, the future trends and perspectives for the ultrafast rechargeable LIBs are discussed. Continuous rapid progress in this area is essential and urgent to endow LIBs with ultrafast charging capability to meet huge demands in the near future.

Dynamical photo-induced electronic properties of molecular junctions

NASA Astrophysics Data System (ADS)

Beltako, K.; Michelini, F.; Cavassilas, N.; Raymond, L.

2018-03-01

Nanoscale molecular-electronic devices and machines are emerging as promising functional elements, naturally flexible and efficient, for next-generation technologies. A deeper understanding of carrier dynamics in molecular junctions is expected to benefit many fields of nanoelectronics and power devices. We determine time-resolved charge current flowing at the donor-acceptor interface in molecular junctions connected to metallic electrodes by means of quantum transport simulations. The current is induced by the interaction of the donor with a Gaussian-shape femtosecond laser pulse. Effects of the molecular internal coupling, metal-molecule tunneling, and light-donor coupling on photocurrent are discussed. We then define the time-resolved local density of states which is proposed as an efficient tool to describe the absorbing molecule in contact with metallic electrodes. Non-equilibrium reorganization of hybridized molecular orbitals through the light-donor interaction gives rise to two phenomena: the dynamical Rabi shift and the appearance of Floquet-like states. Such insights into the dynamical photoelectronic structure of molecules are of strong interest for ultrafast spectroscopy and open avenues toward the possibility of analyzing and controlling the internal properties of quantum nanodevices with pump-push photocurrent spectroscopy.

Dimensionality of nanoscale TiO 2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle

DOE PAGES

Tafen, De Nyago; Long, Run; Prezhdo, Oleg V.

2014-03-10

Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO 2 depends on TiO 2 dimensionality. The injection into a TiO 2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO 2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbantmore » breaks symmetry of delocalized TiO 2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.« less

Dimensionality of nanoscale TiO 2 determines the mechanism of photoinduced electron injection from a CdSe nanoparticle

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tafen, De Nyago; Long, Run; Prezhdo, Oleg V.

Assumptions about electron transfer (ET) mechanisms guide design of catalytic, photovoltaic, and electronic systems. We demonstrate that the mechanism of ET from a CdSe quantum dot (QD) into nanoscale TiO 2 depends on TiO 2 dimensionality. The injection into a TiO 2 QD is adiabatic due to strong donor–acceptor coupling, arising from unsaturated chemical bonds on the QD surface, and low density of acceptor states. In contrast, the injection into a TiO 2 nanobelt (NB) is nonadiabatic, because the state density is high, the donor–acceptor coupling is weak, and multiple phonons accommodate changes in the electronic energy. The CdSe adsorbantmore » breaks symmetry of delocalized TiO 2 NB states, relaxing coupling selection rules, and generating more ET channels. Both mechanisms can give efficient ultrafast injection. Furthermore, the dependence on system properties is very different for the two mechanisms, demonstrating that the fundamental principles leading to efficient charge separation depend strongly on the type of nanoscale material.« less

Phonon-coupled ultrafast interlayer charge oscillation at van der Waals heterostructure interfaces

NASA Astrophysics Data System (ADS)

Zheng, Qijing; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V.; Saidi, Wissam A.; Zhao, Jin

2018-05-01

Van der Waals (vdW) heterostructures of transition-metal dichalcogenide (TMD) semiconductors are central not only for fundamental science, but also for electro- and optical-device technologies where the interfacial charge transfer is a key factor. Ultrafast interfacial charge dynamics has been intensively studied, however, the atomic scale insights into the effects of the electron-phonon (e-p) coupling are still lacking. In this paper, using time dependent ab initio nonadiabatic molecular dynamics, we study the ultrafast interfacial charge transfer dynamics of two different TMD heterostructures MoS2/WS2 and MoSe2/WSe2 , which have similar band structures but different phonon frequencies. We found that MoSe2/WSe2 has softer phonon modes compared to MoS2/WS2 , and thus phonon-coupled charge oscillation can be excited with sufficient phonon excitations at room temperature. In contrast, for MoS2/WS2 , phonon-coupled interlayer charge oscillations are not easily excitable. Our study provides an atomic level understanding on how the phonon excitation and e-p coupling affect the interlayer charge transfer dynamics, which is valuable for both the fundamental understanding of ultrafast dynamics at vdW hetero-interfaces and the design of novel quasi-two-dimensional devices for optoelectronic and photovoltaic applications.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

Ultrafast and nanoscale diodes

NASA Astrophysics Data System (ADS)

Zhang, Peng; Lau, Y. Y.

2016-10-01

Charge carrier transport across interfaces of dissimilar materials (including vacuum) is the essence of all electronic devices. Ultrafast charge transport across a nanometre length scale is of fundamental importance in the miniaturization of vacuum and plasma electronics. With the combination of recent advances in electronics, photonics and nanotechnology, these miniature devices may integrate with solid-state platforms, achieving superior performance. This paper reviews recent modelling efforts on quantum tunnelling, ultrafast electron emission and transport, and electrical contact resistance. Unsolved problems and challenges in these areas are addressed.

A Comparison of Photo-Induced Hysteresis Between Hydrogenated Amorphous Silicon and Amorphous IGZO Thin-Film Transistors.

PubMed

Ha, Tae-Jun; Cho, Won-Ju; Chung, Hong-Bay; Koo, Sang-Mo

2015-09-01

We investigate photo-induced instability in thin-film transistors (TFTs) consisting of amorphous indium-gallium-zinc-oxide (a-IGZO) as active semiconducting layers by comparing with hydrogenated amorphous silicon (a-Si:H). An a-IGZO TFT exhibits a large hysteresis window in the illuminated measuring condition but no hysteresis window in the dark condition. On the contrary, a large hysteresis window measured in the dark condition in a-Si:H was not observed in the illuminated condition. Even though such materials possess the structure of amorphous phase, optical responses or photo instability in TFTs looks different from each other. Photo-induced hysteresis results from initially trapped charges at the interface between semiconductor and dielectric films or in the gate dielectric which possess absorption energy to interact with deep trap-states and affect the movement of Fermi energy level. In order to support our claim, we also perform CV characteristics in photo-induced hysteresis and demonstrate thermal-activated hysteresis. We believe that this work can provide important information to understand different material systems for optical engineering which includes charge transport and band transition.

Femtosecond x-ray scattering study of ultrafast photoinduced structural dynamics in solvated [ Co ( terpy ) 2 ] 2 +

DOE PAGES

Biasin, Elisa; van Driel, Tim Brandt; Kjær, Kasper S.; ...

2016-06-30

Here, we study the structural dynamics of photoexcited [Co(terpy) 2] 2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of themore » high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~7 ps.« less

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.; Cushing, Scott K.; Borja, Lauren J.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si0.25Ge0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M4,5-edge (∼30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons across the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔEgap,Ge,direct=0.8 eV) and Si0.25Ge0.75 indirect gaps (ΔEgap,Si0.25Ge0.75,indirect=0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si0.25Ge0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution. PMID:28653020

High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.

PubMed

Das, Sushanta K; Mahler, Andrew; Wilson, Angela K; D'Souza, Francis

2014-08-25

High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terahertz emission from ultrafast spin-charge current at a Rashba interface

NASA Astrophysics Data System (ADS)

Zhang, Qi; Jungfleisch, Matthias Benjamin; Zhang, Wei; Pearson, John E.; Wen, Haidan; Hoffmann, Axel

Ultrafast broadband terahertz (THz) radiation is highly desired in various fields from fundamental research in condensed matter physics to bio-chemical detection. Conventional ultrafast THz sources rely on either nonlinear optical effects or ultrafast charge currents in semiconductors. Recently, however, it was realized that ultrabroad-band THz radiation can be produced highly effectively by novel spintronics-based emitters that also make use of the electron's spin degree of freedom. Those THz-emitters convert a spin current flow into a terahertz electromagnetic pulse via the inverse spin-Hall effect. In contrast to this bulk conversion process, we demonstrate here that a femtosecond spin current pulse launched from a CoFeB layer can also generate terahertz transients efficiently at a two-dimensional Rashba interface between two non-magnetic materials, i.e., Ag/Bi. Those interfaces have been proven to be efficient means for spin- and charge current interconversion.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

PubMed

Huang, Jier; Huang, Zhuangqun; Yang, Ye; Zhu, Haiming; Lian, Tianquan

2010-04-07

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

Improved solar-driven photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} prepared in-situ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong, Junbo, E-mail: junbozhong@163.com; Li, Jianzhang, E-mail: lschmanuscript@163.com; Huang, Shengtian

Highlights: • Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag{submore » 2}CO{sub 3} has no effect on the crystal phase and bandgap of (BiO){sub 2}CO{sub 3}. The existence of Ag{sub 2}CO{sub 3} in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.« less

Photoinduced charge separation in a colloidal system of exfoliated layered semiconductor controlled by coexisting aluminosilicate clay.

PubMed

Nakato, Teruyuki; Yamada, Yoshimi; Miyamoto, Nobuyoshi

2009-02-05

We investigated photoinduced charge separation occurring in a multicomponent colloidal system composed of oxide nanosheets of photocatalytically active niobate and photochemically inert clay and electron accepting methylviologen dications (MV2+). The inorganic nanosheets were obtained by exfoliation of layered hexaniobate and hectorite clay. The niobate and clay nanosheets were spatially separated in the colloidally dispersed state, and the MV2+ molecules were selectively adsorbed on the clay platelets. UV irradiation of the colloids led to electron transfer from the niobate nanosheets to the MV2+ molecules adsorbed on clay. The photoinduced electron transfer produced methylviologen radical cations (MV*+), which was characterized by high yield and long lifetime. The yield and stability of the MV*+ species were found to depend strongly on the clay content of the colloid: from a few mol % to approximately 70 mol % of the yield and several tens of minutes to more than 40 h of the lifetime. The contents of the niobate nanosheets and MV2+ molecules and the aging of the colloid also affected the photoinduced charge separation. In the absence of MV2+ molecules in the colloid, UV irradiation induced electron accumulation in the niobate nanosheets. The stability of the electron-accumulated state also depended on the clay content. The variation in the photochemical behavior is discussed in relation to the viscosity of the colloid.

Atomistic Time-Domain Simulations of Light-Harvesting and Charge-Transfer Dynamics in Novel Nanoscale Materials for Solar Hydrogen Production.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prezhdo, Oleg V.

2012-03-22

Funded by the DOE grant (i) we continued to study and analyze the atomistic detail of the electron transfer (ET) across the chromophore-TiO2 interface in Gratzel cell systems for solar hydrogen production. (ii) We extensively investigated the nature of photoexcited states and excited state dynamics in semiconductor quantum dots (QD) designed for photovoltaic applications. (iii) We continued a newly initiated research direction focusing on excited state properties and electron-phonon interactions in nanoscale carbon materials. Over the past year, the results of the DOE funded research were summarized in 3 review articles. 12 original manuscripts were written. The research results weremore » reported in 28 invited talks at conferences and university seminars. 20 invitations were accepted for talks in the near future. 2 symposia at national and international meetings have being organized this year on topics closely related to the DOE funded project, and 2 more symposia have been planned for the near future. We summarized the insights into photoinduced dynamics of semiconductor QDs, obtained from our time-domain ab initio studies. QDs exhibit both molecular and bulk properties. Unlike either bulk or molecular materials, QD properties can be modified continuously by changing QD shape and size. However, the chemical and physical properties of molecular and bulk materials often contradict each other, which can lead to differing viewpoints about the behavior of QDs. For example, the molecular view suggests strong electron-hole and charge-phonon interactions, as well as slow energy relaxation due to mismatch between electronic energy gaps and phonon frequencies. In contrast, the bulk view advocates that the kinetic energy of quantum confinement is greater than electron-hole interactions, that charge-phonon coupling is weak, and that the relaxation through quasi-continuous bands is rapid. By synthesizing the bulk and molecular viewpoints, we clarified the controversies and provided a unified atomistic picture of the nature and dynamics of photoexcited states in semiconductor QDs. We also summarized our recent findings about the photoinduced electron dynamics at the chromophore-semiconductor interfaces from a time-domain ab initio perspective. The interface provides the foundation for a new, promising type of solar cell and presents a fundamentally important case study for several fields, including photo-, electro- and analytical chemistries, molecular electronics, and photography. Further, the interface offers a classic example of an interaction between an organic molecular species and an inorganic bulk material. Scientists employ different concepts and terminologies to describe molecular and solid states of matter, and these differences make it difficult to describe the interface with a single model. At the basic atomistic level of description, however, this challenge can be largely overcome. Recent advances in non-adiabatic molecular dynamics and time-domain density functional theory have created a unique opportunity for simulating the ultrafast, photoinduced processes on a computer very similar to the way that they occur in nature. These state-of-the-art theoretical tools offered a comprehensive picture of a variety of electron transfer processes that occur at the interface, including electron injection from the chromophore to the semiconductor, electron relaxation and delocalization inside the semiconductor, back-transfer of the electron to the chromophore and to the electrolyte, and regeneration of the neutral chromophore by the electrolyte. The ab initio time-domain modeling is particularly valuable for understanding these dynamic features of the ultrafast electron transfer processes, which cannot be represented by a simple rate description. We demonstrated using symmetry adapted cluster theory with configuration interaction (SAC-CI) that charging of small PbSe nanocrystals (NCs) greatly modifies their electronic states and optical excitations. Conduction and valence band transitions that are not available in neutral NCs dominate low energy electronic excitations and show weak optical activity. At higher energies these transitions mix with both single excitons (SEs) and multiple excitons (MEs) associated with transitions across the band-gap. As a result, both SEs and MEs are significantly blue-shifted, and ME generation is drastically hampered. The overall contribution of MEs to the electronic excitations of the charged NCs is small even at very high energies. The calculations supported the recent view that the observed strong dependence of the ME yields on the experimental conditions is likely due to the effects of NC charging. The electron-hole excitonic nature of high energy states was investigated in neutral and charged Si clusters, motivated by the ME generation (MEG) process that is highly debated in photovoltaic literature.« less

Distance dependence in photoinduced intramolecular electron transfer. Additional remarks and calculations

NASA Astrophysics Data System (ADS)

Larsson, Sven; Volosov, Andrey

1987-12-01

Rate constants for photoinduced intramolecular electron transfer are calculated for four of the molecules studied by Hush et al. The electronic factor is obtained in quantum chemical calculations using the CNDO/S method. The results agree reasonably well with experiments for the forward reaction. Possible reasons for the disagreement for the charge recombination process are offered.

Ultrafast carrier dynamics in LT-GaAs doped with Si delta layers

NASA Astrophysics Data System (ADS)

Khusyainov, D. I.; Dekeyser, C.; Buryakov, A. M.; Mishina, E. D.; Galiev, G. B.; Klimov, E. A.; Pushkarev, S. S.; Klochkov, A. N.

2017-10-01

We characterized the ultrafast properties of LT-GaAs doped with silicon δ-layers and introduced delta-doping (δ-doping) as efficient method for enhancing the properties of GaAs-based structures which can be useful for terahertz (THz) antenna, ultrafast switches and other high frequency applications. Low temperature grown GaAs (LT-GaAs) became one of the most promising materials for ultrafast optical and THz devices due to its short carrier lifetime and high carrier mobility. Low temperature growth leads to a large number of point defects and an excess of arsenic. Annealing of LT-GaAs creates high resistivity through the formation of As-clusters, which appear due to the excess of arsenic. High resistivity is very important for THz antennas so that voltage can be applied without the risk of breakdown. With δ-Si doping, control of As-clusters is possible, since after annealing, clusters align in the plane where the δ-doping occurs. In this paper, we compare the properties of LT-GaAs-based planar structures with and without δ-Si doping and subsequent annealing. We used pump-probe transient reflectivity as a probe for ultrafast carrier dynamics in LT-GaAs. The results of the experiment were interpreted using the Ortiz model and show that the δ-Si doping increases deep donor and acceptor concentrations and decreases the photoinduced carrier lifetime as compared with LT-GaAs with same growth and annealing temperatures, but without doping.

Time-Domain Ab Initio Analysis of Excitation Dynamics in a Quantum Dot/Polymer Hybrid: Atomistic Description Rationalizes Experiment.

PubMed

Long, Run; Prezhdo, Oleg V

2015-07-08

Hybrid organic/inorganic polymer/quantum dot (QD) solar cells are an attractive alternative to the traditional cells. The original, simple models postulate that one-dimensional polymers have continuous energy levels, while zero-dimensional QDs exhibit atom-like electronic structure. A realistic, atomistic viewpoint provides an alternative description. Electronic states in polymers are molecule-like: finite in size and discrete in energy. QDs are composed of many atoms and have high, bulk-like densities of states. We employ ab initio time-domain simulation to model the experimentally observed ultrafast photoinduced dynamics in a QD/polymer hybrid and show that an atomistic description is essential for understanding the time-resolved experimental data. Both electron and hole transfers across the interface exhibit subpicosecond time scales. The interfacial processes are fast due to strong electronic donor-acceptor, as evidenced by the densities of the photoexcited states which are delocalized between the donor and the acceptor. The nonadiabatic charge-phonon coupling is also strong, especially in the polymer, resulting in rapid energy losses. The electron transfer from the polymer is notably faster than the hole transfer from the QD, due to a significantly higher density of acceptor states. The stronger molecule-like electronic and charge-phonon coupling in the polymer rationalizes why the electron-hole recombination inside the polymer is several orders of magnitude faster than in the QD. As a result, experiments exhibit multiple transfer times for the long-lived hole inside the QD, ranging from subpicoseconds to nanoseconds. In contrast, transfer of the short-lived electron inside the polymer does not occur beyond the first picosecond. The energy lost by the hole on its transit into the polymer is accommodated by polymer's high-frequency vibrations. The energy lost by the electron injected into the QD is accommodated primarily by much lower-frequency collective and QD modes. The electron dynamics is exponential, whereas evolution of the injected hole through the low density manifold of states of the polymer is highly nonexponential. The time scale of the electron-hole recombination at the interface is intermediate between those in pristine polymer and QD and is closer to that in the polymer. The detailed atomistic insights into the photoinduced charge and energy dynamics at the polymer/QD interface provide valuable guidelines for optimization of solar light harvesting and photovoltaic efficiency in modern nanoscale materials.

Photoinduced electron transfer in a ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C60 triad.

PubMed

Liu, Jian-Yong; El-Khouly, Mohamed E; Fukuzumi, Shunichi; Ng, Dennis K P

2012-06-04

A ferrocene-distyryl BODIPY dyad and a ferrocene-distyryl BODIPY-C(60) triad are synthesized and characterized. Upon photoexcitation at the distyryl BODIPY unit, these arrays undergo photoinduced electron transfer to form the corresponding charge-separated species. Based on their redox potentials, determined by cyclic voltammetry, the direction of the charge separation and the energies of these states are revealed. Femtosecond transient spectroscopic studies reveal that a fast charge separation (k(CS) =1.0×10(10) s(-1)) occurs for both the ferrocene-distyryl BODIPY dyad and the ferrocene-distyryl BODIPY-C(60) triad, but that a relatively slow charge recombination is observed only for the triad. The lifetime of the charge-separated state is 500 ps. Charge recombination of the dyad and triad leads to population of the triplet excited sate of ferrocene and the ground state, respectively. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploring Photoinduced Excited State Evolution in Heterobimetallic Ru(II)-Co(III) Complexes.

PubMed

Kuhar, Korina; Fredin, Lisa A; Persson, Petter

2015-06-18

Quantum chemical calculations provide detailed theoretical information concerning key aspects of photoinduced electron and excitation transfer processes in supramolecular donor-acceptor systems, which are particularly relevant to fundamental charge separation in emerging molecular approaches for solar energy conversion. Here we use density functional theory (DFT) calculations to explore the excited state landscape of heterobimetallic Ru-Co systems with varying degrees of interaction between the two metal centers, unbound, weakly bound, and tightly bound systems. The interplay between structural and electronic factors involved in various excited state relaxation processes is examined through full optimizations of multiple charge/spin states of each of the investigated systems. Low-energy relaxed heterobimetallic states of energy transfer and excitation transfer character are characterized in terms of energy, structure, and electronic properties. These findings support the notion of efficient photoinduced charge separation from a Ru(II)-Co(III) ground state, via initial optical excitation of the Ru-center, to low-energy Ru(III)-Co(II) states. The strongly coupled system has significant involvement of the conjugated bridge, qualitatively distinguishing it from the other two weakly coupled systems. Finally, by constructing potential energy surfaces for the three systems where all charge/spin state combinations are projected onto relevant reaction coordinates, excited state decay pathways are explored.

Terahertz emission from ultrafast spin and charge currents at a Rashba interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qi; Jungfleisch, Matthias B.; Zhang, Wei

2017-01-01

Abstract: We demonstrate the efficient single-cycle THz emission from a Rashba interface, i.e., Ag/Bi, in a spintronic heterostructure. Different from the previously reported inversed spin Hall effect mechanism in bulk systems, the observed ultrafast spin-to-charge conversion in a 2D Rashba interface is due to the inversed Rashba-Edelstein effect.

Spatial variation in carrier dynamics along a single CdSSe nanowire

NASA Astrophysics Data System (ADS)

Blake, Jolie C.; Eldridge, Peter S.; Gundlach, Lars

2014-10-01

Ultrafast charge carrier dynamics along individual CdSxSe1-x nanowires has been measured. The use of an improved ultrafast Kerr-gated microscope allows for spatially resolved luminescence measurements along a single nanowire. Amplified spontaneous emission (ASE) was observed at high excitation fluences. Position dependent variations of ultrafast ASE dynamics were observed. SEM and colorimetric measurements showed that the difference in dynamics can be attributed to variations in non-radiative recombination rates along the wire. The dominant Shockley-Read recombination rate can be extracted from ASE dynamics and can be directly related to charge carrier mobility and defect density. Employing ASE as a probe for defect densities provides a new sub-micron spatially resolved, contactless method for measurements of charge carrier mobility.

Photogeneration of Charge Carriers in Bilayer Assemblies of Conjugated Rigid-Rod Polymers

DTIC Science & Technology

1994-07-08

photoinduced electron transfer and exciplex formation at the bilayer interface. Thus photocarrier generation on photoexcitation of the conjugated rigid...rod polymers in the bilayer occurs by photoinduced electron transfer, forming intermolecular exciplexes which dissociate efficiently in electric field...photogeneration, conjugated rigid-rod polymers, is. MACI COD bilayer assemblies, electron transfer, exciplexes . 11. SEOJUTY CLASUICA 10. 51(11MIE CLASSIMIAVION

Time-dependent nonequilibrium soft x-ray response during a spin crossover

NASA Astrophysics Data System (ADS)

van Veenendaal, Michel

2018-03-01

A theoretical framework is developed for better understanding the time-dependent soft-x-ray response of dissipative quantum many-body systems. It is shown how x-ray absorption and resonant inelastic x-ray scattering (RIXS) at transition-metal L edges can provide insight into ultrafast intersystem crossings of importance for energy conversion, ultrafast magnetism, and catalysis. The photoinduced doublet-to-quartet spin crossover on cobalt in Fe-Co Prussian blue analogs is used as a model system to demonstrate how the x-ray response is affected by the nonequilibrium dynamics on a femtosecond time scale. Changes in local spin and symmetry and the underlying mechanism are reflected in strong broadenings, a collapse of clear selection rules during the intersystem crossing, fluctuations in the isotropic branching ratio in x-ray absorption, crystal-field collapse and/or oscillations, and time-dependent anti-Stokes processes in RIXS.

Conformational Dynamics Guides Coherent Exciton Migration in Conjugated Polymer Materials: First-Principles Quantum Dynamical Study

NASA Astrophysics Data System (ADS)

Binder, Robert; Lauvergnat, David; Burghardt, Irene

2018-06-01

We report on high-dimensional quantum dynamical simulations of photoinduced exciton migration in a single-chain oligothiophene segment, in view of elucidating the controversial nature of the elementary exciton transport steps in semiconducting polymers. A novel first-principles parametrized Frenkel J aggregate Hamiltonian is employed that goes significantly beyond the standard Frenkel-Holstein Hamiltonian. Departing from a nonequilibrium state created by photoexcitation, these simulations provide evidence of an ultrafast two-timescale process at low temperatures, involving exciton-polaron formation within tens of femtoseconds (fs), followed by torsional relaxation on an ˜400 fs timescale. The second step is the driving force for exciton migration, as initial conjugation breaks are removed by dynamical planarization. The quantum coherent nature of the elementary exciton migration step is consistent with experimental observations highlighting the correlated and vibrationally coherent nature of the dynamics on ultrafast timescales.

Conformational Dynamics Guides Coherent Exciton Migration in Conjugated Polymer Materials: First-Principles Quantum Dynamical Study.

PubMed

Binder, Robert; Lauvergnat, David; Burghardt, Irene

2018-06-01

We report on high-dimensional quantum dynamical simulations of photoinduced exciton migration in a single-chain oligothiophene segment, in view of elucidating the controversial nature of the elementary exciton transport steps in semiconducting polymers. A novel first-principles parametrized Frenkel J aggregate Hamiltonian is employed that goes significantly beyond the standard Frenkel-Holstein Hamiltonian. Departing from a nonequilibrium state created by photoexcitation, these simulations provide evidence of an ultrafast two-timescale process at low temperatures, involving exciton-polaron formation within tens of femtoseconds (fs), followed by torsional relaxation on an ∼400  fs timescale. The second step is the driving force for exciton migration, as initial conjugation breaks are removed by dynamical planarization. The quantum coherent nature of the elementary exciton migration step is consistent with experimental observations highlighting the correlated and vibrationally coherent nature of the dynamics on ultrafast timescales.

Ultrafast magnetization reversal by picosecond electrical pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yang; Wilson, Richard B.; Gorchon, Jon

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Ultrafast magnetization reversal by picosecond electrical pulses

DOE PAGES

Yang, Yang; Wilson, Richard B.; Gorchon, Jon; ...

2017-11-03

The field of spintronics involves the study of both spin and charge transport in solid-state devices. Ultrafast magnetism involves the use of femtosecond laser pulses to manipulate magnetic order on subpicosecond time scales. Here, we unite these phenomena by using picosecond charge current pulses to rapidly excite conduction electrons in magnetic metals. We observe deterministic, repeatable ultrafast reversal of the magnetization of a GdFeCo thin film with a single sub–10-ps electrical pulse. The magnetization reverses in ~10 ps, which is more than one order of magnitude faster than any other electrically controlled magnetic switching, and demonstrates a fundamentally new electricalmore » switching mechanism that does not require spin-polarized currents or spin-transfer/orbit torques. The energy density required for switching is low, projecting to only 4 fJ needed to switch a (20 nm) 3 cell. This discovery introduces a new field of research into ultrafast charge current–driven spintronic phenomena and devices.« less

Three-dimensional hollow graphene efficiently promotes electron transfer of Ag3PO4 for photocatalytically eliminating phenol

NASA Astrophysics Data System (ADS)

Song, Shaoqing; Meng, Aiyun; Jiang, Shujuan; Cheng, Bei

2018-06-01

The effective transport of photo-induced carriers over semiconductor photocatalyst is critical for enhancing the photocatalytic performance under light excitation. Although oxidized graphene (GO) and/or reduced graphene oxide (rGO) has been used as cocatalyst to promote the transfer and utilization of electrons, however, random diffusion and transfer of photo-induced charges are inevitable from all sides over these actual graphene owing to the limitation of the preparation process and theory. Herein, we utilized three-dimensional hollow carbon graphene (HCG) to promote the efficient electron transfer of Ag3PO4 in the photocatalytic process. Owing to the confinement-induced electron field of HCG, the constructed HCG-Ag3PO4 photocatalytic system demonstrated the enhanced visible-light adsorption, improved transfer of photo-induced charges, and suitable redox potentials as revealed by transient photo-current spectroscopic, surface photovoltage spectroscopy, and electron paramagnetic resonance (EPR). EPR spectra of oxygen species and gas chromatography-mass spectra exhibited high efficiency activity over HCG-Ag3PO4 with Z-scheme photocatalytic mechanism for phenol decomposition by reaction between hexanoic acid and radOH and radO2-. It is noteworthy that photocatalytic performance over optimal HCG-Ag3PO4 is 6, 3.43, 1.92 times of pristine Ag3PO4, GO-Ag3PO4, and rGO-Ag3PO4, respectively. The results may supply a novel perspective to enhance transfer of photo-induced charges for the promotion of photocatalytic technology.

Interlayer‐State‐Coupling Dependent Ultrafast Charge Transfer in MoS2/WS2 Bilayers

PubMed Central

Zhang, Jin; Hong, Hao; Lian, Chao; Ma, Wei; Xu, Xiaozhi; Zhou, Xu; Fu, Huixia

2017-01-01

Light‐induced interlayer ultrafast charge transfer in 2D heterostructures provides a new platform for optoelectronic and photovoltaic applications. The charge separation process is generally hypothesized to be dependent on the interlayer stackings and interactions, however, the quantitative characteristic and detailed mechanism remain elusive. Here, a systematical study on the interlayer charge transfer in model MoS2/WS2 bilayer system with variable stacking configurations by time‐dependent density functional theory methods is demonstrated. The results show that the slight change of interlayer geometry can significantly modulate the charge transfer time from 100 fs to 1 ps scale. Detailed analysis further reveals that the transfer rate in MoS2/WS2 bilayers is governed by the electronic coupling between specific interlayer states, rather than the interlayer distances, and follows a universal dependence on the state‐coupling strength. The results establish the interlayer stacking as an effective freedom to control ultrafast charge transfer dynamics in 2D heterostructures and facilitate their future applications in optoelectronics and light harvesting. PMID:28932669

X-ray imaging using amorphous selenium: a photoinduced discharge readout method for digital mammography.

PubMed

Rowlands, J A; Hunter, D M; Araj, N

1991-01-01

A new digital image readout method for electrostatic charge images on photoconductive plates is described. The method can be used to read out images on selenium plates similar to those used in xeromammography. The readout method, called the air-gap photoinduced discharge method (PID), discharges the latent image pixel by pixel and measures the charge. The PID readout method, like electrometer methods, is linear. However, the PID method permits much better resolution than scanning electrometers while maintaining quantum limited performance at high radiation exposure levels. Thus the air-gap PID method appears to be uniquely superior for high-resolution digital imaging tasks such as mammography.

Fabrication of highly efficient ZnO nanoscintillators

NASA Astrophysics Data System (ADS)

Procházková, Lenka; Gbur, Tomáš; Čuba, Václav; Jarý, Vítězslav; Nikl, Martin

2015-09-01

Photo-induced synthesis of high-efficiency ultrafast nanoparticle scintillators of ZnO was demonstrated. Controlled doping with Ga(III) and La(III) ions together with the optimized method of ZnO synthesis and subsequent two-step annealing in air and under reducing atmosphere allow to achieve very high intensity of UV exciton luminescence, up to 750% of BGO intensity magnitude. Fabricated nanoparticles feature extremely short sub-nanosecond photoluminescence decay times. Temperature dependence of the photoluminescence spectrum within 8-340 K range was investigated and shows the absence of visible defect-related emission within all temperature intervals.

Nonlinear nonlocal infrared plasmonic arrays for pump-probe studies on protein monolayers

NASA Astrophysics Data System (ADS)

Erramilli, Shyamsunder; Adato, Ronen; Gabel, Alan; Yanik, Ahmet Ali; Altug, Hatice; Hong, Mi K.

2010-03-01

Infrared spectroscopy is an exquisite bond-specific tool for studying biomolecules with characteristic vibrational normal modes that serve as a molecular ``fingerprint''. Intrinsic absorption cross-sections for proteins are significant (˜10-19 -10-21 cm^2), although small compared to label-based fluorescence methods. We have shown that carefully designed plasmonic nanoantenna arrays can enhance the vibrational signatures by ˜ 10^5 (Adato et al, Proc Natl Acad Sci USA, 2009). Theoretical modeling combined with polarized FTIR-microscopy show that enhancement is due both to localized effects and nonlocal collective effects, governed by the dielectric properties of silicon and gold nanoantennae, coupled to protein molecules. The resonance properties can be modulated by photoinduced excitation of charge carriers and excitons, causing both a shift in the resonance frequency and a change in the enhancement factor. An ultrafast visible pump laser can then be used to extend visible pump-infrared probe studies to protein molecules even when the molecules lack a chromophore. This provides a toolkit for biophysical studies in which the nonlinear, nonlocal interaction between a 35-fs visible or near-infrared laser and the designed plasmonic nanoantenna arrays are used to study dynamics of protein molecules.

Ultrafast giant magnetic cooling effect in ferromagnetic Co/Pt multilayers.

PubMed

Shim, Je-Ho; Ali Syed, Akbar; Kim, Chul-Hoon; Lee, Kyung Min; Park, Seung-Young; Jeong, Jong-Ryul; Kim, Dong-Hyun; Eon Kim, Dong

2017-10-06

The magnetic cooling effect originates from a large change in entropy by the forced magnetization alignment, which has long been considered to be utilized as an alternative environment-friendly cooling technology compared to conventional refrigeration. However, an ultimate timescale of the magnetic cooling effect has never been studied yet. Here, we report that a giant magnetic cooling (up to 200 K) phenomenon exists in the Co/Pt nano-multilayers on a femtosecond timescale during the photoinduced demagnetization and remagnetization, where the disordered spins are more rapidly aligned, and thus magnetically cooled, by the external magnetic field via the lattice-spin interaction in the multilayer system. These findings were obtained by the extensive analysis of time-resolved magneto-optical responses with systematic variation of laser fluence as well as external field strength and direction. Ultrafast giant magnetic cooling observed in the present study can enable a new avenue to the realization of ultrafast magnetic devices.The forced alignment of magnetic moments leads to a large change in entropy, which can be used to reduce the temperature of a material. Here, the authors show that this magnetic cooling effect occurs on a femtosecond time scale in cobalt-platinum nano-multilayers.

Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

NASA Astrophysics Data System (ADS)

Miaja-Avila, Luis; O'Neil, Galen C.; Joe, Young I.; Alpert, Bradley K.; Damrauer, Niels H.; Doriese, William B.; Fatur, Steven M.; Fowler, Joseph W.; Hilton, Gene C.; Jimenez, Ralph; Reintsema, Carl D.; Schmidt, Daniel R.; Silverman, Kevin L.; Swetz, Daniel S.; Tatsuno, Hideyuki; Ullom, Joel N.

2016-07-01

Experimental tools capable of monitoring both atomic and electronic structure on ultrafast (femtosecond to picosecond) time scales are needed for investigating photophysical processes fundamental to light harvesting, photocatalysis, energy and data storage, and optical display technologies. Time-resolved hard x-ray (>3 keV ) spectroscopies have proven valuable for these measurements due to their elemental specificity and sensitivity to geometric and electronic structures. Here, we present the first tabletop apparatus capable of performing time-resolved x-ray emission spectroscopy. The time resolution of the apparatus is better than 6 ps. By combining a compact laser-driven plasma source with a highly efficient array of microcalorimeter x-ray detectors, we are able to observe photoinduced spin changes in an archetypal polypyridyl iron complex [Fe (2 ,2'-bipyridine)3]2 + and accurately measure the lifetime of the quintet spin state. Our results demonstrate that ultrafast hard x-ray emission spectroscopy is no longer confined to large facilities and now can be performed in conventional laboratories with 10 times better time resolution than at synchrotrons. Our results are enabled, in part, by a 100- to 1000-fold increase in x-ray collection efficiency compared to current techniques.

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

DOE PAGES

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.; ...

2017-06-06

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si 0.25Ge 0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M 4,5-edge (~30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons acrossmore » the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔE gap,Ge,direct = 0.8 eV) and Si 0.25Ge 0.75 indirect gaps (ΔE gap,Si0.25Ge0.75,indirect = 0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si 0.25Ge 0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution.« less

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy† †Electronic supplementary information (ESI) available: Synthesis schemes, experimental methods, NMR spectra, X-ray crystallographic information, emission spectra, cyclic voltammetry, electronic structure calculations, data analysis and numerical methods, and other additional figures. CCDC 1561879. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04055e

PubMed Central

Kohler, Lars; Hadt, Ryan G.; Zhang, Xiaoyi; Liu, Cunming

2017-01-01

The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)–Ru(ii) analogs of the homodinuclear Cu(i)–Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations. PMID:29629153

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si 0.25Ge 0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M 4,5-edge (~30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons acrossmore » the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔE gap,Ge,direct = 0.8 eV) and Si 0.25Ge 0.75 indirect gaps (ΔE gap,Si0.25Ge0.75,indirect = 0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si 0.25Ge 0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution.« less

Hydrogen bonding effects on the reorganization energy for photoinduced charge separation reaction between porphyrin and quinone studied by nanosecond laser flash photolysis.

PubMed

Yago, Tomoaki; Gohdo, Masao; Wakasa, Masanobu

2010-02-25

Alcohol concentration dependences of photoinduced charge separation (CS) reaction of zinc tetraphenyl-porphyrin (ZnTPP) and duroquinone (DQ) were investigated in benzonitrile by a nanosecond laser flash photolysis technique. The photoinduced CS reaction was accelerated by the addition of alcohols, whereas the addition of acetonitrile caused little effect on the CS reactions. The simple theory was developed to calculate an increase in reorganization energies induced by the hydrogen bonding interactions between DQ and alcohols using the chemical equilibrium constants for the hydrogen bonding complexes through the concerted pathway and the stepwise one. The experimental results were analyzed by using the Marcus equation where we took into account the hydrogen bonding effects on the reorganization energy and the reaction free energy for the CS reaction. The observed alcohol concentration dependence of the CS reaction rates was well explained by the formation of the hydrogen bonding complexes through the concerted pathway, demonstrating the increase in the reorganization energy by the hydrogen bonding interactions.

Electron phonon couplings in 2D perovskite probed by ultrafast photoinduced absorption spectroscopy

NASA Astrophysics Data System (ADS)

Huynh, Uyen; Ni, Limeng; Rao, Akshay

We use the time-resolved photoinduced absorption (PIA) spectroscopy with 20fs time resolution to investigate the electron phonon coupling in the self-assembled hybrid organic layered perovskite, the hexyl ammonium lead iodide compound (C6H13NH3)2 (PbI4) . The coupling results in the broadening and asymmetry of its temperature-dependence photoluminescence spectra. The exact time scale of this coupling, however, wasn't reported experimentally. Here we show that using an ultrashort excitation pulse allows us to resolve from PIA kinetics the oscillation of coherent longitudinal optical phonons that relaxes and self-traps electrons to lower energy states within 200 fs. The 200fs relaxation time is equivalent to a coupling strength of 40meV. Two coupled phonon modes are also identified as about 100 cm-1 and 300 cm-1 from the FFT spectrum of the PIA kinetics. The lower energy mode is consistent with previous reports and Raman spectrum but the higher energy one hasn't been observed before.

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Preferential Charge Generation at Aggregate Sites in Narrow Band Gap Infrared Photoresponsive Polymer Semiconductors

DOE PAGES

Sulas, Dana B.; London, Alexander E.; Huang, Lifeng; ...

2018-02-13

Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub–picosecond singlet exciton lifetimes are measured in a structurally related series of infrared–absorbing copolymers that consist of alternating cyclopentadithiophene electron–rich “push” units and strong electron–deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC 71BM infrared photodetectorsmore » is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC 71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single–chain excitons unquenched. Lastly, the results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed.« less

Electron-nuclear corellations for photoinduced dynamics in molecular dimers

NASA Astrophysics Data System (ADS)

Kilin, Dmitri S.; Pereversev, Yuryi V.; Prezhdo, Oleg V.

2003-03-01

Ultrafast photoinduced dynamics of electronic excitation in molecular dimers is drastically affected by dynamic reorganization of of inter- and intra- molecular nuclear configuration modelled by quantized nuclear degree of freedom [1]. The dynamics of the electronic population and nuclear coherence is analyzed with help of both numerical solution of the chain of coupled differential equations for mean coordinate, population inversion, electronic-vibrational correlation etc.[2] and by propagating the Gaussian wavepackets in relevant adiabatic potentials. Intriguing results were obtained in the approximation of small energy difference and small change of nuclear equilibrium configuration for excited electronic states. In the limiting case of resonance between electronic states energy difference and frequency of the nuclear mode these results have been justified by comparison to exactly solvable Jaynes-Cummings model. It has been found that the photoinduced processes in dimer are arranged according to their time scales:(i) fast scale of nuclear motion,(ii) intermediate scale of dynamical redistribution of electronic population between excited states as well as growth and dynamics of electronic -nuclear correlation,(iii) slow scale of electronic population approaching to the quasiequilibrium distribution, decay of electronic-nuclear correlation, and diminishing the amplitude of mean coordinate oscillations, accompanied by essential growth of the nuclear coordinate dispersion associated with the overall nuclear wavepacket width. Demonstrated quantum-relaxational features of photoinduced vibronic dinamical processess in molecular dimers are obtained by simple method, applicable to large biological systems with many degrees of freedom. [1] J. A. Cina, D. S. Kilin, T. S. Humble, J. Chem. Phys. (2003) in press. [2] O. V. Prezhdo, J. Chem. Phys. 117, 2995 (2002).

Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces.

PubMed

Ravikumar, Abhilash; Kladnik, Gregor; Müller, Moritz; Cossaro, Albano; Bavdek, Gregor; Patera, Laerte L; Sánchez-Portal, Daniel; Venkataraman, Latha; Morgante, Alberto; Brivio, Gian Paolo; Cvetko, Dean; Fratesi, Guido

2018-05-03

We compare the ultrafast charge transfer dynamics of molecules on epitaxial graphene and bilayer graphene grown on Ni(111) interfaces through first principles calculations and X-ray resonant photoemission spectroscopy. We use 4,4'-bipyridine as a prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection of electrons from a substrate to a molecule on a femtosecond timescale. We show that the ultrafast injection of electrons from the substrate to the molecule is ∼4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces.

Photophysics of charge transfer in a polyfluorene/violanthrone blend

NASA Astrophysics Data System (ADS)

Cabanillas-Gonzalez, J.; Virgili, T.; Lanzani, G.; Yeates, S.; Ariu, M.; Nelson, J.; Bradley, D. D. C.

2005-01-01

We present a study of the photophysical and photovoltaic properties of blends of violanthrone in poly[9, 9-bis (2-ethylhexyl)-fluorene-2, 7-diyl ] (PF2/6) . Photoluminescence quenching and photocurrent measurements show moderate efficiencies for charge generation, characteristic of such polymer/dye blends. Pump-probe measurements on blend films suggest that while ˜47% of the total exciton population dissociates within 4ps of photoexcitation, only ˜32% subsequently results in the formation of dye anions. We attribute the discrepancy to the likely formation of complex species with long lifetimes, such as stabilized interface charge pairs or exciplexes. This conclusion is supported by the appearance of a long lifetime component of 2.4ns in the dynamics of the photoinduced absorption signal associated to polarons in photoinduced absorption bands centered at 560nm .

Augmenting Photoinduced Charge Transport in a Single-Component Gel System: Controlled In Situ Gel-Crystal Transformation at Room Temperature.

PubMed

Satapathy, Sitakanta; Prabakaran, Palani; Prasad, Edamana

2018-04-20

Smart single-component materials with versatile functions require pre-programming of a higher order molecular assembly. An electroactive supergelator (c=0.07 wt %) triphenylamine core-appended poly(aryl ether) dendron (TPAPAE) is described, where substantial dendritic effects improve the order and crystallinity by switching the local minima from self-assembled molecular wires to thermodynamically favorable global minima of ordered crystals, ripened within the fibers. Controlled in situ phase change at room temperature ultimately stabilized the mixed valence states in the single-component supramolecular assembly with photoluminescence and photoinduced charge transport amplified by two orders of magnitude. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

PubMed

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

NASA Astrophysics Data System (ADS)

Ponseca, C. S., Jr.; Sundström, V.

2016-03-01

Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

Charge Generation Dynamics in Efficient All-Polymer Solar Cells: Influence of Polymer Packing and Morphology.

PubMed

Gautam, Bhoj R; Lee, Changyeon; Younts, Robert; Lee, Wonho; Danilov, Evgeny; Kim, Bumjoon J; Gundogdu, Kenan

2015-12-23

All-polymer solar cells exhibit rapid progress in power conversion efficiency (PCE) from 2 to 7.7% over the past few years. While this improvement is primarily attributed to efficient charge transport and balanced mobility between the carriers, not much is known about the charge generation dynamics in these systems. Here we measured exciton relaxation and charge separation dynamics using ultrafast spectroscopy in polymer/polymer blends with different molecular packing and morphology. These measurements indicate that preferential face-on configuration with intermixed nanomorphology increases the charge generation efficiency. In fact, there is a direct quantitative correlation between the free charge population in the ultrafast time scales and the external quantum efficiency, suggesting not only the transport but also charge generation is key for the design of high performance all polymer solar cells.

Bunch evolution study in optimization of MeV ultrafast electron diffraction

NASA Astrophysics Data System (ADS)

Lu, Xian-Hai; Du, Ying-Chao; Huang, Wen-Hui; Tang, Chuan-Xiang

2014-12-01

Megaelectronvolt ultrafast electron diffraction (UED) is a promising detection tool for ultrafast processes. The quality of diffraction image is determined by the transverse evolution of the probe bunch. In this paper, we study the contributing terms of the emittance and space charge effects to the bunch evolution in the MeV UED scheme, employing a mean-field model with an ellipsoidal distribution as well as particle tracking simulation. The small transverse dimension of the drive laser is found to be critical to improve the reciprocal resolution, exploiting both smaller emittance and larger transverse bunch size before the solenoid. The degradation of the reciprocal spatial resolution caused by the space charge effects should be carefully controlled.

Structural Transformation of LiFePO4 during Ultrafast Delithiation.

PubMed

Kuss, Christian; Trinh, Ngoc Duc; Andjelic, Stefan; Saulnier, Mathieu; Dufresne, Eric M; Liang, Guoxian; Schougaard, Steen B

2017-12-21

The prolific lithium battery electrode material lithium iron phosphate (LiFePO 4 ) stores and releases lithium ions by undergoing a crystallographic phase change. Nevertheless, it performs unexpectedly well at high rate and exhibits good cycling stability. We investigate here the ultrafast charging reaction to resolve the underlying mechanism while avoiding the limitations of prevailing electrochemical methods by using a gaseous oxidant to deintercalate lithium from the LiFePO 4 structure. Oxidizing LiFePO 4 with nitrogen dioxide gas reveals structural changes through in situ synchrotron X-ray diffraction and electronic changes through in situ UV/vis reflectance spectroscopy. This study clearly shows that ultrahigh rates reaching 100% state of charge in 10 s does not lead to a particle-wide union of the olivine and heterosite structures. An extensive solid solution phase is therefore not a prerequisite for ultrafast charge/discharge.

Effect of Carrier Thermalization Dynamics on Light Emission and Amplification in Organometal Halide Perovskites.

PubMed

Chen, Kai; Barker, Alex J; Morgan, Francis L C; Halpert, Jonathan E; Hodgkiss, Justin M

2015-01-02

The remarkable rise of organometal halide perovskites as solar photovoltaic materials has been followed by promising developments in light-emitting devices, including lasers. Here we present unique insights into the processes leading to photon emission in these materials. We employ ultrafast broadband photoluminescence (PL) and transient absorption spectroscopies to directly link density dependent ultrafast charge dynamics to PL. We find that exceptionally strong PL at the band edge is preceded by thermalization of free charge carriers. Short-lived PL above the band gap is clear evidence of nonexcitonic emission from hot carriers, and ultrafast PL depolarization confirms that uncorrelated charge pairs are precursors to photon emission. Carrier thermalization has a profound effect on amplified stimulated emission at high fluence; the delayed onset of optical gain we resolve within the first 10 ps and the unusual oscillatory behavior are both consequences of the kinetic interplay between carrier thermalization and optical gain.

Structural Transformation of LiFePO 4 during Ultrafast Delithiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuss, Christian; Trinh, Ngoc Duc; Andjelic, Stefan

The prolific lithium battery electrode material lithium iron phosphate (LiFePO 4) stores and releases lithium ions by undergoing a crystallographic phase change. Nevertheless, it performs unexpectedly well at high rate and exhibits good cycling stability. Here we investigate here the ultrafast charging reaction to resolve the underlying mechanism while avoiding the limitations of prevailing electrochemical methods by using a gaseous oxidant to deintercalate lithium from the LiFePO 4 structure. Oxidizing LiFePO 4 with nitrogen dioxide gas reveals structural changes through in situ synchrotron X-ray diffraction and electronic changes through in situ UV/vis reflectance spectroscopy. This study clearly shows that ultrahighmore » rates reaching 100% state of charge in 10 s does not lead to a particle-wide union of the olivine and heterosite structures. An extensive solid solution phase is therefore not a prerequisite for ultrafast charge/discharge.« less

Structural Transformation of LiFePO 4 during Ultrafast Delithiation

DOE PAGES

Kuss, Christian; Trinh, Ngoc Duc; Andjelic, Stefan; ...

2017-12-05

The prolific lithium battery electrode material lithium iron phosphate (LiFePO 4) stores and releases lithium ions by undergoing a crystallographic phase change. Nevertheless, it performs unexpectedly well at high rate and exhibits good cycling stability. Here we investigate here the ultrafast charging reaction to resolve the underlying mechanism while avoiding the limitations of prevailing electrochemical methods by using a gaseous oxidant to deintercalate lithium from the LiFePO 4 structure. Oxidizing LiFePO 4 with nitrogen dioxide gas reveals structural changes through in situ synchrotron X-ray diffraction and electronic changes through in situ UV/vis reflectance spectroscopy. This study clearly shows that ultrahighmore » rates reaching 100% state of charge in 10 s does not lead to a particle-wide union of the olivine and heterosite structures. An extensive solid solution phase is therefore not a prerequisite for ultrafast charge/discharge.« less

Terahertz response in the quantum-Hall-effect regime of a quantum-well-based charge-sensitive infrared phototransistor

NASA Astrophysics Data System (ADS)

Nakagawa, Daisuke; Takizawa, Kazuhiro; Ikushima, Kenji; Kim, Sunmi; Patrashin, Mikhail; Hosako, Iwao; Komiyama, Susumu

2018-04-01

The characteristics of a charge-sensitive infrared phototransistor (CSIP) based on a GaAs/AlGaAs multiple quantum-well (QW) structure are studied under a magnetic field. In the CSIP, the upper QWs serve as a floating gate that is charged by photoexcitation. The photoinduced charges are detected using the resistance of the lowest QW conducting channel. The conducting channel exhibits the integer quantum Hall effect (QHE) in a perpendicular high magnetic field, yielding the magnetic field dependence of the terahertz (THz) response ΔR. We found two different features of ΔR. One is that ΔR switches sign across the QHE plateau, which is explained simply by an increased electron density in the conducting channel. The other feature is observed as an enhanced positive ΔR when a potential barrier is formed in the conducting channel. The latter mechanism can be interpreted as the promotion of edge/bulk scattering due to photoinduced charges. These findings suggest ways to enhance the THz response by using magnetic fields and potential barriers.

Development of a novel direct X-ray detector using photoinduced discharge (PID) readout for digital radiography

NASA Astrophysics Data System (ADS)

Heo, D.; Jeon, S.; Kim, J.-S.; Kim, R. K.; Cha, B. K.; Moon, B. J.; Yoon, J.

2013-02-01

We developed a novel direct X-ray detector using photoinduced discharge (PID) readout for digital radiography. The pixel resolution is 512 × 512 with 200 μm pixel and the overall active dimensions of the X-ray imaging panel is 10.24 cm × 10.24 cm. The detector consists of an X-ray absorption layer of amorphous selenium, a charge accumulation layer of metal, and a PID readout layer of amorphous silicon. In particular, the charge accumulation is pixelated because image charges generated by X-ray should be stored pixel by pixel. Here the image charges, or holes, are recombined with electrons generated by the PID method. We used a 405 nm laser diode and cylindrical lens to make a line beam source with a width of 50 μm for PID readout, which generates charges for each pixel lines during the scan. We obtained spatial frequencies of about 1.0 lp/mm for the X-direction (lateral direction) and 0.9 lp/mm for the Y-direction (scanning direction) at 50% modulation transfer function.

Plastic Electronics and Optoelectronics: New Science and Technology from Soluble Semiconducting Polymers and Bulk Heterojunction Solar Cells Fabricated from Soluble Semiconducting Polymers

DTIC Science & Technology

2011-11-03

fundamental discovery of photoinduced ultrafast electron transfer from conjugated polymers to fullerenes . Many groups in the U.S., Europe and Asia are...electron transfer from conjugated polymers to fullerenes . Many groups in the U.S., Europe and Asia are now making important contributions. Nevertheless...This confirms that the middle curve in Fig. 1 utilizes the correct assumptions.          2ln 1 c heBPolymer HOMO Fullerene LUMOoc N

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

PubMed Central

Yang, Ding-Shyue; Baum, Peter; Zewail, Ahmed H.

2016-01-01

Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V−V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions. PMID:27376103

Ultrafast Light Switching of Ferromagnetism in EuSe

NASA Astrophysics Data System (ADS)

Henriques, A. B.; Gratens, X.; Usachev, P. A.; Chitta, V. A.; Springholz, G.

2018-05-01

We demonstrate that light resonant with the band gap forces the antiferromagnetic semiconductor EuSe to enter ferromagnetic alignment in the picosecond timescale. A photon generates an electron-hole pair, whose electron forms a supergiant spin polaron of magnetic moment of nearly 6000 Bohr magnetons. By increasing the light intensity, the whole of the illuminated region can be fully magnetized. The key to the novel large photoinduced magnetization mechanism is the huge enhancement of the magnetic susceptibility when both antiferromagnetic and ferromagnetic interactions are present in the material and are of nearly equal magnitude, as is the case in EuSe.

Picosecond absorption studies of photoinduced charge separation in polyelectrolyte bound aromatic chromophores

NASA Astrophysics Data System (ADS)

Shand, M. A.; Rodgers, M. A. J.; Webber, S. E.

1991-02-01

Picosecond absorption studies of photoinduced electron transfer between aromatic chromophores bound to polymethacrylic acid (P) and methylviologen (MV 2+ have been carried out in aqueous solution. The diphenylanthracene copolymer/viologen system at pH 2.8 shows the corresponding redox products DPA + rad and MV + rad arising from the singlet state of DPA with a forward rate constant of electron transfer of 2.6 × 10 9 s -1. At pH 9.0 the quenching of the S 1 state of DPA occurs with no charge separated products being observed. The pyrene copolymer shows no evidence of charge separated products at any pH in the range 2.8-9.0. It is proposed that the differences in the radical pair kinetics arise from differences in the degree of binding of the ground state complexes formed by the donor and acceptor species.

Inhomogeneity of the ultrafast insulator-to-metal transition dynamics of VO2.

PubMed

O'Callahan, Brian T; Jones, Andrew C; Hyung Park, Jae; Cobden, David H; Atkin, Joanna M; Raschke, Markus B

2015-04-21

The insulator-metal transition (IMT) of vanadium dioxide (VO2) has remained a long-standing challenge in correlated electron physics since its discovery five decades ago. Most interpretations of experimental observations have implicitly assumed a homogeneous material response. Here we reveal inhomogeneous behaviour of even individual VO2 microcrystals using pump-probe microscopy and nanoimaging. The timescales of the ultrafast IMT vary from 40±8 fs, that is, shorter than a suggested phonon bottleneck, to 200±20 fs, uncorrelated with crystal size, transition temperature and initial insulating structural phase, with average value similar to results from polycrystalline thin-film studies. In combination with the observed sensitive variations in the thermal nanodomain IMT behaviour, this suggests that the IMT is highly susceptible to local changes in, for example, doping, defects and strain. Our results suggest an electronic mechanism dominating the photoinduced IMT, but also highlight the difficulty to deduce microscopic mechanisms when the true intrinsic material response is yet unclear.

Ultrafast Band Engineering and Transient Spin Currents in Antiferromagnetic Oxides

NASA Astrophysics Data System (ADS)

Gu, Mingqiang; Rondinelli, James M.

2016-04-01

We report a dynamic structure and band engineering strategy with experimental protocols to induce indirect-to-direct band gap transitions and coherently oscillating pure spin-currents in three-dimensional antiferromagnets (AFM) using selective phononic excitations. In the Mott insulator LaTiO3, we show that a photo-induced nonequilibrium phonon mode amplitude destroys the spin and orbitally degenerate ground state, reduces the band gap by 160 meV and renormalizes the carrier masses. The time scale of this process is a few hundreds of femtoseconds. Then in the hole-doped correlated metallic titanate, we show how pure spin-currents can be achieved to yield spin-polarizations exceeding those observed in classic semiconductors. Last, we demonstrate the generality of the approach by applying it to the non-orbitally degenerate AFM CaMnO3. These results advance our understanding of electron-lattice interactions in structures out-of-equilibrium and establish a rational framework for designing dynamic phases that may be exploited in ultrafast optoelectronic and optospintronic devices.

Ultrafast Band Engineering and Transient Spin Currents in Antiferromagnetic Oxides.

PubMed

Gu, Mingqiang; Rondinelli, James M

2016-04-29

We report a dynamic structure and band engineering strategy with experimental protocols to induce indirect-to-direct band gap transitions and coherently oscillating pure spin-currents in three-dimensional antiferromagnets (AFM) using selective phononic excitations. In the Mott insulator LaTiO3, we show that a photo-induced nonequilibrium phonon mode amplitude destroys the spin and orbitally degenerate ground state, reduces the band gap by 160 meV and renormalizes the carrier masses. The time scale of this process is a few hundreds of femtoseconds. Then in the hole-doped correlated metallic titanate, we show how pure spin-currents can be achieved to yield spin-polarizations exceeding those observed in classic semiconductors. Last, we demonstrate the generality of the approach by applying it to the non-orbitally degenerate AFM CaMnO3. These results advance our understanding of electron-lattice interactions in structures out-of-equilibrium and establish a rational framework for designing dynamic phases that may be exploited in ultrafast optoelectronic and optospintronic devices.

Ultrafast diffraction conoscopy of the structural phase transition in VO2: Evidence of two lattice distortions

NASA Astrophysics Data System (ADS)

Kumar, Nardeep; Rúa, Armando; Fernández, Félix E.; Lysenko, Sergiy

2017-06-01

Photoinduced phase transitions in complex correlated systems occur very rapidly and involve the interplay between various electronic and lattice degrees of freedom. For these materials to be considered for practical applications, it is important to discover how their phase transitions take place. Here we use a novel ultrafast diffraction conoscopy technique to study the evolution of vanadium dioxide (VO2) from biaxial to uniaxial symmetry. A key finding in this study is an additional relaxation process through which the phase transition takes place. Our results show that the biaxial monoclinic crystal initially, within the first 100-300 fs, transforms to a transient biaxial crystal, and within the next 300-400 fs converts into a uniaxial rutile crystal. The characteristic times for these transitions depend on film morphology and are presumably altered by misfit strain. We take advantage of Landau phenomenology to describe the complex dynamics of VO2 phase transition in the femtosecond regime.

On the dynamical nature of the active center in a single-site photocatalyst visualized by 4D ultrafast electron microscopy

PubMed Central

Yoo, Byung-Kuk; Su, Zixue; Thomas, John Meurig; Zewail, Ahmed H.

2016-01-01

Understanding the dynamical nature of the catalytic active site embedded in complex systems at the atomic level is critical to developing efficient photocatalytic materials. Here, we report, using 4D ultrafast electron microscopy, the spatiotemporal behaviors of titanium and oxygen in a titanosilicate catalytic material. The observed changes in Bragg diffraction intensity with time at the specific lattice planes, and with a tilted geometry, provide the relaxation pathway: the Ti4+=O2− double bond transformation to a Ti3+−O1− single bond via the individual atomic displacements of the titanium and the apical oxygen. The dilation of the double bond is up to 0.8 Å and occurs on the femtosecond time scale. These findings suggest the direct catalytic involvement of the Ti3+−O1− local structure, the significance of nonthermal processes at the reactive site, and the efficient photo-induced electron transfer that plays a pivotal role in many photocatalytic reactions. PMID:26729878

Ultrafast band engineering and transient spin currents in antiferromagnetic oxides

DOE PAGES

Gu, Mingqiang; Rondinelli, James M.

2016-04-29

Here, we report a dynamic structure and band engineering strategy with experimental protocols to induce indirect-to-direct band gap transitions and coherently oscillating pure spin-currents in three-dimensional antiferromagnets (AFM) using selective phononic excitations. In the Mott insulator LaTiO 3, we show that a photo-induced nonequilibrium phonon mode amplitude destroys the spin and orbitally degenerate ground state, reduces the band gap by 160 meV and renormalizes the carrier masses. The time scale of this process is a few hundreds of femtoseconds. Then in the hole-doped correlated metallic titanate, we show how pure spin-currents can be achieved to yield spin-polarizations exceeding those observedmore » in classic semiconductors. Last, we demonstrate the generality of the approach by applying it to the non-orbitally degenerate AFM CaMnO 3. These results advance our understanding of electron-lattice interactions in structures out-of-equilibrium and establish a rational framework for designing dynamic phases that may be exploited in ultrafast optoelectronic and optospintronic devices.« less

Ultrafast Band Engineering and Transient Spin Currents in Antiferromagnetic Oxides

PubMed Central

Gu, Mingqiang; Rondinelli, James M.

2016-01-01

We report a dynamic structure and band engineering strategy with experimental protocols to induce indirect-to-direct band gap transitions and coherently oscillating pure spin-currents in three-dimensional antiferromagnets (AFM) using selective phononic excitations. In the Mott insulator LaTiO3, we show that a photo-induced nonequilibrium phonon mode amplitude destroys the spin and orbitally degenerate ground state, reduces the band gap by 160 meV and renormalizes the carrier masses. The time scale of this process is a few hundreds of femtoseconds. Then in the hole-doped correlated metallic titanate, we show how pure spin-currents can be achieved to yield spin-polarizations exceeding those observed in classic semiconductors. Last, we demonstrate the generality of the approach by applying it to the non-orbitally degenerate AFM CaMnO3. These results advance our understanding of electron-lattice interactions in structures out-of-equilibrium and establish a rational framework for designing dynamic phases that may be exploited in ultrafast optoelectronic and optospintronic devices. PMID:27126354

Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott–Hubbard material

DOE PAGES

Lantz, G.; Mansart, B.; Grieger, D.; ...

2017-01-09

Photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behavior, including non-thermal phases and photoinduced phase transitions. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states of matter inaccessible by quasi-adiabatic pathways. We present a study of the ultrafast non-equilibrium evolution of the prototype Mott-Hubbard material V 2O 3, which presents a transient non-thermal phase developing immediately after photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configurationmore » is triggered by the excitation of electrons into the bonding a 1g orbital, and is then stabilized by a lattice distortion characterized by a marked hardening of the A 1g coherent phonon. Furthermore, this configuration is in stark contrast with the thermally accessible ones - the A 1g phonon frequency actually softens when heating the material. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are of particular relevance for the optical manipulation of strongly correlated systems, whose electronic and structural properties are often strongly intertwinned.« less

Ultrafast evolution and transient phases of a prototype out-of-equilibrium Mott–Hubbard material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lantz, G.; Mansart, B.; Grieger, D.

Photoexcited strongly correlated materials is attracting growing interest since their rich phase diagram often translates into an equally rich out-of-equilibrium behavior, including non-thermal phases and photoinduced phase transitions. With femtosecond optical pulses, electronic and lattice degrees of freedom can be transiently decoupled, giving the opportunity of stabilizing new states of matter inaccessible by quasi-adiabatic pathways. We present a study of the ultrafast non-equilibrium evolution of the prototype Mott-Hubbard material V 2O 3, which presents a transient non-thermal phase developing immediately after photoexcitation and lasting few picoseconds. For both the insulating and the metallic phase, the formation of the transient configurationmore » is triggered by the excitation of electrons into the bonding a 1g orbital, and is then stabilized by a lattice distortion characterized by a marked hardening of the A 1g coherent phonon. Furthermore, this configuration is in stark contrast with the thermally accessible ones - the A 1g phonon frequency actually softens when heating the material. Our results show the importance of selective electron-lattice interplay for the ultrafast control of material parameters, and are of particular relevance for the optical manipulation of strongly correlated systems, whose electronic and structural properties are often strongly intertwinned.« less

Ultrafast electron-lattice coupling dynamics in VO2 and V2O3 thin films

NASA Astrophysics Data System (ADS)

Abreu, Elsa; Gilbert Corder, Stephanie N.; Yun, Sun Jin; Wang, Siming; Ramírez, Juan Gabriel; West, Kevin; Zhang, Jingdi; Kittiwatanakul, Salinporn; Schuller, Ivan K.; Lu, Jiwei; Wolf, Stuart A.; Kim, Hyun-Tak; Liu, Mengkun; Averitt, Richard D.

2017-09-01

Ultrafast optical pump-optical probe and optical pump-terahertz probe spectroscopy were performed on vanadium dioxide (VO2) and vanadium sesquioxide (V2O3 ) thin films over a wide temperature range. A comparison of the experimental data from these two different techniques and two different vanadium oxides, in particular a comparison of the spectral weight oscillations generated by the photoinduced longitudinal acoustic modulation, reveals the strong electron-phonon coupling that exists in both materials. The low-energy Drude response of V2O3 appears more amenable than VO2 to ultrafast strain control. Additionally, our results provide a measurement of the temperature dependence of the sound velocity in both systems, revealing a four- to fivefold increase in VO2 and a three- to fivefold increase in V2O3 across the insulator-to-metal phase transition. Our data also confirm observations of strong damping and phonon anharmonicity in the metallic phase of VO2, and suggest that a similar phenomenon might be at play in the metallic phase of V2O3 . More generally, our simple table-top approach provides relevant and detailed information about dynamical lattice properties of vanadium oxides, paving the way to similar studies in other complex materials.

Correlating electronic and vibrational motions in charge transfer systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khalil, Munira

2014-06-27

The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

Probing ultrafast changes of spin and charge density profiles with resonant XUV magnetic reflectivity at the free-electron laser FERMI.

PubMed

Gutt, C; Sant, T; Ksenzov, D; Capotondi, F; Pedersoli, E; Raimondi, L; Nikolov, I P; Kiskinova, M; Jaiswal, S; Jakob, G; Kläui, M; Zabel, H; Pietsch, U

2017-09-01

We report the results of resonant magnetic XUV reflectivity experiments performed at the XUV free-electron laser FERMI. Circularly polarized XUV light with the photon energy tuned to the Fe M 2,3 edge is used to measure resonant magnetic reflectivities and the corresponding Q -resolved asymmetry of a Permalloy/Ta/Permalloy trilayer film. The asymmetry exhibits ultrafast changes on 240 fs time scales upon pumping with ultrashort IR laser pulses. Depending on the value of the wavevector transfer Q z , we observe both decreasing and increasing values of the asymmetry parameter, which is attributed to ultrafast changes in the vertical spin and charge density profiles of the trilayer film.

Evidence for a Peierls phase-transition in a three-dimensional multiple charge-density waves solid

PubMed Central

Mansart, Barbara; Cottet, Mathieu J. G.; Penfold, Thomas J.; Dugdale, Stephen B.; Tediosi, Riccardo; Chergui, Majed; Carbone, Fabrizio

2012-01-01

The effect of dimensionality on materials properties has become strikingly evident with the recent discovery of graphene. Charge ordering phenomena can be induced in one dimension by periodic distortions of a material’s crystal structure, termed Peierls ordering transition. Charge-density waves can also be induced in solids by strong coulomb repulsion between carriers, and at the extreme limit, Wigner predicted that crystallization itself can be induced in an electrons gas in free space close to the absolute zero of temperature. Similar phenomena are observed also in higher dimensions, but the microscopic description of the corresponding phase transition is often controversial, and remains an open field of research for fundamental physics. Here, we photoinduce the melting of the charge ordering in a complex three-dimensional solid and monitor the consequent charge redistribution by probing the optical response over a broad spectral range with ultrashort laser pulses. Although the photoinduced electronic temperature far exceeds the critical value, the charge-density wave is preserved until the lattice is sufficiently distorted to induce the phase transition. Combining this result with ab initio electronic structure calculations, we identified the Peierls origin of multiple charge-density waves in a three-dimensional system for the first time. PMID:22451898

Coherent control of alkali cluster fragmentation dynamics

NASA Astrophysics Data System (ADS)

Lindinger, Albrecht; Lupulescu, Cosmin; Bartelt, Andreas; Vajda, Štefan; Wöste, Ludger

2003-06-01

Metal clusters exhibit extraordinary chemical and catalytic properties, which sensitively depend upon their size. This behavior makes them interesting candidates for the real-time analysis of ultrafast photo-induced processes—ultimately leading to coherent control scenarii. We have performed transient multi-photon ionization experiments on small alkali clusters of different size in order to probe their wave packet dynamics, structural reorientations, charge transfers and dissociative events in different vibrationally excited electronic states including their ground state. The observed processes were highly dependent on the irradiated pulse parameters, like its phase, amplitude and duration; an emphasis to employ a feedback control system for generating the optimum pulse shapes. Their spectral and temporal behavior reflects interesting properties about the investigated system and the irradiated photochemical process. We present first the vibrational dynamics of bound, dissociated, and pre-dissociated electronically excited states of alkali dimers and trimers. The scheme for observing the wave packet dynamics in the electronic ground state using stimulated Raman-pumping is shown. Since the employed pulse parameters significantly influence the efficiency of the irradiated dynamic pathways photo-induced fragmentation experiments on bifurcating reaction channels were carried out. In these experiments different branching ionization and fragmentation pathways of electronically excited Na 2K were investigated. By employing an evolutionary algorithm for optimizing the phase and amplitude of the applied laser field, the yield of the resulting parent or fragment ions could significantly be influenced and interesting features could be concluded from the obtained optimum pulse shapes revealing the characteristic molecular oscillation period. Moreover, the influence on the optimal pulse shape due to fragmentation from larger clusters into NaK is obtained. The substructure of the optimal pulse shape thereby offers new insight into the fragmentation channel during the control process. Characteristic motions of the involved wave packets are proposed, in order to explain the optimized dynamic dissociation pathways.

Amplitude-Mode Spectroscopy of Charge Excitations in PTB7 π -Conjugated Donor-Acceptor Copolymer for Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Baniya, Sangita; Vardeny, Shai R.; Lafalce, Evan; Peygambarian, Nasser; Vardeny, Z. Valy

2017-06-01

We measure the spectra of resonant Raman scattering and doping-induced absorption of pristine films of the π -conjugated donor-acceptor (D -A ) copolymer, namely, thieno[3,4 b]thiophene-alt-benzodithiophene (PTB7), as well as photoinduced absorption spectrum in a blend of PTB7 with fullerene phenyl-C61-butyric acid methyl ester molecules used for organic photovoltaic (OPV) applications. We find that the D -A copolymer contains six strongly coupled vibrational modes having relatively strong Raman-scattering intensity, which are renormalized upon adding charge polarons onto the copolymer chains either by doping or photogeneration. Since the lower-energy charge-polaron absorption band overlaps with the renormalized vibrational modes, they appear as antiresonance lines superposed onto the induced polaron absorption band in the photoinduced absorption spectrum but less so in the doping-induced absorption spectrum. We show that the Raman-scattering, doping-, and photoinduced absorption spectra of PTB7 are well explained by the amplitude mode model, where a single vibrational propagator describes the renormalized modes and their related intensities in detail. From the relative strengths of the induced infrared activity of the polaron-related vibrations and electronic transitions, we obtain the polaron effective kinetic mass in PTB7 using the amplitude mode model to be approximately 3.8 m* , where m* is the electron effective mass. The enhanced polaronic mass in PTB7 may limit the charge mobility, which, in turn, reduces the OPV solar-cell efficiency based on the PTB7-fullerene blend.

Photoinduced charge transfer from vacuum-deposited molecules to single-layer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Osada, Kazuki; Tanaka, Masatoshi; Ohno, Shinya; Suzuki, Takanori

2016-06-01

Variations of photoluminescence (PL) and Raman spectra of single-layer MoS2, MoSe2, WS2, and WSe2 due to the vacuum deposition of C60 or copper phthalocyanine (CuPc) molecules have been investigated. PL spectra are decomposed into two competitive components, an exciton and a charged exciton (trion), depending on carrier density. The variation of PL spectra is interpreted in terms of charge transfer across the interfaces between transition metal dichalcogenides (TMDs) and dopant molecules. We find that deposited C60 molecules inject photoexcited electrons into MoS2, MoSe2, and WS2 or holes into WSe2. CuPc molecules also inject electrons into MoS2, MoSe2, and WS2, while holes are depleted from WSe2 to CuPc. We then propose a band alignment between TMDs and dopant molecules. Peak shifts of Raman spectra and doped carrier density estimated using a three-level model also support the band alignment. We thus demonstrate photoinduced charge transfer from dopant molecules to single-layer TMDs.

The ultrafast dynamics and conductivity of photoexcited graphene at different Fermi energies

PubMed Central

Turchinovich, Dmitry; Kläui, Mathias; Hendry, Euan; Polini, Marco

2018-01-01

For many of the envisioned optoelectronic applications of graphene, it is crucial to understand the subpicosecond carrier dynamics immediately following photoexcitation and the effect of photoexcitation on the electrical conductivity—the photoconductivity. Whereas these topics have been studied using various ultrafast experiments and theoretical approaches, controversial and incomplete explanations concerning the sign of the photoconductivity, the occurrence and significance of the creation of additional electron-hole pairs, and, in particular, how the relevant processes depend on Fermi energy have been put forward. We present a unified and intuitive physical picture of the ultrafast carrier dynamics and the photoconductivity, combining optical pump–terahertz probe measurements on a gate-tunable graphene device, with numerical calculations using the Boltzmann equation. We distinguish two types of ultrafast photo-induced carrier heating processes: At low (equilibrium) Fermi energy (EF ≲ 0.1 eV for our experiments), broadening of the carrier distribution involves interband transitions (interband heating). At higher Fermi energy (EF ≳ 0.15 eV), broadening of the carrier distribution involves intraband transitions (intraband heating). Under certain conditions, additional electron-hole pairs can be created [carrier multiplication (CM)] for low EF, and hot carriers (hot-CM) for higher EF. The resultant photoconductivity is positive (negative) for low (high) EF, which in our physical picture, is explained using solely electronic effects: It follows from the effect of the heated carrier distributions on the screening of impurities, consistent with the DC conductivity being mostly due to impurity scattering. The importance of these insights is highlighted by a discussion of the implications for graphene photodetector applications. PMID:29756035

Multiobjective optimizations of a novel cryocooled dc gun based ultrafast electron diffraction beam line

NASA Astrophysics Data System (ADS)

Gulliford, Colwyn; Bartnik, Adam; Bazarov, Ivan

2016-09-01

We present the results of multiobjective genetic algorithm optimizations of a single-shot ultrafast electron diffraction beam line utilizing a 225 kV dc gun with a novel cryocooled photocathode system and buncher cavity. Optimizations of the transverse projected emittance as a function of bunch charge are presented and discussed in terms of the scaling laws derived in the charge saturation limit. Additionally, optimization of the transverse coherence length as a function of final rms bunch length at the sample location have been performed for three different sample radii: 50, 100, and 200 μ m , for two final bunch charges: 1 05 electrons (16 fC) and 1 06 electrons (160 fC). Example optimal solutions are analyzed, and the effects of disordered induced heating estimated. In particular, a relative coherence length of Lc ,x/σx=0.27 nm /μ m was obtained for a final bunch charge of 1 05 electrons and final bunch length of σt≈100 fs . For a final charge of 1 06 electrons the cryogun produces Lc ,x/σx≈0.1 nm /μ m for σt≈100 - 200 fs and σx≥50 μ m . These results demonstrate the viability of using genetic algorithms in the design and operation of ultrafast electron diffraction beam lines.

Is back-electron transfer process in Betaine-30 coherent?

NASA Astrophysics Data System (ADS)

Rafiq, Shahnawaz; Scholes, Gregory D.

2017-09-01

The possible role of coherent vibrational motion in ultrafast photo-induced electron transfer remains unclear despite considerable experimental and theoretical advances. We revisited this problem by tracking the back-electron transfer (bET) process in Betaine-30 with broadband pump-probe spectroscopy. Dephasing time constant of certain high-frequency vibrations as a function of solvent shows a trend similar to the ET rates. In the purview of Bixon-Jortner model, high-frequency quantum vibrations bridge the reactant-product energy gap by providing activationless vibronic channels. Such interaction reduces the effective coupling significantly and thereby the coherence effects are eliminated due to energy gap fluctuations, making the back-electron transfer incoherent.

Ultrafast molecular processes mapped by femtosecond x-ray diffraction

NASA Astrophysics Data System (ADS)

Elsaesser, Thomas

2012-02-01

X-ray diffraction with a femtosecond time resolution allows for mapping photoinduced structural dynamics on the length scale of a chemical bond and in the time domain of atomic and molecular motion. In a pump-probe approach, a femtosecond excitation pulse induces structural changes which are probed by diffracting a femtosecond hard x-ray pulse from the excited sample. The transient angular positions and intensities of diffraction peaks give insight into the momentary atomic or molecular positions and into the distribution of electronic charge density. The simultaneous measurement of changes on different diffraction peaks is essential for determining atom positions and charge density maps with high accuracy. Recent progress in the generation of ultrashort hard x-ray pulses (Cu Kα, wavelength λ=0.154 nm) in laser-driven plasma sources has led to the implementation of the powder diffraction and the rotating crystal method with a time resolution of 100 fs. In this contribution, we report new results from powder diffraction studies of molecular materials. A first series of experiments gives evidence of a so far unknown concerted transfer of electrons and protons in ammonium sulfate [(NH4)2SO4], a centrosymmetric structure. Charge transfer from the sulfate groups results in the sub-100 fs generation of a confined electron channel along the c-axis of the unit cell which is stabilized by transferring protons from the adjacent ammonium groups into the channel. Time-dependent charge density maps display a periodic modulation of the channel's charge density by low-frequency lattice motions with a concerted electron and proton motion between the channel and the initial proton binding site. A second study addresses atomic rearrangements and charge dislocations in the non-centrosymmetric potassium dihydrogen phosphate [KH2PO4, KDP]. Photoexcitation generates coherent low-frequency motions along the LO and TO phonon coordinates, leaving the average atomic positions unchanged. The time-dependent maps of electron density demonstrate a concomitant oscillatory relocation of electronic charge with a spatial amplitude of the order of a chemical bond length, two orders of magnitude larger than the vibrational amplitudes. The coherent phonon motions drive the charge relocation, similar to a soft mode driven phase transition between the ferro- and paraelectric phase of KDP.

Facile synthesis of bismuth oxyhalide nanosheet films with distinct conduction type and photo-induced charge carrier behavior

NASA Astrophysics Data System (ADS)

Jia, Huimin; He, Weiwei; Zhang, Beibei; Yao, Lei; Yang, Xiaokai; Zheng, Zhi

2018-05-01

A modified successive ionic layer adsorption and reaction (SILAR) method was developed to fabricate 2D ordered BiOX (X = CI, Br, I) nanosheet array films on FTO substrates at room temperature. The formation of BiOX films were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-vis absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). The semiconductor surface states determine the type of semiconductor. Although BiOCI, BiOBr and BiOI belong to the bismuth oxyhalide semiconductor family and possess similar crystal and electronic structures, they show different conductivity types due to their respective surface states. Mott-Schottky curve results demonstrate that the BiOCl and BiOI nanosheet arrays display n-type semiconductor properties, while the BiOBr films exhibit p-type semiconductor properties. Assisted by surface photovoltage (SPV) and transient photovoltage (TPV) techniques, the photoinduced charge transfer dynamics on the surface/interface of the BiOX/FTO nanosheet films were systematically and comparatively investigated. As revealed by the results, both the separation and transfer dynamics of the photo-induced carrier are influenced by film thickness.

Photoinduced discommensuration of the commensurate charge-density wave phase in 1 T -Ta S2

NASA Astrophysics Data System (ADS)

Tanimura, Katsumi

2018-06-01

The dynamics induced by femtosecond-laser excitation of the commensurate phase of the charge-density wave (CDW) in 1 T -Ta S2 have been studied using both time-resolved electron diffraction and the time-resolved spectroscopy of coherent-phonon dynamics. Electron diffraction results show that the commensurate CDW phase is transformed into a new phase with CDW order that is similar to the nearly commensurate phase with threshold-type transition rates; the threshold excitation density of 0.2 per 13 Ta atoms is evaluated. Coherent-phonon spectroscopy results show that, together with the amplitude mode of CDW with a frequency of 2.41 THz, two other modes with frequencies of 2.34 and 2.07 THz are excited in the photoexcited commensurate CDW phase over a timescale of several tens of picoseconds after excitation. Spectroscopic, temporal, and excitation-intensity dependent characteristics of the three coherent phonons reveal that a photoinduced decomposition of the commensurate CDW order into an ensemble of domains with different CDW orders is induced before the CDW-phase transition occurs. The physics underlying the photoinduced decomposition and evolution into discommensurations responsible for the CDW-order transformation are discussed.

Ultrafast electron microscopy: Instrument response from the single-electron to high bunch-charge regimes

NASA Astrophysics Data System (ADS)

Plemmons, Dayne A.; Flannigan, David J.

2017-09-01

We determine the instrument response of an ultrafast electron microscope equipped with a conventional thermionic electron gun and absent modifications beyond the optical ports. Using flat, graphite-encircled LaB6 cathodes, we image space-charge effects as a function of photoelectron-packet population and find that an applied Wehnelt bias has a negligible effect on the threshold levels (>103 electrons per pulse) but does appear to suppress blurring at the upper limits (∼105 electrons). Using plasma lensing, we determine the instrument-response time for 700-fs laser pulses and find that single-electron packets are laser limited (1 ps), while broadening occurs well below the space-charge limit.

Mapping momentum-dependent electron-phonon coupling and nonequilibrium phonon dynamics with ultrafast electron diffuse scattering

NASA Astrophysics Data System (ADS)

Stern, Mark J.; René de Cotret, Laurent P.; Otto, Martin R.; Chatelain, Robert P.; Boisvert, Jean-Philippe; Sutton, Mark; Siwick, Bradley J.

2018-04-01

Despite their fundamental role in determining material properties, detailed momentum-dependent information on the strength of electron-phonon and phonon-phonon coupling (EPC and PPC, respectively) across the entire Brillouin zone has remained elusive. Here we demonstrate that ultrafast electron diffuse scattering (UEDS) directly provides such information. By exploiting symmetry-based selection rules and time resolution, scattering from different phonon branches can be distinguished even without energy resolution. Using graphite as a model system, we show that UEDS patterns map the relative EPC and PPC strength through their profound sensitivity to photoinduced changes in phonon populations. We measure strong EPC to the K -point TO phonon of A1' symmetry (K -A1' ) and along the entire TO branch between Γ -K , not only to the Γ -E2 g phonon. We also determine that the subsequent phonon relaxation of these strongly coupled optical phonons involve three stages: decay via several identifiable channels to TA and LA phonons (1 -2 ps), intraband thermalization of the non-equilibrium TA/LA phonon populations (30 -40 ps) and interband relaxation of the TA/LA modes (115 ps). Combining UEDS with ultrafast angle-resolved photoelectron spectroscopy will yield a complete picture of the dynamics within and between electron and phonon subsystems, helping to unravel complex phases in which the intertwined nature of these systems has a strong influence on emergent properties.

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

Exciton versus free carrier photogeneration in organometal trihalide perovskites probed by broadband ultrafast polarization memory dynamics.

PubMed

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z Valy

2015-03-20

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH(3)NH(3)PbI(3) and CH(3)NH(3)PbI(1.1)Br(1.9) using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH(3)NH(3)PbI(3) with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH(3)NH(3)PbI(1.1)Br(1.9). Surprisingly, we also discovered in CH(3)NH(3)PbI(3), but not in CH(3)NH(3)PbI(1.1)Br(1.9), transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH(3)NH(3)PbI(3), D≈0.01  cm(2) s(-1).

Exciton versus Free Carrier Photogeneration in Organometal Trihalide Perovskites Probed by Broadband Ultrafast Polarization Memory Dynamics

NASA Astrophysics Data System (ADS)

Sheng, ChuanXiang; Zhang, Chuang; Zhai, Yaxin; Mielczarek, Kamil; Wang, Weiwei; Ma, Wanli; Zakhidov, Anvar; Vardeny, Z. Valy

2015-03-01

We studied the ultrafast transient response of photoexcitations in two hybrid organic-inorganic perovskite films used for high efficiency photovoltaic cells, namely, CH3NH3PbI3 and CH3NH3PbI1.1Br1.9 using polarized broadband pump-probe spectroscopy in the spectral range of 0.3-2.7 eV with 300 fs time resolution. For CH3NH3PbI3 with above-gap excitation we found both photogenerated carriers and excitons, but only carriers are photogenerated with below-gap excitation. In contrast, mainly excitons are photogenerated in CH3NH3PbI1.1Br1.9 . Surprisingly, we also discovered in CH3NH3PbI3 , but not in CH3NH3PbI1.1Br1.9 , transient photoinduced polarization memory for both excitons and photocarriers, which is also reflected in the steady state photoluminescence. From the polarization memory dynamics we obtained the excitons diffusion constant in CH3NH3PbI3 , D ≈0.01 cm2 s-1 .

Quantum simulation of ultrafast dynamics using trapped ultracold atoms.

PubMed

Senaratne, Ruwan; Rajagopal, Shankari V; Shimasaki, Toshihiko; Dotti, Peter E; Fujiwara, Kurt M; Singh, Kevin; Geiger, Zachary A; Weld, David M

2018-05-25

Ultrafast electronic dynamics are typically studied using pulsed lasers. Here we demonstrate a complementary experimental approach: quantum simulation of ultrafast dynamics using trapped ultracold atoms. Counter-intuitively, this technique emulates some of the fastest processes in atomic physics with some of the slowest, leading to a temporal magnification factor of up to 12 orders of magnitude. In these experiments, time-varying forces on neutral atoms in the ground state of a tunable optical trap emulate the electric fields of a pulsed laser acting on bound charged particles. We demonstrate the correspondence with ultrafast science by a sequence of experiments: nonlinear spectroscopy of a many-body bound state, control of the excitation spectrum by potential shaping, observation of sub-cycle unbinding dynamics during strong few-cycle pulses, and direct measurement of carrier-envelope phase dependence of the response to an ultrafast-equivalent pulse. These results establish cold-atom quantum simulation as a complementary tool for studying ultrafast dynamics.

Time-dependent mobility and recombination of the photoinduced charge carriers in conjugated polymer/fullerene bulk heterojunction solar cells

NASA Astrophysics Data System (ADS)

Mozer, A. J.; Dennler, G.; Sariciftci, N. S.; Westerling, M.; Pivrikas, A.; Österbacka, R.; Juška, G.

2005-07-01

Time-dependent mobility and recombination in the blend of poly[2-methoxy-5-(3,7-dimethyloctyloxy)-phenylene vinylene] (MDMO-PPV) and 1-(3-methoxycarbonyl)propyl-1-phenyl-(6,6)- C61 (PCBM) is studied simultaneously using the photoinduced charge carrier extraction by linearly increasing voltage technique. The charge carriers are photogenerated by a strongly absorbed, 3 ns laser flash, and extracted by the application of a reverse bias voltage pulse after an adjustable delay time (tdel) . It is found that the mobility of the extracted charge carriers decreases with increasing delay time, especially shortly after photoexcitation. The time-dependent mobility μ(t) is attributed to the energy relaxation of the charge carriers towards the tail states of the density of states distribution. A model based on a dispersive bimolecular recombination is formulated, which properly describes the concentration decay of the extracted charge carriers at all measured temperatures and concentrations. The calculated bimolecular recombination coefficient β(t) is also found to be time-dependent exhibiting a power law dependence as β(t)=β0t-(1-γ) with increasing slope (1-γ) with decreasing temperatures. The temperature dependence study reveals that both the mobility and recombination of the photogenerated charge carriers are thermally activated processes with activation energy in the range of 0.1 eV. Finally, the direct comparison of μ(t) and β(t) shows that the recombination of the long-lived charge carriers is controlled by diffusion.

Ultrafast Photodetection in the Quantum Wells of Single AlGaAs/GaAs-Based Nanowires.

PubMed

Erhard, N; Zenger, S; Morkötter, S; Rudolph, D; Weiss, M; Krenner, H J; Karl, H; Abstreiter, G; Finley, J J; Koblmüller, G; Holleitner, A W

2015-10-14

We investigate the ultrafast optoelectronic properties of single Al0.3Ga0.7As/GaAs core-shell nanowires. The nanowires contain GaAs-based quantum wells. For a resonant excitation of the quantum wells, we find a picosecond photocurrent which is consistent with an ultrafast lateral expansion of the photogenerated charge carriers. This Dember-effect does not occur for an excitation of the GaAs-based core of the nanowires. Instead, the core exhibits an ultrafast displacement current and a photothermoelectric current at the metal Schottky contacts. Our results uncover the optoelectronic dynamics in semiconductor core-shell nanowires comprising quantum wells, and they demonstrate the possibility to use the low-dimensional quantum well states therein for ultrafast photoswitches and photodetectors.

Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

PubMed

Flynn, Daniel C; Ramakrishna, Guda; Yang, Hai-Bo; Northrop, Brian H; Stang, Peter J; Goodson, Theodore

2010-02-03

New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling.

PubMed

Guzelturk, Burak; Belisle, Rebecca A; Smith, Matthew D; Bruening, Karsten; Prasanna, Rohit; Yuan, Yakun; Gopalan, Venkatraman; Tassone, Christopher J; Karunadasa, Hemamala I; McGehee, Michael D; Lindenberg, Aaron M

2018-03-01

Unusual photophysical properties of organic-inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3 NH 3 PbI 3 ) following photoexcitation, enabling an ultrafast probe of charge separation, hot-carrier transport, and carrier-lattice coupling under 1-sun-equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hot and band-edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot-carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz-frequency lattice distortions, associated with reorganizations of the lead-iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier-lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far-above-gap photoexcitation. This study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Terahertz Emission from Hybrid Perovskites Driven by Ultrafast Charge Separation and Strong Electron-Phonon Coupling

DOE PAGES

Guzelturk, Burak; Belisle, Rebecca A.; Smith, Matthew D.; ...

2018-01-23

Unusual photophysical properties of organic–inorganic hybrid perovskites have not only enabled exceptional performance in optoelectronic devices, but also led to debates on the nature of charge carriers in these materials. This study makes the first observation of intense terahertz (THz) emission from the hybrid perovskite methylammonium lead iodide (CH 3NH 3PbI 3) following photoexcitation, enabling an ultrafast probe of charge separation, hot–carrier transport, and carrier–lattice coupling under 1–sun–equivalent illumination conditions. Using this approach, the initial charge separation/transport in the hybrid perovskites is shown to be driven by diffusion and not by surface fields or intrinsic ferroelectricity. Diffusivities of the hotmore » and band–edge carriers along the surface normal direction are calculated by analyzing the emitted THz transients, with direct implications for hot–carrier device applications. Furthermore, photogenerated carriers are found to drive coherent terahertz–frequency lattice distortions, associated with reorganizations of the lead–iodide octahedra as well as coupled vibrations of the organic and inorganic sublattices. This strong and coherent carrier–lattice coupling is resolved on femtosecond timescales and found to be important both for resonant and far–above–gap photoexcitation. As a result, this study indicates that ultrafast lattice distortions play a key role in the initial processes associated with charge transport.« less

Conductive scanning probe microscopy of the semicontinuous gold film and its SERS enhancement toward two-step photo-induced charge transfer and effect of the supportive layer

NASA Astrophysics Data System (ADS)

Sinthiptharakoon, K.; Sapcharoenkun, C.; Nuntawong, N.; Duong, B.; Wutikhun, T.; Treetong, A.; Meemuk, B.; Kasamechonchung, P.; Klamchuen, A.

2018-05-01

The semicontinuous gold film, enabling various electronic applications including development of surface-enhanced Raman scattering (SERS) substrate, is investigated using conductive atomic force microscopy (CAFM) and Kelvin probe force microscopy (KPFM) to reveal and investigate local electronic characteristics potentially associated with SERS generation of the film material. Although the gold film fully covers the underlying silicon surface, CAFM results reveal that local conductivity of the film is not continuous with insulating nanoislands appearing throughout the surface due to incomplete film percolation. Our analysis also suggests the two-step photo-induced charge transfer (CT) play the dominant role in the enhancement of SERS intensity with strong contribution from free electrons of the silicon support. Silicon-to-gold charge transport is illustrated by KPFM results showing that Fermi level of the gold film is slightly inhomogeneous and far below the silicon conduction band. We propose that inhomogeneity of the film workfunction affecting chemical charge transfer between gold and Raman probe molecule is associated with the SERS intensity varying across the surface. These findings provide deeper understanding of charge transfer mechanism for SERS which can help in design and development of the semicontinuous gold film-based SERS substrate and other electronic applications.

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

DOE PAGES

Wang, Han; Bang, Junhyeok; Sun, Yiyang; ...

2016-05-10

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.« less

The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Han; Bang, Junhyeok; Sun, Yiyang

Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.« less

Photoinduced charge separation at polymer-fullerene interfaces of BHJ solar cells (Conference Presentation)

NASA Astrophysics Data System (ADS)

Poluektov, Oleg G.; Niklas, Jens; Mardis, Kristy

2016-09-01

While photovoltaic cells are highly promising man-made devices for direct solar energy utilization, a number of fundamental questions about how the organic bulk heterojunction cell enables efficient long-lived and long-range charge separation remain unanswered. These questions were address by employing an advanced suite of EPR spectroscopy in combination with DFT calculations to study mechanism of charge separation at the polymer-fullerene interfaces of photo-active BHJ. Observed charge delocalization in BHJ upon photoinduced ET is analogous to that in organic donor-acceptor material. This is an efficient mechanism of charge stabilization in photosynthetic assemblies. Time-resolved EPR spectra show a strong polarization pattern for all polymer-fullerene blends under study, which is caused by non-Boltzmann population of the electron spin energy levels in the radical pairs. The first observation of this phenomenon was reported in natural and artificial photosynthetic assemblies, and comparison with these systems allows us to better understand charge separation processes in OPVs. The spectral analysis presented here, in combination with DFT calculations, shows that CS processes in OPV materials are similar to that in organic photosynthetic systems. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC02-06CH11357 at Argonne National Laboratory.

Photoinduced High-Frequency Charge Oscillations in Dimerized Systems

NASA Astrophysics Data System (ADS)

Yonemitsu, Kenji

2018-04-01

Photoinduced charge dynamics in dimerized systems is studied on the basis of the exact diagonalization method and the time-dependent Schrödinger equation for a one-dimensional spinless-fermion model at half filling and a two-dimensional model for κ-(bis[ethylenedithio]tetrathiafulvalene)2X [κ-(BEDT-TTF)2X] at three-quarter filling. After the application of a one-cycle pulse of a specifically polarized electric field, the charge densities at half of the sites of the system oscillate in the same phase and those at the other half oscillate in the opposite phase. For weak fields, the Fourier transform of the time profile of the charge density at any site after photoexcitation has peaks for finite-sized systems that correspond to those of the steady-state optical conductivity spectrum. For strong fields, these peaks are suppressed and a new peak appears on the high-energy side, that is, the charge densities mainly oscillate with a single frequency, although the oscillation is eventually damped. In the two-dimensional case without intersite repulsion and in the one-dimensional case, this frequency corresponds to charge-transfer processes by which all the bonds connecting the two classes of sites are exploited. Thus, this oscillation behaves as an electronic breathing mode. The relevance of the new peak to a recently found reflectivity peak in κ-(BEDT-TTF)2X after photoexcitation is discussed.

Ultra-fast photon counting with a passive quenching silicon photomultiplier in the charge integration regime

NASA Astrophysics Data System (ADS)

Zhang, Guoqing; Lina, Liu

2018-02-01

An ultra-fast photon counting method is proposed based on the charge integration of output electrical pulses of passive quenching silicon photomultipliers (SiPMs). The results of the numerical analysis with actual parameters of SiPMs show that the maximum photon counting rate of a state-of-art passive quenching SiPM can reach ~THz levels which is much larger than that of the existing photon counting devices. The experimental procedure is proposed based on this method. This photon counting regime of SiPMs is promising in many fields such as large dynamic light power detection.

Ultrafast collinear scattering and carrier multiplication in graphene.

PubMed

Brida, D; Tomadin, A; Manzoni, C; Kim, Y J; Lombardo, A; Milana, S; Nair, R R; Novoselov, K S; Ferrari, A C; Cerullo, G; Polini, M

2013-01-01

Graphene is emerging as a viable alternative to conventional optoelectronic, plasmonic and nanophotonic materials. The interaction of light with charge carriers creates an out-of-equilibrium distribution, which relaxes on an ultrafast timescale to a hot Fermi-Dirac distribution, that subsequently cools emitting phonons. Although the slower relaxation mechanisms have been extensively investigated, the initial stages still pose a challenge. Experimentally, they defy the resolution of most pump-probe setups, due to the extremely fast sub-100 fs carrier dynamics. Theoretically, massless Dirac fermions represent a novel many-body problem, fundamentally different from Schrödinger fermions. Here we combine pump-probe spectroscopy with a microscopic theory to investigate electron-electron interactions during the early stages of relaxation. We identify the mechanisms controlling the ultrafast dynamics, in particular the role of collinear scattering. This gives rise to Auger processes, including charge multiplication, which is key in photovoltage generation and photodetectors.

Ultrafast studies of coexisting electronic order in cuprate superconductors

NASA Astrophysics Data System (ADS)

Hinton, James; Thewalt, Eric; Alpichshev, Zhanybek; Sternbach, Aaron; McLeod, Alex; Ji, L.; Veit, Mike; Dorrow, Chelsey; Koralek, Jake; Xhao, Xudong; Barisic, Neven; Kemper, Alexander; Gedik, Nuh; Greven, Martin; Basov, Dimitri; Orenstein, Joe

The cuprate family of high temperature superconductors displays a variety of electronic phases which emerge when charge carriers are added to the antiferromagnetic parent compound. These electronic phases are characterized by subtle differences in the low energy electronic excitations. Ultrafast time-resolved reflectivity (TRR) provides an ideal tool for investigating the cuprate phase diagram, as small changes in the electronic structure can produce significant contrast in the non-equilibrium reflectivity. Here we present TRR measurements of cuprate superconductors, focusing on the model single-layer cuprate HgBa2CuO4+δ. We observe a cusp-like feature in the quasiparticle lifetime near the superconducting transition temperature Tc. This feature can be understood using a model of coherently-mixed charge-density wave and superconducting pairing. We propose extending this technique to the nanoscale using ultrafast scattering scanning near-field microscopy (u-SNOM). This will allow us to explore how these electronic phases coexist and compete in real-space.

Exploring coherent electron excitation and migration dynamics by electron diffraction with ultrashort X-ray pulses.

PubMed

Yuan, Kai-Jun; Bandrauk, André D

2017-10-04

Exploring ultrafast charge migration is of great importance in biological and chemical reactions. We present a scheme to monitor attosecond charge migration in molecules by electron diffraction with spatial and temporal resolutions from ab initio numerical simulations. An ultraviolet pulse creates a coherent superposition of electronic states, after which a time-delayed attosecond X-ray pulse is used to ionize the molecule. It is found that diffraction patterns in the X-ray photoelectron spectra show an asymmetric structure, which is dependent on the time delay between the pump-probe pulses, encoding the information of molecular orbital symmetry and chemical bonding. We describe these phenomena by developing an electronic time-dependent ultrafast molecular photoionization model of a coherent superposition state. The periodical distortion of electron diffraction patterns illustrates the evolution of the electronic coherence, providing a tool for attosecond imaging of ultrafast molecular reaction processes.

Ultrafast photodimerization dynamics in α-cyano-4-hydroxycinnamic and sinapinic acid crystals

NASA Astrophysics Data System (ADS)

Hoyer, Theo; Tuszynski, Wilfried; Lienau, Christoph

2007-07-01

We report a sub-picosecond time-resolved fluorescence spectroscopic study of different cinnamic acid crystals, model systems for solid-state photodimerization reactions. For α-cyano-4-hydroxycinnamic acid (α-CHC), we identify the emission spectra of both monomers and dimers, allowing us to directly probe the photoinduced dynamics of both species. The dimerization occurs on a timescale of 10 ps and results in a long-lived dimer product, stable for hours. For sinapinic acid, we find an extremely fast, sub-picosecond dimerization reaction and a short-lived dimer. This first sub-picosecond time-resolved dimerization study in cinnamic acid crystals provides a new basis for relating their structural properties and microscopic reaction dynamics.

Ultrafast dynamics in co-sensitized photocatalysts under visible and NIR light irradiation.

PubMed

Patwari, Jayita; Chatterjee, Arka; Sardar, Samim; Lemmens, Peter; Pal, Samir Kumar

2018-04-18

Co-sensitization to achieve a broad absorption window is a widely accepted technique in light harvesting nanohybrid synthesis. Protoporphyrin (PPIX) and squaraine (SQ2) are two organic sensitizers absorbing in the visible and NIR wavelength regions of the solar spectrum, respectively. In the present study, we have sensitized zinc oxide (ZnO) nanoparticles using PPIX and SQ2 simultaneously for their potential use in broad-band solar light harvesting in photocatalysis. Förster resonance energy transfer (FRET) from PPIX to SQ2 in close proximity to the ZnO surface has been found to enhance visible light photocatalysis. In order to confirm the effect of intermolecular FRET in photocatalysis, the excited state lifetime of the energy donor dye PPIX has been modulated by inserting d10 (ZnII) and d7 (CoII) metal ions in the central position of the dye (PP(Zn) and PP(Co)). In the case of PP(Co)-SQ2, extensive photo-induced ligand to metal charge transfer counteracts the FRET efficiency while efficient FRET has been observed for the PP(Zn)-SQ2 pair. This observation has been justified by the comparison of the visible light photocatalysis of the respective nanohybrids with several control studies. We have also investigated the NIR photocatalysis of the co-sensitized nanohybrids which reveals that reduced aggregation of SQ2 due to co-sensitization of PPIX increases the NIR photocatalysis. However, core-metalation of PPIX reduces the NIR photocatalytic efficacy, most probably due to excited state charge transfer from SQ2 to the metal centre of PP(Co)/PP(Zn) through the conduction band of the host ZnO nanoparticles.

Ultrafast Electron Transfer Kinetics in the LM Dimer of Bacterial Photosynthetic Reaction Center from Rhodobacter sphaeroides.

PubMed

Sun, Chang; Carey, Anne-Marie; Gao, Bing-Rong; Wraight, Colin A; Woodbury, Neal W; Lin, Su

2016-06-23

It has become increasingly clear that dynamics plays a major role in the function of many protein systems. One system that has proven particularly facile for studying the effects of dynamics on protein-mediated chemistry is the bacterial photosynthetic reaction center from Rhodobacter sphaeroides. Previous experimental and computational analysis have suggested that the dynamics of the protein matrix surrounding the primary quinone acceptor, QA, may be particularly important in electron transfer involving this cofactor. One can substantially increase the flexibility of this region by removing one of the reaction center subunits, the H-subunit. Even with this large change in structure, photoinduced electron transfer to the quinone still takes place. To evaluate the effect of H-subunit removal on electron transfer to QA, we have compared the kinetics of electron transfer and associated spectral evolution for the LM dimer with that of the intact reaction center complex on picosecond to millisecond time scales. The transient absorption spectra associated with all measured electron transfer reactions are similar, with the exception of a broadening in the QX transition and a blue-shift in the QY transition bands of the special pair of bacteriochlorophylls (P) in the LM dimer. The kinetics of the electron transfer reactions not involving quinones are unaffected. There is, however, a 4-fold decrease in the electron transfer rate from the reduced bacteriopheophytin to QA in the LM dimer compared to the intact reaction center and a similar decrease in the recombination rate of the resulting charge-separated state (P(+)QA(-)). These results are consistent with the concept that the removal of the H-subunit results in increased flexibility in the region around the quinone and an associated shift in the reorganization energy associated with charge separation and recombination.

Photoinduced electron transfer in covalent ruthenium-anthraquinone dyads: relative importance of driving-force, solvent polarity, and donor-bridge energy gap.

PubMed

Hankache, Jihane; Wenger, Oliver S

2012-02-28

Four rigid rod-like molecules comprised of a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer, a 9,10-anthraquinone electron acceptor, and a molecular bridge connecting the two redox partners were synthesized and investigated by optical spectroscopic and electrochemical means. An attempt was made to assess the relative importance of driving-force, solvent polarity, and bridge variation on the rates of photoinduced electron transfer in these molecules. Expectedly, introduction of tert-butyl substituents in the bipyridine ligands of the ruthenium complex and a change in solvent from dichloromethane to acetonitrile lead to a significant acceleration of charge transfer rates. In dichloromethane, photoinduced electron transfer is not competitive with the inherent excited-state deactivation processes of the photosensitizer. In acetonitrile, an increase in driving-force by 0.2 eV through attachment of tert-butyl substituents to the bpy ancillary ligands causes an increase in electron transfer rates by an order of magnitude. Replacement of a p-xylene bridge by a p-dimethoxybenzene spacer entails an acceleration of charge transfer rates by a factor of 3.5. In the dyads from this study, the relative order of importance of individual influences on electron transfer rates is therefore as follows: solvent polarity ≥ driving-force > donor-bridge energy gap.

Photo-induced persistent inversion of germanium in a 200-nm-deep surface region.

PubMed

Prokscha, T; Chow, K H; Stilp, E; Suter, A; Luetkens, H; Morenzoni, E; Nieuwenhuys, G J; Salman, Z; Scheuermann, R

2013-01-01

The controlled manipulation of the charge carrier concentration in nanometer thin layers is the basis of current semiconductor technology and of fundamental importance for device applications. Here we show that it is possible to induce a persistent inversion from n- to p-type in a 200-nm-thick surface layer of a germanium wafer by illumination with white and blue light. We induce the inversion with a half-life of ~12 hours at a temperature of 220 K which disappears above 280 K. The photo-induced inversion is absent for a sample with a 20-nm-thick gold capping layer providing a Schottky barrier at the interface. This indicates that charge accumulation at the surface is essential to explain the observed inversion. The contactless change of carrier concentration is potentially interesting for device applications in opto-electronics where the gate electrode and gate oxide could be replaced by the semiconductor surface.

Inter-Fullerene Electronic Coupling Controls the Efficiency of Photoinduced Charge Generation in Organic Bulk Heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, Bryon W.; Reid, Obadiah G.; Coffey, David C.

2016-09-26

Photoinduced charge generation (PCG) dynamics are notoriously difficult to correlate with specific molecular properties in device relevant polymer:fullerene organic photovoltaic blend films due to the highly complex nature of the solid state blend morphology. Here, this study uses six judiciously selected trifluoromethylfullerenes blended with the prototypical polymer poly(3-hexylthiophene) and measure the PCG dynamics in 50 fs-500 ns time scales with time-resolved microwave conductivity and femtosecond transient absorption spectroscopy. The isomeric purity and thorough chemical characterization of the fullerenes used in this study allow for a detailed correlation between molecular properties, driving force, local intermolecular electronic coupling and, ultimately, the efficiencymore » of PCG yield. The findings show that the molecular design of the fullerene not only determines inter-fullerene electronic coupling, but also influences the decay dynamics of free holes in the donor phase even when the polymer microstructure remains unchanged.« less

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

PubMed

Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

2015-05-01

A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sessler, J. L.; Sathiosatham, M.; Brown, C. T.

The synthesis of a new, noncovalent anthracene-dimethylaniline dyad (ensemble I) held together via guanosine-cytidine Watson-Crick base-pairing interactions is reported. Upon excitation at 420 nm, photoinduced electron-transfer from the dimethylaniline donor to the singlet excited state of the anthracene acceptor occurs, as inferred from a combination of time-resolved fluorescence quenching and transient absorption measurements. In toluene at room temperature, the rate constants for photoinduced intraensemble electron-transfer and subsequent back-electron-transfer (charge recombination) are k{sub CS} = (3.5 {+-} 0.03) x 10{sup 10} s{sup -1} and k{sub CR} = (1.42 {+-} 0.03) x 10{sup 9} s{sup -1}, respectively.

Molecular packing and electronic processes in amorphous-like polymer bulk heterojunction solar cells with fullerene intercalation.

PubMed

Xiao, Ting; Xu, Haihua; Grancini, Giulia; Mai, Jiangquan; Petrozza, Annamaria; Jeng, U-Ser; Wang, Yan; Xin, Xin; Lu, Yong; Choon, Ng Siu; Xiao, Hu; Ong, Beng S; Lu, Xinhui; Zhao, Ni

2014-06-09

The interpenetrating morphology formed by the electron donor and acceptor materials is critical for the performance of polymer:fullerene bulk heterojunction (BHJ) photovoltaic (PV) cells. In this work we carried out a systematic investigation on a high PV efficiency (>6%) BHJ system consisting of a newly developed 5,6-difluorobenzo[c] thiadiazole-based copolymer, PFBT-T20TT, and a fullerene derivative. Grazing incidence X-ray scattering measurements reveal the lower-ordered nature of the BHJ system as well as an intermixing morphology with intercalation of fullerene molecules between the PFBT-T20TT lamella. Steady-state and transient photo-induced absorption spectroscopy reveal ultrafast charge transfer (CT) at the PFBT-T20TT/fullerene interface, indicating that the CT process is no longer limited by exciton diffusion. Furthermore, we extracted the hole mobility based on the space limited current (SCLC) model and found that more efficient hole transport is achieved in the PFBT-T20TT:fullerene BHJ as compared to pure PFBT-T20TT, showing a different trend as compared to the previously reported highly crystalline polymer:fullerene blend with a similar intercalation manner. Our study correlates the fullerene intercalated polymer lamella morphology with device performance and provides a coherent model to interpret the high photovoltaic performance of some of the recently developed weakly-ordered BHJ systems based on conjugated polymers with branched side-chain.

Photoinduced Dynamics and Toxicity of a Cancer Drug in Proximity of Inorganic Nanoparticles under Visible Light.

PubMed

Chaudhuri, Siddhi; Sardar, Samim; Bagchi, Damayanti; Dutta, Shreyasi; Debnath, Sushanta; Saha, Partha; Lemmens, Peter; Pal, Samir Kumar

2016-01-18

Drug sensitization with various inorganic nanoparticles (NPs) has proved to be a promising and an emergent concept in the field of nanomedicine. Rose bengal (RB), a notable photosensitizer, triggers the formation of reactive oxygen species under green-light irradiation, and consequently, it induces cytotoxicity and cell death. In the present study, the effect of photoinduced dynamics of RB upon complexation with semiconductor zinc oxide NPs is explored. To accomplish this, we successfully synthesized nanohybrids of RB with ZnO NPs with a particle size of 24 nm and optically characterized them. The uniform size and integrity of the particles were confirmed by high-resolution transmission electron microscopy. UV/Vis absorption and steady-state fluorescence studies reveal the formation of the nanohybrids. ultrafast picosecond-resolved fluorescence studies of RB-ZnO nanohybrids demonstrate an efficient electron transfer from the photoexcited drug to the semiconductor NPs. Picosecond-resolved Förster resonance energy transfer from ZnO NPs to RB unravel the proximity of the drug to the semiconductor at the molecular level. The photoinduced ROS formation was monitored using a dichlorofluorescin oxidation assay, which is a conventional oxidative stress indicator. It is observed that the ROS generation under green light illumination is greater at low concentrations of RB-ZnO nanohybrids compared with free RB. Substantial photodynamic activity of the nanohybrids in bacterial and fungal cell lines validated the in vitro toxicity results. Furthermore, the cytotoxic effect of the nanohybrids in HeLa cells, which was monitored by MTT assay, is also noteworthy. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking the coherent generation of polaron pairs in conjugated polymers

NASA Astrophysics Data System (ADS)

de Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita; Réhault, Julien; Sommer, Ephraim; Lim, James; Huelga, Susana F.; Plenio, Martin B.; Rozzi, Carlo Andrea; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

2016-12-01

The optical excitation of organic semiconductors not only generates charge-neutral electron-hole pairs (excitons), but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period peak oscillations persisting for up to about 1 ps as distinct signatures of vibronic quantum coherence at room temperature. The measured two-dimensional spectra show pronounced peak splittings revealing that the elementary optical excitations of this polymer are hybridized exciton-polaron-pairs, strongly coupled to a dominant underdamped vibrational mode. Coherent vibronic coupling induces ultrafast polaron pair formation, accelerates the charge separation dynamics and makes it insensitive to disorder. These findings open up new perspectives for tailoring light-to-current conversion in organic materials.

Polarization dependent photo-induced bias stress effect in organic transistors.

NASA Astrophysics Data System (ADS)

Podzorov, Vitaly; Choi, Hyun Ho; Najafov, Hikmet; Saranin, Danila; Kharlamov, Nikolai A.; Kuznetzov, Denis V.; Didenko, Sergei I.; Cho, Kilwon; Briseno, Alejandro L.; Rutgers-Misis Collaboration; Ru-P Collaboration; Ru-Um Collaboration; Um-P Collaboration

Photo-induced charge transfer between a semiconductor and a gate insulator that occurs in organic transistors operating under illumination leads to a shift of the onset gate voltage in these devices. Here we report an observation of a polarization dependent photo-induced bias-stress effect in two prototypical single-crystal organic field-effect transistors, based on rubrene and TPBIQ. We find that the rate of the effect is a periodic function of polarization angle of a linearly polarized photoexcitation, with a periodicity of π. The observed phenomenon provides an effective tool for addressing the relationship between molecular packing and parameter drift in organic transistors under illumination. The work was carried out with financial support from the Ministry of Education and Science of the Russian Federation in the framework of Increase Competitiveness Program of NUST «MISiS» (No. K3-2016-004), by gov. decree 16/03/2013, N 211.

Optical studies of native defects in π-conjugated donor-acceptor copolymers

NASA Astrophysics Data System (ADS)

Baniya, Sangita; Khanal, Dipak; Lafalce, Evan; You, Wei; Valy Vardeny, Z.

2018-04-01

We used multiple spectroscopies such as photoinduced absorption (PIA), magneto photoinduced absorption, and doping induced absorption for studying native defects in π-conjugated donor-acceptor copolymer chains of benzodithio-phene fluorinated benzotriazole. The PIA spectrum contains characteristic photoinduced absorption bands that are due to polarons and triplet exciton species, whose strengths have different dependencies on the modulation frequency, temperature, and laser excitation, as well as magnetic field response. We found that the native defects in the copolymer chains serve as efficient traps that ionize the photoexcited excitons, thereby generating charge carriers whose characteristic optical properties are similar, but not equal to those of intrachain polarons formed by doping. The native defects density is of the order of 1017 cm-3 indicating that most of the copolymer chains contain native defects upon synthesis; however, this does not preclude their used-for photovoltaic applications.

The perspectives of femtosecond imaging and spectroscopy of complex materials using electrons

NASA Astrophysics Data System (ADS)

Ruan, Chong-Yu; Duxbury, Phiilp M.; Berz, Martin

2014-09-01

The coexistence of various electronic and structural phases that are close in free-energy is a hallmark in strongly correlated electron systems with emergent properties, such as metal-insulator transition, colossal magnetoresistance, and high-temperature superconductivity. The cooperative phase transitions from one functional state to another can involve entanglements between the electronically and structurally ordered states, hence deciphering the fundamental mechanisms is generally difficult and remains very active in condensed matter physics and functional materials research. We outline the recent ultrafast characterizations of 2D charge-density wave materials, including the nonequilibrium electron dynamics unveiled by ultrafast optical spectroscopy-based techniques sensitive to the electronic order parameter. We also describe the most recent findings from ultrafast electron crystallography, which provide structural aspects to correlate lattice dynamics with electronic evolutions to address the two sides of a coin in the ultrafast switching of a cooperative state. Combining these results brings forth new perspectives and a fuller picture in understanding lightmatter interactions and various switching mechanisms in cooperative systems with many potential applications. We also discuss the prospects of implementing new ultrafast electron imaging as a local probe incorporated with femtosecond select-area diffraction, imaging and spectroscopy to provide a full scope of resolution to tackle the more challenging complex phase transitions on the femtosecond-nanometer scale all at once based on a recent understanding of the spacespace- charge-driven emittance limitation on the ultimate performance of these devices. The projection shows promising parameter space for conducting ultrafast electron micordiffraction at close to single-shot level, which is supported by the latest experimental characterization of such a system.

Oligothiophene/graphene supramolecular ensembles managing light induced processes: preparation, characterization, and femtosecond transient absorption studies leading to charge-separation

NASA Astrophysics Data System (ADS)

Stergiou, A.; Gobeze, H. B.; Petsalakis, I. D.; Zhao, S.; Shinohara, H.; D'Souza, F.; Tagmatarchis, N.

2015-09-01

Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles.Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles. Electronic supplementary information (ESI) available: NMR, MS, ATR-IR, UV-Vis spectra, CV graphs, femto- and nano-second transient absorption spectra of oligothiophenes and their ensembles with exfoliated graphene. See DOI: 10.1039/c5nr04875c

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially separated insulator and metal islands) and, more importantly, their dynamic evolution in response to optical excitation.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study.

PubMed

Guo, Xugeng; Yuan, Huijuan; An, Beibei; Zhu, Qiuling; Zhang, Jinglai

2016-04-21

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S1 state, which may undergo an ultrafast non-radiative deactivation to the S0 state. The lifetime of the S1 state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solventwater has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in watersolution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.

Wavelength-dependent ultrafast charge carrier separation in the WO 3/BiVO 4 coupled system

DOE PAGES

Grigioni, Ivan; Stamplecoskie, Kevin G.; Jara, Danilo H.; ...

2017-05-08

Due to its ~2.4 eV band gap, BiVO 4 is a very promising photoanode material for harvesting the blue portion of the solar light for photoelectrochemical (PEC) water splitting applications. In WO 3/BiVO 4 heterojunction films, the electrons photoexcited in BiVO 4 are injected into WO 3, overcoming the lower charge carriers’ diffusion properties limiting the PEC performance of BiVO 4 photoanodes. Here, we investigate by ultrafast transient absorption spectroscopy the charge carrier interactions occurring at the interface between the two oxides in heterojunction systems to directly unveil their wavelength dependence. Under selective BiVO 4 excitation, a favorable electron transfermore » from photoexcited BiVO 4 to WO 3 occurs immediately after excitation and leads to an increase of the trapped holes’ lifetime in BiVO4. However, a recombination channel opens when both oxides are simultaneously excited, evidenced by a shorter lifetime of trapped holes in BiVO 4. As a result, PEC measurements reveal the implication of these wavelength-dependent ultrafast interactions on the performances of the WO 3/BiVO 4 heterojunction.« less

Wavelength-dependent ultrafast charge carrier separation in the WO 3/BiVO 4 coupled system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grigioni, Ivan; Stamplecoskie, Kevin G.; Jara, Danilo H.

Due to its ~2.4 eV band gap, BiVO 4 is a very promising photoanode material for harvesting the blue portion of the solar light for photoelectrochemical (PEC) water splitting applications. In WO 3/BiVO 4 heterojunction films, the electrons photoexcited in BiVO 4 are injected into WO 3, overcoming the lower charge carriers’ diffusion properties limiting the PEC performance of BiVO 4 photoanodes. Here, we investigate by ultrafast transient absorption spectroscopy the charge carrier interactions occurring at the interface between the two oxides in heterojunction systems to directly unveil their wavelength dependence. Under selective BiVO 4 excitation, a favorable electron transfermore » from photoexcited BiVO 4 to WO 3 occurs immediately after excitation and leads to an increase of the trapped holes’ lifetime in BiVO4. However, a recombination channel opens when both oxides are simultaneously excited, evidenced by a shorter lifetime of trapped holes in BiVO 4. As a result, PEC measurements reveal the implication of these wavelength-dependent ultrafast interactions on the performances of the WO 3/BiVO 4 heterojunction.« less

Resonance-Raman spectro-electrochemistry of intermediates in molecular artificial photosynthesis of bimetallic complexes.

PubMed

Zedler, Linda; Guthmuller, Julien; Rabelo de Moraes, Inês; Kupfer, Stephan; Krieck, Sven; Schmitt, Michael; Popp, Jürgen; Rau, Sven; Dietzek, Benjamin

2014-05-25

The sequential order of photoinduced charge transfer processes and accompanying structure changes were analyzed by UV-vis and resonance-Raman spectroscopy of intermediates of a Ru(ii) based photocatalytic hydrogen evolving system obtained by electrochemical reduction.

Optical backbone-sidechain charge transfer transitions in proteins sensitive to secondary structure and modifications.

PubMed

Mandal, I; Paul, S; Venkatramani, R

2018-04-17

The absorption of light by proteins can induce charge transfer (CT) transitions in the UV-visible range of the electromagnetic spectrum. Metal-ligand complexes or active site prosthetic groups which absorb in the visible region exhibit prominent CT transitions. Furthermore, the protein backbone also exhibits CT transitions in the far UV range. In this manuscript, we present a detailed computational study of new near UV-visible CT transitions that involve amino acids with charged side chains. Specifically, using time dependent density functional theory calculations, we examine the absorption spectra of naturally charged amino acids (Lys, Glu, Arg, Asp and His), extracted from solution phase protein structures generated by classical molecular dynamics simulations, and phosphorylated amino acids (Tyr, Thr and Ser) from experimentally determined protein structures. We show that amino acids with charged sidechains present a directed electronic donor-bridge-acceptor paradigm, with the lowest energy optical excitations demonstrating peptide backbone-sidechain charge separations. The UV-visible spectral range of the backbone-sidechain CT transitions is determined by the chemical nature of the donor, bridge and acceptor groups within each amino acid, amino acid conformation and the protein secondary structure where the amino acids are located. Photoinduced CT occurs in opposite directions for the anionic and cationic amino acids along the ground state dipole moment vector for the chromophores. We find that photoinduced charge separation is more facile for the anionic amino acids (Asp, Glu, pSer, pThr and pTyr) relative to that for the cationic amino acids (Lys, Arg and Hsp). Our results provide a foundation for the development of spectroscopic markers based on the recently proposed Protein Charge Transfer Spectra (ProCharTS) which are relevant for the study of DNA-binding or intrinsically disordered proteins that are rich in charged amino acids.

Photoinduced charge-transfer electronic excitation of tetracyanoethylene/tetramethylethylene complex in dichloromethane

NASA Astrophysics Data System (ADS)

Xu, Long-Kun; Bi, Ting-Jun; Ming, Mei-Jun; Wang, Jing-Bo; Li, Xiang-Yuan

2017-07-01

Based on the previous work on nonequilibrium solvation model by the authors, Intermolecular charge-transfer electronic excitation of tetracyanoethylene (TCE)/tetramethylethylene (TME) π -stacked complex in dichloromethane (DCM) has been investigated. For weak interaction correction, dispersion corrected functional DFT-D3 is adopted for geometry optimization. In order to identify the excitation metric, dipole moment components of each Cartesian direction, atomic charge, charge separation and Δr index are analyzed for TCE/TME complex. Calculation shows that the calculated excitation energy is dependent on the functional choice, when conjuncted with suitable time-dependent density functional, the modified nonequilibrium expression gives satisfied results for intermolecular charge-transfer electronic excitation.

The influence of charge and magnetic order on polaron and acoustic phonon dynamics in LuFe 2O 4

DOE PAGES

Lee, J.; Trugman, S. A.; Zhang, C. L.; ...

2015-07-27

Femtosecond optical pump-probe spectroscopy is used to reveal the influence of charge and magnetic order on polarondynamics and coherent acoustic phonon oscillations in single crystals of charge-ordered, ferrimagnetic LuFe 2O 4. We experimentally observed the influence of magnetic order on polarondynamics. We also observed a correlation between charge order and the amplitude of the acoustic phonon oscillations, due to photoinduced changes in the lattice constant that originate from the photoexcited electrons. As a result, this provides insight into the general behavior of coherent acoustic phonon oscillations in charge-ordered materials.

Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr2IrO4.

PubMed

Dean, M P M; Cao, Y; Liu, X; Wall, S; Zhu, D; Mankowsky, R; Thampy, V; Chen, X M; Vale, J G; Casa, D; Kim, Jungho; Said, A H; Juhas, P; Alonso-Mori, R; Glownia, J M; Robert, A; Robinson, J; Sikorski, M; Song, S; Kozina, M; Lemke, H; Patthey, L; Owada, S; Katayama, T; Yabashi, M; Tanaka, Yoshikazu; Togashi, T; Liu, J; Rayan Serrao, C; Kim, B J; Huber, L; Chang, C-L; McMorrow, D F; Först, M; Hill, J P

2016-06-01

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity. Recently, photo-excitation has been used to induce similarly exotic states transiently. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr2IrO4. We find that the non-equilibrium state, 2 ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. The marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.

Watching the dynamics of electrons and atoms at work in solar energy conversion.

PubMed

Canton, S E; Zhang, X; Liu, Y; Zhang, J; Pápai, M; Corani, A; Smeigh, A L; Smolentsev, G; Attenkofer, K; Jennings, G; Kurtz, C A; Li, F; Harlang, T; Vithanage, D; Chabera, P; Bordage, A; Sun, L; Ott, S; Wärnmark, K; Sundström, V

2015-01-01

The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium-cobalt dyads, which belong to the large family of donor-bridge-acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfer processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.

Ultrafast dynamics of photogenerated electrons in CdS nanocluster multilayers assembled on solid substrates: effects of assembly and electrode potential.

PubMed

Yagi, Ichizo; Mikami, Kensuke; Okamura, Masayuki; Uosaki, Kohei

2013-07-22

The ultrafast dynamics of photogenerated electrons in multilayer assemblies of CdS nanoparticles prepared on quartz and indium-tin oxide (ITO) substrates were followed by femtosecond (fs) visible-pump/mid-IR probe spectroscopy. Based on the observation of the photoinduced transient absorption spectra in the broad mid-IR range at the multilayer assembly of CdS nanoparticles, the occupation and fast relaxation of higher electronic states (1P(e)) were clarified. As compared with the electron dynamics of isolated (dispersed in solution) nanoparticles, the decay of photoexcited electrons in the multilayer assembly was clearly accelerated probably due to both electron hopping and scattering during interparticle electron tunneling. By using an ITO electrode as a substrate, the effect of the electric field on the photoelectron dynamics in the multilayer assembly was also investigated in situ. Both the amplitude and lifetime of photoexcited electrons gradually reduced as the potential became more positive. This result was explained by considering the reduction of the interparticle tunneling probability and the increase in the electron-transfer rate from the CdS nanoparticle assembly to the ITO electrode. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast primary processes of an iron-(III) azido complex in solution induced with 266 nm light.

PubMed

Vennekate, Hendrik; Schwarzer, Dirk; Torres-Alacan, Joel; Krahe, Oliver; Filippou, Alexander C; Neese, Frank; Vöhringer, Peter

2012-05-14

The ultrafast photo-induced primary processes of the iron-(III) azido complex, [Fe(III)N(3)(cyclam-acetato)] PF(6) (1), in acetonitrile solution at room temperature were studied using femtosecond spectroscopy with ultraviolet (UV) excitation and mid-infrared (MIR) detection. Following the absorption of a 266 nm photon, the complex undergoes an internal conversion back to the electronic doublet ground state at a time scale below 2 ps. Subsequently, the electronic ground state vibrationally cools with a characteristic time constant of 13 ps. A homolytic bond cleavage was also observed by the appearance of ground state azide radicals, which were identified by their asymmetric stretching vibration at 1659 cm(-1). The azide radical recombines in a geminate fashion with the iron containing fragment within 20 ps. The cage escape leading to well separated fragments after homolytic Fe-N bond breakage was found to occur with a quantum yield of 35%. Finally, non-geminate recombination at nanosecond time scales was seen to further reduce the photolytic quantum yield to below 20% at a wavelength of 266 nm. This journal is © the Owner Societies 2012

Charge Versus Energy Transfer in Atomically Thin Graphene-Transition Metal Dichalcogenide van der Waals Heterostructures

NASA Astrophysics Data System (ADS)

Froehlicher, Guillaume; Lorchat, Etienne; Berciaud, Stéphane

2018-01-01

Made from stacks of two-dimensional materials, van der Waals heterostructures exhibit unique light-matter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report an original study of interlayer charge and energy transfer in atomically thin metal-semiconductor [i.e., graphene-transition metal dichalcogenide (TMD, here molybdenum diselenide, MoSe2 )] heterostructures using a combination of microphotoluminescence and Raman scattering spectroscopies. The photoluminescence intensity in graphene /MoSe2 is quenched by more than 2 orders of magnitude and rises linearly with the incident photon flux, demonstrating a drastically shortened (about 1 ps) room-temperature MoSe2 exciton lifetime. Key complementary insights are provided from a comprehensive analysis of the graphene and MoSe2 Raman modes, which reveals net photoinduced electron transfer from MoSe2 to graphene and hole accumulation in MoSe2 . Remarkably, the steady-state Fermi energy of graphene saturates at 290 ±15 meV above the Dirac point. This reproducible behavior is observed both in ambient air and in vacuum and is discussed in terms of intrinsic factors (i.e., band offsets) and environmental effects. In this saturation regime, balanced photoinduced flows of electrons and holes may transfer to graphene, a mechanism that effectively leads to energy transfer. Using a broad range of incident photon fluxes and diverse environmental conditions, we find that the presence of net photoinduced charge transfer has no measurable impact on the near-unity photoluminescence quenching efficiency in graphene /MoSe2 . This absence of correlation strongly suggests that energy transfer to graphene (either in the form of electron exchange or dipole-dipole interaction) is the dominant interlayer coupling mechanism between atomically thin TMDs and graphene.

Acceleration of Singlet Fission in an Aza-Derivative of TIPS-Pentacene.

PubMed

Herz, Julia; Buckup, Tiago; Paulus, Fabian; Engelhart, Jens; Bunz, Uwe H F; Motzkus, Marcus

2014-07-17

The influence of the carbon to nitrogen substitution on the photoinduced dynamics of TIPS-pentacene was investigated by ultrafast transient absorption measurements on spin-coated thin films in the visible and in the near-infrared spectral region. A global target analysis was performed to provide a detailed picture of the excited-state dynamics. We found that the chemical modification has a high impact on the triplet formation and leads to shorter dynamics; hence it speeds up the singlet fission process. A faster relaxation from the singlet into the triplet manifold implies a higher efficiency because other relaxation channels are avoided. The air-stable aza-derivatives have the potential to exceed the energy conversion efficiency of TIPS-pentacene.

Ultrafast dynamics of ligand and substrate interaction in endothelial nitric oxide synthase under Soret excitation.

PubMed

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S

2016-01-01

Ultrafast transient absorption spectroscopy of endothelial NOS oxygenase domain (eNOS-oxy) was performed to study dynamics of ligand or substrate interaction under Soret band excitation. Photo-excitation dissociates imidazole ligand in <300fs, then followed by vibrational cooling and recombination within 2ps. Such impulsive bond breaking and late rebinding generate proteinquakes, which relaxes in several tens of picoseconds. The photo excited dynamics of eNOS-oxy with L-arginine substrate mainly occurs at the local site of heme, including ultrafast internal conversion within 400fs, vibrational cooling, charge transfer, and complete ground-state recovery within 1.4ps. The eNOS-oxy without additive is partially bound with water molecule, thus its photoexcited dynamics also shows ligand dissociation in <800fs. Then it followed by vibrational cooling coupled with charge transfer in 4.8ps, and recombination of ligand to distal side of heme in 12ps. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultrafast X-Ray Spectroscopy of Conical Intersections

NASA Astrophysics Data System (ADS)

Neville, Simon P.; Chergui, Majed; Stolow, Albert; Schuurman, Michael S.

2018-06-01

Ongoing developments in ultrafast x-ray sources offer powerful new means of probing the complex nonadiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical intersections, which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high-level ab initio quantum dynamics simulations, we studied time-resolved x-ray absorption (TRXAS) and photoelectron spectroscopy (TRXPS) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2(π π*) state. The TRXAS, in particular, is highly sensitive to all aspects of the ensuing dynamics. These x-ray spectroscopies provide a clear signature of the wave packet dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast x-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

Enhanced photocatalytic activity of BiOCl by C70 modification and mechanism insight

NASA Astrophysics Data System (ADS)

Ma, Dongmei; Zhong, Junbo; Li, Jianzhang; Wang, Li; Peng, Rufang

2018-06-01

As an excellent photocatalyst which can compete with TiO2, BiOCl has triggered increasing attention. However, the practical application of BiOCl has been significantly limited by the fast recombination of the photoinduced electron-hole charge pairs. In this study, to further enhance the separation efficiency of photoinduced electron-hole charge pairs of BiOCl, a series of efficient BiOCl photocatalysts were prepared by C70 surface modification. The trapping experiments reveal that the main active species were determined to be superoxide radicals (O2rad -) and holes (h+) under simulated sunlight irradiation. The surface photovoltage spectroscopy (SPS) demonstrates that separation of the photoinduced electron-hole pairs has been significantly promoted, forming more radOH, proven by terephthalic acid photoluminescence probing technique. The photocatalytic evaluation results display that the C70/BiOCl photocatalysts exhibit much higher photocatalytic activity in decolorization of rhodamine B (RhB) than that of the bare BiOCl under the simulated sunlight irradiation. The excellent electron acceptability of C70 is conducive to the separation of the photogenerated carriers and results in efficient formation of O2rad -, proven by the results of SPS and electron spin-resonance (ESR), therefore the photocatalytic performance of C70/BiOCl has been greatly improved. Based on all these observations, an enhancement mechanism in photocatalytic performance of C70/BiOCl was proposed.

Photo-inducible Crosslinked Nanoassemblies for pH-Controlled Drug Release

PubMed Central

Dickerson, Matthew; Winquist, Nickolas; Bae, Younsoo

2014-01-01

Purpose To control drug release from block copolymer nanoassemblies by variation in the degree of photo-crosslinking and inclusion of acid sensitive linkers. Methods Poly(ethylene glycol)-poly(aspartate-hydrazide-cinnamate) (PEG-CNM) block copolymers were prepared and conjugated with a model drug, doxorubicin (DOX), through acid sensitive hydrazone linkers. The block copolymers formed photo-inducible, self-assembled nanoassemblies (piSNAs), which were used to produce photo-inducible crosslinked nanoassemblies (piCNAs) through UV crosslinking. The nanoassemblies were characterized to determine particle size, surface charge, pH- and crosslinking-dependent DOX release, in vitro cytotoxicity, and intracellular uptake as a function of photo-crosslinking degree. Results Nanoassemblies with varying photo-crosslinking degrees were successfully prepared while retaining particle size and surface charge. Photo-crosslinking caused no noticeable change in DOX release from the nanoassemblies at pH 7.4, but the DOX-loaded nanoassemblies modulated drug release as a function of crosslinking at pH 6.0. The nanoassemblies showed similar cytotoxicity regardless of crosslinking degrees, presumably due to the low cellular uptake and cell nucleus drug accumulation. Conclusion Photo-crosslinking is useful to control drug release from pH-sensitive block copolymer nanoassemblies as a function of crosslinking without altering the particle properties, and thus providing unique tools to investigate the pharmaceutical effects of drug release on cellular response. PMID:24254196

Probing π-π stacking modulation of g-C3N4/graphene heterojunctions and corresponding role of graphene on photocatalytic activity.

PubMed

Ma, Xinguo; Wei, Yang; Wei, Zhen; He, Hua; Huang, Chuyun; Zhu, Yongfa

2017-12-15

The photoelectrochemical properties of g-C 3 N 4 sheet are modified by the π-π stacking interaction with graphene, and the corresponding role of graphene on the surface chemical reactions is investigated by density functional theory. The calculated cohesive energies and the lattice mismatch energies indicate that g-C 3 N 4 and graphene are in parallel contact and can form a stable heterojunction. According to our calculated energy band structures and work functions of g-C 3 N 4 /graphene heterojunctions, the band edge modulations by graphene are discussed and corresponding photoinduced charge transfer processes are analyzed in detail. It is found that the incorporating of graphene into g-C 3 N 4 facilitates the separation of photoinduced e - /h + pairs and the oxidation capacity enhancement of the photoinduced holes with the downshifting of the valence band edge of g-C 3 N 4 layer. It is identified that the inhomogeneous onsite energies between interlayer and the band edge modulations are induced by the inhomogeneous charge redistribution between interlayer caused by graphene. Further, the initial dynamic reaction processes of oxygen atoms in g-C 3 N 4 /graphene heterojunctions also confirm the significant role of graphene on the surface chemical reactions. Copyright © 2017 Elsevier Inc. All rights reserved.

Ultrafast fluorescence upconversion technique and its applications to proteins.

PubMed

Chosrowjan, Haik; Taniguchi, Seiji; Tanaka, Fumio

2015-08-01

The basic principles and main characteristics of the ultrafast time-resolved fluorescence upconversion technique (conventional and space-resolved), including requirements for nonlinear crystals, mixing spectral bandwidth, acceptance angle, etc., are presented. Applications to flavoproteins [wild-type (WT) FMN-binding protein and its W32Y, W32A, E13R, E13K, E13Q and E13T mutants] and photoresponsive proteins [WT photoactive yellow protein and its R52Q mutant in solution and as single crystals] are demonstrated. For flavoproteins, investigations elucidating the effects of ionic charges on ultrafast electron transfer (ET) dynamics are summarized. It is shown that replacement of the ionic amino acid Glu13 and the resulting modification of the electrostatic charge distribution in the protein chromphore-binding pocket substantially alters the ultrafast fluorescence quenching dynamics and ET rate in FMN-binding protein. It is concluded that, together with donor-acceptor distances, electrostatic interactions between ionic photoproducts and other ionic groups in the proteins are important factors influencing the ET rates. In WT photoactive yellow protein and the R52Q mutant, ultrafast photoisomerization dynamics of the chromophore (deprotonated trans-p-coumaric acid) in liquid and crystal phases are investigated. It is shown that the primary dynamics in solution and single-crystal phases are quite similar; hence, the photocycle dynamics and structural differences observed at longer time scales arise mostly from the structural restraints imposed by the crystal lattice rigidity versus the flexibility in solution. © 2014 FEBS.

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

Ultrafast universal quantum control of a quantum-dot charge qubit using Landau–Zener–Stückelberg interference

PubMed Central

Cao, Gang; Li, Hai-Ou; Tu, Tao; Wang, Li; Zhou, Cheng; Xiao, Ming; Guo, Guang-Can; Jiang, Hong-Wen; Guo, Guo-Ping

2013-01-01

A basic requirement for quantum information processing is the ability to universally control the state of a single qubit on timescales much shorter than the coherence time. Although ultrafast optical control of a single spin has been achieved in quantum dots, scaling up such methods remains a challenge. Here we demonstrate complete control of the quantum-dot charge qubit on the picosecond scale, orders of magnitude faster than the previously measured electrically controlled charge- or spin-based qubits. We observe tunable qubit dynamics in a charge-stability diagram, in a time domain, and in a pulse amplitude space of the driven pulse. The observations are well described by Landau–Zener–Stückelberg interference. These results establish the feasibility of a full set of all-electrical single-qubit operations. Although our experiment is carried out in a solid-state architecture, the technique is independent of the physical encoding of the quantum information and has the potential for wider applications. PMID:23360992

Lead Telluride Quantum Dot Solar Cells Displaying External Quantum Efficiencies Exceeding 120%

PubMed Central

2015-01-01

Multiple exciton generation (MEG) in semiconducting quantum dots is a process that produces multiple charge-carrier pairs from a single excitation. MEG is a possible route to bypass the Shockley-Queisser limit in single-junction solar cells but it remains challenging to harvest charge-carrier pairs generated by MEG in working photovoltaic devices. Initial yields of additional carrier pairs may be reduced due to ultrafast intraband relaxation processes that compete with MEG at early times. Quantum dots of materials that display reduced carrier cooling rates (e.g., PbTe) are therefore promising candidates to increase the impact of MEG in photovoltaic devices. Here we demonstrate PbTe quantum dot-based solar cells, which produce extractable charge carrier pairs with an external quantum efficiency above 120%, and we estimate an internal quantum efficiency exceeding 150%. Resolving the charge carrier kinetics on the ultrafast time scale with pump–probe transient absorption and pump–push–photocurrent measurements, we identify a delayed cooling effect above the threshold energy for MEG. PMID:26488847

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandit, Bill; Jackson, Nicholas E.; Zheng, Tianyue

Rational design strategies for controlling the energetics of conjugated “donor–acceptor” copolymers are ubiquitous in the literature, as they allow for simple energy-level tuning strategies to be employed for photovoltaic and transistor applications. Utilizing the recently reported PTRn series of conjugated polymers closely related to the widely implemented material PTB7, we investigate the effect of local copolymer block energetics on the generation of transient excitonic and charge carrier species. It is clearly demonstrated that local copolymer block energetics play a much larger role than is apparent from simple energy-level tuning arguments, and drastically affect the ultrafast generation of free-charge carrier andmore » trap state populations. Specifically, we observe an almost complete reversal in the efficient generation of free-charge in PTB7 to the ultrafast creation of a high percentage of trapped pseudo charge-transfer states. The implications of this secondary effect of “donor–acceptor” energy level tuning are discussed, along with strategies for avoiding the generation of trap states in “donor–acceptor” copolymers.« less

InAs Band-Edge Exciton Fine Structure

DTIC Science & Technology

2015-07-29

Chapter 1 InAs Band-Edge Exciton Fine Structure 1.1 Contributions This work was carried out in collaboration with Oscar Sandoval, a summer student at...diffusion,1,2 charg- ing,2,3 and excitonic fine structure.1,3–9 While spectral diffusion and charging are most likely photoinduced effects and thus can be...unavoidable. A complete understanding of the excitonic 1 Distribution A: Public Release energy landscape enables us to determine dephasing rates

Synthesis of Nb doped TiO2 nanotube/reduced graphene oxide heterostructure photocatalyst with high visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Niu, Xiaoyou; Yan, Weijing; Zhao, Hongli; Yang, Jingkai

2018-05-01

Limited by the narrowed photoresponse range and unsatisfactory recombination of photoinduced electron-hole pairs, the photocatalytic efficiency of TiO2 is still far below what is expected. Here, we initially doped TiO2 nanotubes (TNTS) by transition metal ion Nb, then it is coupled with reduced graphene oxide (rGO) to construct a heterostructure photocatalyst. The defect state presented in TiO2 leading to the formation of localized midgap states (MS) in the bandgap, which regulating the band structure of TiO2 and extending the optical absorption to visible light region. The internal charge transport and transfer behavior analyzed by electrochemical impedance spectroscopy (EIS) reveal that the coupling of rGO with TNTS results in the formation of electron transport channel in the heterostructure, which makes a great contribution to the photoinduced charge separation. As expected, the Nb-TNTS/rGO exhibits a stable and remarkably enhanced photocatalytic activity in the visible-light irradiation degradation of methylene blue (MB), up to ∼5 times with respect to TNTS, which is attributed to the effective inhibition of charge recombination, the reduction of bandgap and higher redox potential, as well as the great adsorptivity.

Ultrafast gating of a mid-infrared laser pulse by a sub-pC relativistic electron beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cesar, D. B.; Musumeci, P.; Alesini, D.

In this paper we discuss a relative time-of-arrival measurement scheme between an electron beam and a mid-infrared laser pulse based on the electron-beam controlled transmission in semiconductor materials. This technique can be used as a time-stamping diagnostic in ultrafast electron diffraction or microscopy. In particular, our characterization of Germanium demonstrates that sub-ps time-of-arrival sensitivity could be achieved in a single shot and with very low charge beams (<1 pC). Detailed measurements as a function of the beam charge and the laser wavelength offer insights on the free carrier dynamics in the semiconductor upon excitation by the electron beam.

Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex.

PubMed

Santos, Willy G; Budkina, Darya S; Deflon, Victor M; Tarnovsky, Alexander N; Cardoso, Daniel R; Forbes, Malcolm D E

2017-06-14

Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (k obs < 10 12 s -1 ) and twisted (k obs ∼ 10 10 s -1 ) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V •+ ).

Modeling time-coincident ultrafast electron transfer and solvation processes at molecule-semiconductor interfaces

NASA Astrophysics Data System (ADS)

Li, Lesheng; Giokas, Paul G.; Kanai, Yosuke; Moran, Andrew M.

2014-06-01

Kinetic models based on Fermi's Golden Rule are commonly employed to understand photoinduced electron transfer dynamics at molecule-semiconductor interfaces. Implicit in such second-order perturbative descriptions is the assumption that nuclear relaxation of the photoexcited electron donor is fast compared to electron injection into the semiconductor. This approximation breaks down in systems where electron transfer transitions occur on 100-fs time scale. Here, we present a fourth-order perturbative model that captures the interplay between time-coincident electron transfer and nuclear relaxation processes initiated by light absorption. The model consists of a fairly small number of parameters, which can be derived from standard spectroscopic measurements (e.g., linear absorbance, fluorescence) and/or first-principles electronic structure calculations. Insights provided by the model are illustrated for a two-level donor molecule coupled to both (i) a single acceptor level and (ii) a density of states (DOS) calculated for TiO2 using a first-principles electronic structure theory. These numerical calculations show that second-order kinetic theories fail to capture basic physical effects when the DOS exhibits narrow maxima near the energy of the molecular excited state. Overall, we conclude that the present fourth-order rate formula constitutes a rigorous and intuitive framework for understanding photoinduced electron transfer dynamics that occur on the 100-fs time scale.

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

Modulation of ultrafast photoinduced electron transfer in H-bonding environment: PET from aniline to coumarin 153 in the presence of an inert co-solvent cyclohexane.

PubMed

Barman, Nabajeet; Hossen, Tousif; Mondal, Koushik; Sahu, Kalyanasis

2015-12-28

Despite intensive research, the role of the H-bonding environment on ultrafast PET remains illusive. For example, coumarin 153 (C153) undergoes ultrafast photoinduced electron transfer (PET) in electron-donating solvents, in both aniline (AN) and N,N-dimethylaniline (DMA), despite their very different H-bonding abilities. Thus, donor-acceptor (AN-C153) H-bonding may have only a minor role in PET (Yoshihara and co-workers, J. Phys. Chem. A, 1998, 102, 3089). However, donor-acceptor H-bonding may be somehow less effective in the neat H-bonding environment but could become dominant in the presence of an inert solvent (Phys. Chem. Chem. Phys., 2014, 16, 6159). We successfully applied and tested the proposal here. The nature of PET modulation of C153 in the presence of a passive component cyclohexane is found to be very different for aniline and DMA. Upon addition of cyclohexane to DMA, the PET process gradually becomes retarded but in the case of AN, the PET rate was indeed found to be accelerated at some intermediate composition (mole fraction of aniline, XAN∼ 0.74) compared to that of neat aniline. It is intuitive that cyclohexane may replace some of the donors (AN or DMA) from the vicinity of the acceptor and, thus, should disfavour PET. However, in the hydrogen bonding environment using molecular dynamics simulation, for the first time, we show that the average number of aniline molecules orienting their N-H group in the proximity of the C=O group of C153 is actually higher at the intermediate mole fraction (0.74) of aniline in a mixture rather than in neat aniline. This small but finite excess of C153-AN H-bonding already present in the ground state may possibly account for the anomalous effect. The TD-DFT calculations presented here showed that the intermolecular H-bonding between C153 and AN strengthens from 21.1 kJ mol(-1) in the ground state to 33.0 kJ mol(-1) in the excited state and, consequently, H-bonding may assist PET according to the Zhao and Han model. Thus, we not only justified both the theoretical prediction (efficient H-bond assisted PET within the C153-AN pair) and experimental observation (minor H-bond assisted PET in neat solvent) but also established our previous hypothesis that an inert co-solvent can enhance the effect of H-bonding from molecular insights.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

PubMed

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Boning; Liang, Min; Zmich, Nicole

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

Wu, Boning; Liang, Min; Zmich, Nicole; ...

2018-01-29

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Early bacteriopheophytin reduction in charge separation in reaction centers of Rhodobacter sphaeroides.

PubMed

Zhu, Jingyi; van Stokkum, Ivo H M; Paparelli, Laura; Jones, Michael R; Groot, Marie Louise

2013-06-04

A question at the forefront of biophysical sciences is, to what extent do quantum effects and protein conformational changes play a role in processes such as biological sensing and energy conversion? At the heart of photosynthetic energy transduction lie processes involving ultrafast energy and electron transfers among a small number of tetrapyrrole pigments embedded in the interior of a protein. In the purple bacterial reaction center (RC), a highly efficient ultrafast charge separation takes place between a pair of bacteriochlorophylls: an accessory bacteriochlorophyll (B) and bacteriopheophytin (H). In this work, we applied ultrafast spectroscopy in the visible and near-infrared spectral region to Rhodobacter sphaeroides RCs to accurately track the timing of the electron on BA and HA via the appearance of the BA and HA anion bands. We observed an unexpectedly early rise of the HA⁻ band that challenges the accepted simple picture of stepwise electron transfer with 3 ps and 1 ps time constants. The implications for the mechanism of initial charge separation in bacterial RCs are discussed in terms of a possible adiabatic electron transfer step between BA and HA, and the effect of protein conformation on the electron transfer rate. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei

Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less

Interaction of proflavin with aromatic amines in homogeneous and micellar media: Photoinduced electron transfer probed by magnetic field effect

NASA Astrophysics Data System (ADS)

Chakraborty, Brotati; Basu, Samita

2010-02-01

Photoinduced electron transfer (PET) between proflavin (PF +) and two aromatic amines viz., dimethylaniline (DMA) and 4,4'-bis(dimethylamino)diphenylmethane (DMDPM) is studied in homogeneous and heterogeneous media using steady-state as well as time-resolved fluorescence spectroscopy and laser flash photolysis with an associated magnetic field. Ionic micelles have been used to study the effect of charge of proflavin on PET with amines. Magnetic field effect on PET reactions reveals that the parent spin-state of precursors of PET for DMA-PF + system is singlet while for DMDPM-PF + system is triplet, implying that the dynamics of PET is influenced by the structure of the donor.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, R.; Calvin, M.

1984-01-24

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospholipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transferring electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

Photoinduced Oxidative DNA Damage Revealed by an Agarose Gel Nicking Assay: A Biophysical Chemistry Laboratory Experiment

NASA Astrophysics Data System (ADS)

Shafirovich, Vladimir; Singh, Carolyn; Geacintov, Nicholas E.

2003-11-01

Oxidative damage of DNA molecules associated with electron-transfer reactions is an important phenomenon in living cells, which can lead to mutations and contribute to carcinogenesis and the aging processes. This article describes the design of several simple experiments to explore DNA damage initiated by photoinduced electron-transfer reactions sensitized by the acridine derivative, proflavine (PF). A supercoiled DNA agarose gel nicking assay is employed as a sensitive probe of DNA strand cleavage. A low-cost experimental and computer-interfaced imaging apparatus is described allowing for the digital recording and analysis of the gel electrophoresis results. The first experiment describes the formation of direct strand breaks in double-stranded DNA induced by photoexcitation of the intercalated PF molecules. The second experiment demonstrates that the addition of the well-known electron acceptor, methylviologen, gives rise to a significant enhancement of the photochemical DNA strand cleavage effect. This occurs by an electron transfer step to methylviologen that renders the inital photoinduced charge separation between photoexcited PF and DNA irreversible. The third experiment demonstrates that the action spectrum of the DNA photocleavage matches the absorption spectrum of DNA-bound, intercalated PF molecules, which differs from that of free PF molecules. This result demonstrates that the photoinduced DNA strand cleavage is initiated by intercalated rather than free PF molecules.

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy

PubMed Central

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H.

2014-01-01

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material’s electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier–carrier scatterings which are mirrored in the energy of material’s secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces. PMID:24469803

Visualization of carrier dynamics in p(n)-type GaAs by scanning ultrafast electron microscopy.

PubMed

Cho, Jongweon; Hwang, Taek Yong; Zewail, Ahmed H

2014-02-11

Four-dimensional scanning ultrafast electron microscopy is used to investigate doping- and carrier-concentration-dependent ultrafast carrier dynamics of the in situ cleaved single-crystalline GaAs(110) substrates. We observed marked changes in the measured time-resolved secondary electrons depending on the induced alterations in the electronic structure. The enhancement of secondary electrons at positive times, when the electron pulse follows the optical pulse, is primarily due to an energy gain involving the photoexcited charge carriers that are transiently populated in the conduction band and further promoted by the electron pulse, consistent with a band structure that is dependent on chemical doping and carrier concentration. When electrons undergo sufficient energy loss on their journey to the surface, dark contrast becomes dominant in the image. At negative times, however, when the electron pulse precedes the optical pulse (electron impact), the dynamical behavior of carriers manifests itself in a dark contrast which indicates the suppression of secondary electrons upon the arrival of the optical pulse. In this case, the loss of energy of material's electrons is by collisions with the excited carriers. These results for carrier dynamics in GaAs(110) suggest strong carrier-carrier scatterings which are mirrored in the energy of material's secondary electrons during their migration to the surface. The approach presented here provides a fundamental understanding of materials probed by four-dimensional scanning ultrafast electron microscopy, and offers possibilities for use of this imaging technique in the study of ultrafast charge carrier dynamics in heterogeneously patterned micro- and nanostructured material surfaces and interfaces.

Molecular implementation of molecular shift register memories

NASA Technical Reports Server (NTRS)

Beratan, David N. (Inventor); Onuchic, Jose N. (Inventor)

1991-01-01

An electronic shift register memory (20) at the molecular level is described. The memory elements are based on a chain of electron transfer molecules (22) and the information is shifted by photoinduced (26) electron transfer reactions. Thus, multi-step sequences of charge transfer reactions are used to move charge with high efficiency down a molecular chain. The device integrates compositions of the invention onto a VLSI substrate (36), providing an example of a molecular electronic device which may be fabricated. Three energy level schemes, molecular implementation of these schemes, optical excitation strategies, charge amplification strategies, and error correction strategies are described.

Ab initio multiple spawning on laser-dressed states: a study of 1,3-cyclohexadiene photoisomerization via light-induced conical intersections

NASA Astrophysics Data System (ADS)

Kim, Jaehee; Tao, Hongli; Martinez, Todd J.; Bucksbaum, Phil

2015-08-01

We extend the ab initio multiple spawning method to include both field-free and field-induced nonadiabatic transitions. We apply this method to describe ultrafast pump-probe experiments of the photoinduced ring-opening of gas phase 1,3-cyclohexadiene. In the absence of a control field, nonadiabatic transitions mediated by a conical intersection (CoIn) lead to rapid ground state recovery with both 1,3-cyclohexadiene and ring-opened hexatriene products. However, application of a control field within the first 200 fs after photoexcitation results in suppression of the hexatriene product. We demonstrate that this is a consequence of population dumping prior to reaching the CoIn and further interpret this in terms of light-induced CoIns created by the control field.

Note: A flexible light emitting diode-based broadband transient-absorption spectrometer

NASA Astrophysics Data System (ADS)

Gottlieb, Sean M.; Corley, Scott C.; Madsen, Dorte; Larsen, Delmar S.

2012-05-01

This Note presents a simple and flexible ns-to-ms transient absorption spectrometer based on pulsed light emitting diode (LED) technology that can be incorporated into existing ultrafast transient absorption spectrometers or operate as a stand-alone instrument with fixed-wavelength laser sources. The LED probe pulses from this instrument exhibit excellent stability (˜0.5%) and are capable of producing high signal-to-noise long-time (>100 ns) transient absorption signals either in a broadband multiplexed (spanning 250 nm) or in tunable narrowband (20 ns) operation. The utility of the instrument is demonstrated by measuring the photoinduced ns-to-ms photodynamics of the red/green absorbing fourth GMP phosphodiesterase/adenylyl cyclase/FhlA domain of the NpR6012 locus of the nitrogen-fixing cyanobacterium Nostoc punctiforme.

Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

PubMed Central

2015-01-01

The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

Ultrafast electronic dynamics driven by nuclear motion

NASA Astrophysics Data System (ADS)

Vendrell, Oriol

2016-05-01

The transfer of electrical charge on a microscopic scale plays a fundamental role in chemistry, in biology, and in technological applications. In this contribution, we will discuss situations in which nuclear motion plays a central role in driving the electronic dynamics of photo-excited or photo-ionized molecular systems. In particular, we will explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we will illustrate how the double hole can be transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. We thank the Hamburg Centre for Ultrafast Imaging and the Volkswagen Foundation for financial support.

Development of Scanning Ultrafast Electron Microscope Capability.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, Kimberlee Chiyoko; Talin, Albert Alec; Chandler, David W.

Modern semiconductor devices rely on the transport of minority charge carriers. Direct examination of minority carrier lifetimes in real devices with nanometer-scale features requires a measurement method with simultaneously high spatial and temporal resolutions. Achieving nanometer spatial resolutions at sub-nanosecond temporal resolution is possible with pump-probe methods that utilize electrons as probes. Recently, a stroboscopic scanning electron microscope was developed at Caltech, and used to study carrier transport across a Si p-n junction [ 1 , 2 , 3 ] . In this report, we detail our development of a prototype scanning ultrafast electron microscope system at Sandia National Laboratoriesmore » based on the original Caltech design. This effort represents Sandia's first exploration into ultrafast electron microscopy.« less

Influence of disorder on the photoinduced excitations in phenyl substituted polythiophenes

NASA Astrophysics Data System (ADS)

Brabec, Christoph J.; Winder, Christoph; Scharber, Markus C.; Sariciftci, N. Serdar; Hummelen, Jan C.; Svensson, Mattias; Andersson, Mats R.

2001-10-01

Regioregular poly(3-(4'-(1″,4″,7″-trioxaoctyl)phenyl)thiophenes) (PEOPTs) exhibit interesting properties for the use in polymer electronics. Exposing thin films of the amorphous, disordered phase (orange phase) of the "as prepared" polymer to chloroform vapor or annealing them by heat treatment results in a redshift of the absorption maximum due to the formation of nanocrystals in an ordered phase (blue phase). As such, PEOPT thus is a very interesting conjugated polymeric material, which exhibits two different phases with well-defined order/disorder characters on one-and-the-same material. This property opens up the unique possibility to investigate the role of order/disorder on the photoexcited pattern without being obscured by the differences in chemical structure by using different materials with different crystallinity. The fact, that blue phase PEOPT exhibits absorption edges at relatively low energies around 1.8 eV, thereby demonstrating an enhanced spectral absorption range as compared to the orange phase, makes them attractive for use in photodiodes and solar cells as well. The photoinduced charge generation efficiency in both phases of PEOPT is significantly enhanced by the addition of a strong electron acceptor such as fullerene C60, as observed by quenching of the luminescence and by photoinduced absorption measurements in the infrared and uv-visible regime. The average number and the lifetime of photoinduced carriers in composites of PEOPT with a methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM) are found to depend on the crystallinity of PEOPT in thin films, which gives rise to charged photoexcitations delocalized between polymer chains. Stronger bimolecular recombination in composites of the blue phase PEOPT with PCBM is observed as compared to the orange phase PEOPT/PCBM films. The origin of this enhanced recombination is found to be related to the hole mobility of the polymer.

Ultrafast Graphene Light Emitters.

PubMed

Kim, Young Duck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Bae, Myung-Ho; Kim, Hyungsik; Seo, Dongjea; Choi, Heon-Jin; Kim, Suk Hyun; Nemilentsau, Andrei; Low, Tony; Tan, Cheng; Efetov, Dmitri K; Taniguchi, Takashi; Watanabe, Kenji; Shepard, Kenneth L; Heinz, Tony F; Englund, Dirk; Hone, James

2018-02-14

Ultrafast electrically driven nanoscale light sources are critical components in nanophotonics. Compound semiconductor-based light sources for the nanophotonic platforms have been extensively investigated over the past decades. However, monolithic ultrafast light sources with a small footprint remain a challenge. Here, we demonstrate electrically driven ultrafast graphene light emitters that achieve light pulse generation with up to 10 GHz bandwidth across a broad spectral range from the visible to the near-infrared. The fast response results from ultrafast charge-carrier dynamics in graphene and weak electron-acoustic phonon-mediated coupling between the electronic and lattice degrees of freedom. We also find that encapsulating graphene with hexagonal boron nitride (hBN) layers strongly modifies the emission spectrum by changing the local optical density of states, thus providing up to 460% enhancement compared to the gray-body thermal radiation for a broad peak centered at 720 nm. Furthermore, the hBN encapsulation layers permit stable and bright visible thermal radiation with electronic temperatures up to 2000 K under ambient conditions as well as efficient ultrafast electronic cooling via near-field coupling to hybrid polaritonic modes under electrical excitation. These high-speed graphene light emitters provide a promising path for on-chip light sources for optical communications and other optoelectronic applications.

Scanning ultrafast electron microscopy.

PubMed

Yang, Ding-Shyue; Mohammed, Omar F; Zewail, Ahmed H

2010-08-24

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability.

Probing Ultrafast Electron Dynamics at Surfaces Using Soft X-Ray Transient Reflectivity Spectroscopy

NASA Astrophysics Data System (ADS)

Baker, L. Robert; Husek, Jakub; Biswas, Somnath; Cirri, Anthony

The ability to probe electron dynamics with surface sensitivity on the ultrafast time scale is critical for understanding processes such as charge separation, injection, and surface trapping that mediate efficiency in catalytic and energy conversion materials. Toward this goal, we have developed a high harmonic generation (HHG) light source for femtosecond soft x-ray reflectivity. Using this light source we investigated the ultrafast carrier dynamics at the surface of single crystalline α-Fe2O3, polycrystalline α-Fe2O3, and the mixed metal oxide, CuFeO2. We have recently demonstrated that CuFeO2 in particular is a selective catalyst for photo-electrochemical CO2 reduction to acetate; however, the role of electronic structure and charge carrier dynamics in mediating catalytic selectivity has not been well understood. Soft x-ray reflectivity measurements probe the M2,3, edges of the 3d transition metals, which provide oxidation and spin state resolution with element specificity. In addition to chemical state specificity, these measurements are also surface sensitive, and by independently simulating the contributions of the real and imaginary components of the complex refractive index, we can differentiate between surface and sub-surface contributions to the excited state spectrum. Accordingly, this work demonstrates the ability to probe ultrafast carrier dynamics in catalytic materials with element and chemical state specificity and with surface sensitivity.

Ultrafast energy- and momentum-resolved dynamics of magnetic correlations in the photo-doped Mott insulator Sr 2IrO 4

DOE PAGES

Dean, M. P. M.; Cao, Y.; Liu, X.; ...

2016-05-09

Measuring how the magnetic correlations evolve in doped Mott insulators has greatly improved our understanding of the pseudogap, non-Fermi liquids and high-temperature superconductivity 1, 2, 3, 4. Recently, photo-excitation has been used to induce similarly exotic states transiently 5, 6, 7. However, the lack of available probes of magnetic correlations in the time domain hinders our understanding of these photo-induced states and how they could be controlled. Here, we implement magnetic resonant inelastic X-ray scattering at a free-electron laser to directly determine the magnetic dynamics after photo-doping the Mott insulator Sr 2IrO 4. We find that the non-equilibrium state, 2more » ps after the excitation, exhibits strongly suppressed long-range magnetic order, but hosts photo-carriers that induce strong, non-thermal magnetic correlations. These two-dimensional (2D) in-plane Néel correlations recover within a few picoseconds, whereas the three-dimensional (3D) long-range magnetic order restores on a fluence-dependent timescale of a few hundred picoseconds. In conclusion, the marked difference in these two timescales implies that the dimensionality of magnetic correlations is vital for our understanding of ultrafast magnetic dynamics.« less

Full observation of ultrafast cascaded radiationless transitions from S{sub 2}(ππ{sup ∗}) state of pyrazine using vacuum ultraviolet photoelectron imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horio, Takuya; Spesyvtsev, Roman; Nagashima, Kazuki

A photoexcited molecule undergoes multiple deactivation and reaction processes simultaneously or sequentially, which have been observed by combinations of various experimental methods. However, a single experimental method that enables complete observation of the photo-induced dynamics would be of great assistance for such studies. Here we report a full observation of cascaded electronic dephasing from S{sub 2}(ππ{sup *}) in pyrazine (C{sub 4}N{sub 2}H{sub 4}) by time-resolved photoelectron imaging (TRPEI) using 9.3-eV vacuum ultraviolet pulses with a sub-20 fs time duration. While we previously demonstrated a real-time observation of the ultrafast S{sub 2}(ππ{sup *}) → S{sub 1}(nπ{sup *}) internal conversion in pyrazinemore » using TRPEI with UV pulses, this study presents a complete observation of the dynamics including radiationless transitions from S{sub 1} to S{sub 0} (internal conversion) and T{sub 1}(nπ{sup *}) (intersystem crossing). Also discussed are the role of {sup 1}A{sub u}(nπ{sup *}) in the internal conversion and the configuration interaction of the S{sub 2}(ππ{sup *}) electronic wave function.« less

Ultrafast photoconductivity of undoped cuprates

NASA Astrophysics Data System (ADS)

Dodge, J. Steven; Farahani, Amir; Petersen, Jesse; Liang, Ruixing; Bozovic, Ivan

2010-03-01

Using a visible pump-THz probe technique, we studied the ultrafast transient photoconductivity of the insulating cuprate La2CuO4, and compared it with earlier measurements of Sr2CuO2Cl2 and YBa2Cu3O6. In all these compounds, we observe a rapid onset of photoconductivity that is followed by a non-exponential relaxation on a picosecond time scales, the dynamics of which are independent of photocarrier concentration ranging from 0.2 to 1.5 percent. The photoconductivity decay is qualitatively similar to the decay of the photoinduced gap absorption in Sr2CuO2Cl2,footnotetextJ. S. Dodge, arXiv:0910.5048 indicating a common origin for the two effects. Assuming a quantum efficiency of unity, the estimated peak mobility for all three compounds is within 0.1-0.4 cm^2/V.s; this is lower than the Hall mobility in chemically doped systems with similar carrier concentrations,footnotetext Ando et al, Phys. Rev. Lett. 87, 017001 (2001) but orders of magnitude larger than earlier DC photoconductivity results.footnotetextThio et al, Phys. Rev. B 42, 10800 (1990) The similarity of the peak photoconductivity across three different compounds indicates that it is an intrinsic feature of the copper oxide plane.

Photoionization and electron radical recombination dynamics in photoactive yellow protein investigated by ultrafast spectroscopy in the visible and near-infrared spectral region.

PubMed

Zhu, Jingyi; Paparelli, Laura; Hospes, Marijke; Arents, Jos; Kennis, John T M; van Stokkum, Ivo H M; Hellingwerf, Klaas J; Groot, Marie Louise

2013-09-26

Photoinduced ionization of the chromophore inside photoactive yellow protein (PYP) was investigated by ultrafast spectroscopy in the visible and near-infrared spectral regions. An absorption band that extended from around 550 to 850 nm was observed and ascribed to solvated electrons, ejected from the p-hydroxycinnamic acid anion chromophore upon the absorption of two 400 nm photons. Global kinetic analysis showed that the solvated electron absorption decayed in two stages: a shorter phase of around 10 ps and a longer phase of more than 3 ns. From a simulation based on a diffusion model we conclude that the diffusion rate of the electron is about 0.8 Å(2)/ps in wild type PYP, and that the electron is ejected to a short distance of only several angstroms away from the chromophore. The chromophore-protein pocket appears to provide a water-similar local environment for the electron. Because mutations at different places around the chromophore have different effect on the electron recombination dynamics, we suggest that solvated electrons could provide a new method to investigate the local dielectric environment inside PYP and thus help to understand the role of the protein in the photoisomerization process.

Watching the dynamics of electrons and atoms at work in solar energy conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canton, S. E.; Zhang, X.; Liu, Y.

2015-07-06

The photochemical reactions performed by transition metal complexes have been proposed as viable routes towards solar energy conversion and storage into other forms that can be conveniently used in our everyday applications. In order to develop efficient materials, it is necessary to identify, characterize and optimize the elementary steps of the entire process on the atomic scale. To this end, we have studied the photoinduced electronic and structural dynamics in two heterobimetallic ruthenium–cobalt dyads, which belong to the large family of donor–bridge–acceptor systems. Using a combination of ultrafast optical and X-ray absorption spectroscopies, we can clock the light-driven electron transfermore » processes with element and spin sensitivity. In addition, the changes in local structure around the two metal centers are monitored. These experiments show that the nature of the connecting bridge is decisive for controlling the forward and the backward electron transfer rates, a result supported by quantum chemistry calculations. More generally, this work illustrates how ultrafast optical and X-ray techniques can disentangle the influence of spin, electronic and nuclear factors on the intramolecular electron transfer process. Finally, some implications for further improving the design of bridged sensitizer-catalysts utilizing the presented methodology are outlined.« less

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

CdSe quantum dot-fullerene hybrid nanocomposite for solar energy conversion: electron transfer and photoelectrochemistry.

PubMed

Bang, Jin Ho; Kamat, Prashant V

2011-12-27

The development of organic/inorganic hybrid nanocomposite systems that enable efficient solar energy conversion has been important for applications in solar cell research. Nanostructured carbon-based systems, in particular C(60), offer attractive strategies to collect and transport electrons generated in a light harvesting assembly. We have assembled CdSe-C(60) nanocomposites by chemically linking CdSe quantum dots (QDs) with thiol-functionalized C(60). The photoinduced charge separation and collection of electrons in CdSe QD-C(60) nanocomposites have been evaluated using transient absorption spectroscopy and photoelectrochemical measurements. The rate constant for electron transfer between excited CdSe QD and C(60) increased with the decreasing size of the CdSe QD (7.9 × 10(9) s(-1) (4.5 nm), 1.7 × 10(10) s(-1) (3.2 nm), and 9.0 × 10(10) s(-1) (2.6 nm)). Slower hole transfer and faster charge recombination and transport events were found to dominate over the forward electron injection process, thus limiting the deliverance of maximum power in CdSe QD-C(60)-based solar cells. The photoinduced charge separation between CdSe QDs and C(60) opens up new design strategies for developing light harvesting assemblies.

Ultrafast charge separation dynamics in opaque, operational dye-sensitized solar cells revealed by femtosecond diffuse reflectance spectroscopy

PubMed Central

Ghadiri, Elham; Zakeeruddin, Shaik M.; Hagfeldt, Anders; Grätzel, Michael; Moser, Jacques-E.

2016-01-01

Efficient dye-sensitized solar cells are based on highly diffusive mesoscopic layers that render these devices opaque and unsuitable for ultrafast transient absorption spectroscopy measurements in transmission mode. We developed a novel sub-200 femtosecond time-resolved diffuse reflectance spectroscopy scheme combined with potentiostatic control to study various solar cells in fully operational condition. We studied performance optimized devices based on liquid redox electrolytes and opaque TiO2 films, as well as other morphologies, such as TiO2 fibers and nanotubes. Charge injection from the Z907 dye in all TiO2 morphologies was observed to take place in the sub-200 fs time scale. The kinetics of electron-hole back recombination has features in the picosecond to nanosecond time scale. This observation is significantly different from what was reported in the literature where the electron-hole back recombination for transparent films of small particles is generally accepted to occur on a longer time scale of microseconds. The kinetics of the ultrafast electron injection remained unchanged for voltages between +500 mV and –690 mV, where the injection yield eventually drops steeply. The primary charge separation in Y123 organic dye based devices was clearly slower occurring in two picoseconds and no kinetic component on the shorter femtosecond time scale was recorded. PMID:27095505

Charge transfer in the weak driving force limit in blends of MDMO-PPV and dithienylthiazolo[5,4-d]thiazoles towards organic photovoltaics with high V(OC).

PubMed

Nevil, Nissy; Ling, Yun; Van Mierloo, Sarah; Kesters, Jurgen; Piersimoni, Fortunato; Adriaensens, Peter; Lutsen, Laurence; Vanderzande, Dirk; Manca, Jean; Maes, Wouter; Van Doorslaer, Sabine; Goovaerts, Etienne

2012-12-05

A series of three 5'-aryl-2,5-dithienylthiazolo[5,4-d]thiazole (DTTzTz) semiconducting molecules with different aryl substituents has been investigated as alternative acceptor materials in combination with the donor polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) in order to evaluate the photoinduced charge transfer (CT) efficiency in the resulting blends, designed towards possible application in organic photovoltaics. Photoluminescence quenching together with polaron detection by electron paramagnetic resonance and photoinduced absorption (PIA) demonstrate an increasing charge transfer efficiency when the DTTzTz substituents are varied from thien-2-yl to 4-trifluoromethylphenyl and 4-cyanophenyl groups, correlating well with the increasing acceptor strength in this series of molecules. In line with this observation, there is a decrease in the effective optical bandgap relative to pure MDMO-PPV that becomes more pronounced along this series of acceptor compounds, reaching 0.12 eV in the blend with 4-CN-Ph-DTTzTz. Intermolecular interactions between the blend components lead to lower energy transitions which are found to contribute significantly to the device external quantum efficiency. The high V(OC) reached in devices based on MDMO-PPV:4-CN-Ph-DTTzTz blends meets the expectations for such a donor:acceptor combination. However, thermal activation of charge carrier recombination occurs because of the weak driving force for charge transfer, as shown by time-dependent PIA measurements, and this is suggested as a cause for the observed low photovoltaic performance.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None, None

Coulomb interaction between charged particles inside a bunch is one of the most importance collective effects in beam dynamics, becoming even more significant as the energy of the particle beam is lowered to accommodate analytical and low-Z material imaging purposes such as in the time resolved Ultrafast Electron Microscope (UEM) development currently underway at Michigan State University. In addition, space charge effects are the key limiting factor in the development of ultrafast atomic resolution electron imaging and diffraction technologies and are also correlated with an irreversible growth in rms beam emittance due to fluctuating components of the nonlinear electron dynamics.more » In the short pulse regime used in the UEM, space charge effects also lead to virtual cathode formation in which the negative charge of the electrons emitted at earlier times, combined with the attractive surface field, hinders further emission of particles and causes a degradation of the pulse properties. Space charge and virtual cathode effects and their remediation are core issues for the development of the next generation of high-brightness UEMs. Since the analytical models are only applicable for special cases, numerical simulations, in addition to experiments, are usually necessary to accurately understand the space charge effect. In this paper we will introduce a grid-free differential algebra based multiple level fast multipole algorithm, which calculates the 3D space charge field for n charged particles in arbitrary distribution with an efficiency of O(n), and the implementation of the algorithm to a simulation code for space charge dominated photoemission processes.« less

Novel photoinduced phase transitions in transition metal oxides and diluted magnetic semiconductors.

PubMed

Mizokawa, Takashi

2012-10-23

Some transition metal oxides have frustrated electronic states under multiphase competition due to strongly correlated d electrons with spin, charge, and orbital degrees of freedom and exhibit drastic responses to external stimuli such as optical excitation. Here, we present photoemission studies on Pr0.55(Ca1 - ySry)0.45MnO3 (y = 0.25), SrTiO3, and Ti1 - xCoxO2 (x = 0.05, 0.10) under laser illumination and discuss electronic structural changes induced by optical excitation in these strongly correlated oxides. We discuss the novel photoinduced phase transitions in these transition metal oxides and diluted magnetic semiconductors on the basis of polaronic pictures such as orbital, ferromagnetic, and ferroelectric polarons.

Photo-induced electron transfer method

DOEpatents

Wohlgemuth, Roland; Calvin, Melvin

1984-01-01

The efficiency of photo-induced electron transfer reactions is increased and the back transfer of electrons in such reactions is greatly reduced when a photo-sensitizer zinc porphyrin-surfactant and an electron donor manganese porphyrin-surfactant are admixed into phospho-lipid membranes. The phospholipids comprising said membranes are selected from phospholipids whose head portions are negatively charged. Said membranes are contacted with an aqueous medium in which an essentially neutral viologen electron acceptor is admixed. Catalysts capable of transfering electrons from reduced viologen electron acceptor to hydrogen to produce elemental hydrogen are also included in the aqueous medium. An oxidizable olefin is also admixed in the phospholipid for the purpose of combining with oxygen that coordinates with oxidized electron donor manganese porphyrin-surfactant.

Electrically-driven GHz range ultrafast graphene light emitter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kim, Youngduck; Gao, Yuanda; Shiue, Ren-Jye; Wang, Lei; Aslan, Ozgur Burak; Kim, Hyungsik; Nemilentsau, Andrei M.; Low, Tony; Taniguchi, Takashi; Watanabe, Kenji; Bae, Myung-Ho; Heinz, Tony F.; Englund, Dirk R.; Hone, James

2017-02-01

Ultrafast electrically driven light emitter is a critical component in the development of the high bandwidth free-space and on-chip optical communications. Traditional semiconductor based light sources for integration to photonic platform have therefore been heavily studied over the past decades. However, there are still challenges such as absence of monolithic on-chip light sources with high bandwidth density, large-scale integration, low-cost, small foot print, and complementary metal-oxide-semiconductor (CMOS) technology compatibility. Here, we demonstrate the first electrically driven ultrafast graphene light emitter that operate up to 10 GHz bandwidth and broadband range (400 1600 nm), which are possible due to the strong coupling of charge carriers in graphene and surface optical phonons in hBN allow the ultrafast energy and heat transfer. In addition, incorporation of atomically thin hexagonal boron nitride (hBN) encapsulation layers enable the stable and practical high performance even under the ambient condition. Therefore, electrically driven ultrafast graphene light emitters paves the way towards the realization of ultrahigh bandwidth density photonic integrated circuits and efficient optical communications networks.

Conductive polymer/fullerene blend thin films with honeycomb framework for transparent photovoltaic application

DOEpatents

Cotlet, Mircea; Wang, Hsing-Lin; Tsai, Hsinhan; Xu, Zhihua

2015-04-21

Optoelectronic devices and thin-film semiconductor compositions and methods for making same are disclosed. The methods provide for the synthesis of the disclosed composition. The thin-film semiconductor compositions disclosed herein have a unique configuration that exhibits efficient photo-induced charge transfer and high transparency to visible light.

Photodetachment process for beam neutralization

DOEpatents

Fink, Joel H. [Livermore, CA; Frank, Alan M. [Livermore, CA

1979-02-20

A process for neutralization of accelerated ions employing photo-induced charge detachment. The process involves directing a laser beam across the path of a negative ion beam such as to effect photodetachment of electrons from the beam ions. The frequency of the laser beam employed is selected to provide the maximum cross-section for the photodetachment process.

Exciplexes versus Loose Ion Pairs: How Does the Driving Force Impact the Initial Product Ratio of Photoinduced Charge Separation Reactions?

PubMed Central

2014-01-01

Many donor–acceptor systems can undergo a photoinduced charge separation reaction, yielding loose ion pairs (LIPs). LIPs can be formed either directly via (distant) electron transfer (ET) or indirectly via the dissociation of an initially formed exciplex or tight ion pair. Establishing the prevalence of one of the reaction pathways is challenging because differentiating initially formed exciplexes from LIPs is difficult due to similar spectroscopic footprints. Hence, no comprehensive reaction model has been established for moderately polar solvents. Here, we employ an approach based on the time-resolved magnetic field effect (MFE) of the delayed exciplex luminescence to distinguish the two reaction channels. We focus on the effects of the driving force of ET and the solvent permittivity. We show that, surprisingly, the exciplex channel is significant even for an exergonic ET system with a free energy of ET of −0.58 eV and for the most polar solutions studied (butyronitrile). Our findings demonstrate that exciplexes play a crucial role even in polar solvents and at moderate driving forces, contrary to what is usually assumed. PMID:25243054

Photo-induced interaction of thioglycolic acid (TGA)-capped CdTe quantum dots with cyanine dyes

NASA Astrophysics Data System (ADS)

Abdelbar, Mostafa F.; Fayed, Tarek A.; Meaz, Talaat M.; Ebeid, El-Zeiny M.

2016-11-01

The photo-induced interaction of three different sizes of thioglycolic acid (TGA)-capped CdTe quantum dots (CdTe QDs) with two monomethine cyanine dyes belonging to the thiazole orange (TO) family has been studied. Positively charged cyanines interact with QDs surface which is negatively charged due to capping agent carboxylate ions. The energy transfer parameters including Stern-Volmer constant, Ksv, number of binding sites, n, quenching sphere radius, r, the critical energy transfer distance, R0, and energy transfer efficiencies, E have been calculated. The effect of structure and the number of aggregating molecules have been studied as a function of CdTe QDs particle size. Combining organic and inorganic semiconductors leads to increase of the effective absorption cross section of the QDs which can be utilized in novel nanoscale designs for light-emitting, photovoltaic and sensor applications. A synthesized triplet emission of the studied dyes was observed using CdTe QDs as donors and this is expected to play a potential role in molecular oxygen sensitization and in photodynamic therapy (PDT) applications.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors

NASA Astrophysics Data System (ADS)

Zhang, Xian-Fu; Feng, Nan

2018-01-01

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism. All measured data and quantum chemical results suggest that these systems can be viewed as electron donor-acceptor (D-A) pair (BODIPY acts as the acceptor), photoinduced charge transfer (PCT) or photoinduced electron transfer (PET) occurs upon photo excitation (D-A + hν → Dδ +-Aδ -, 0 < δ ≤ 1), and the charge recombination induced the formation of triplet state (Dδ +-Aδ - → D-A (T1). These novel PCT- or PET-based photosensitizers (PSs) show different features from traditional PSs, such as the strong tunability by facile structural modification and good selectivity upon medium polarity. The new character for this type of PSs can lead to important applications in organic oxygenation reactions and photodynamic therapy of tumors.

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

Photoinduced ICT vs. excited rotamer intercoversion in two quadrupolar polyaromatic N-methylpyridinium cations.

PubMed

Cesaretti, A; Carlotti, B; Elisei, F; Fortuna, C G; Spalletti, A

2018-01-24

The excited state dynamics of two quadrupolar polyaromatic N-methylpyridinium cations have been fully investigated in order to acquire detailed information on their photo-induced behavior. The two molecules are symmetric push-pull compounds having a D-π-A + -π-D motif, with the same electron-acceptor central unit (A = N-methylpyridinium) and two distinctive electron-donor polyaromatic side groups (D), namely naphthyl and pyrenyl substituents. Both molecules undergo charge transfer during the absorption, as revealed by a significant solvatochromism exhibited with solvent polarity, but the fate of their excited state was found to be markedly different. The careful analysis of the data gathered from femtosecond-resolved fluorescence up-conversion and transient absorption experiments, supported by DFT quantum mechanical calculations and temperature-dependent stationary measurements, shows the leading role of intramolecular charge transfer, assisted by symmetry breaking, in the pyrenyl derivative and that of rotamer interconversion in the naphthtyl one. Both excited state processes are controlled by the viscosity rather than polarity of the solvent, and they occur during inertial solvation in low-viscous media and lengthening up to tens of picoseconds in highly viscous solvents.

Ultrafast dynamics of colloidal semiconductor nanocrystals relevant to solar fuels production

NASA Astrophysics Data System (ADS)

Cogan, Nicole M. B.; Liu, Cunming; Qiu, Fen; Burke, Rebeckah; Krauss, Todd D.

2017-05-01

Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. Ultrafast transient absorption spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts reveal extremely fast ET, and provide a fundamental explanation for the exceptional photocatalytic H2 activity. Additionally, by studying H2 production of the Ni catalyst with CdSe/CdS nanoparticles of various structures, it was determined that surface charge density plays an important role in charge transfer and ultimately H2 production activity.

Ultrafast exciton dynamics and light-driven H2 evolution in colloidal semiconductor nanorods and Pt-tipped nanorods.

PubMed

Wu, Kaifeng; Zhu, Haiming; Lian, Tianquan

2015-03-17

Colloidal quantum confined one-dimensional (1D) semiconductor nanorods (NRs) and related semiconductor-metal heterostructures are promising new materials for efficient solar-to-fuel conversion because of their unique physical and chemical properties. NRs can simultaneously exhibit quantum confinement effects in the radial direction and bulk like carrier transport in the axial direction. The former implies that concepts well-established in zero-dimensional quantum dots, such as size-tunable energetics and wave function engineering through band alignment in heterostructures, can also be applied to NRs; while the latter endows NRs with fast carrier transport to achieve long distance charge separation. Selective growth of catalytic metallic nanoparticles, such as Pt, at the tips of NRs provides convenient routes to multicomponent heterostructures with photocatalytic capabilities and controllable charge separation distances. The design and optimization of such materials for efficient solar-to-fuel conversion require the understanding of exciton and charge carrier dynamics. In this Account, we summarize our recent studies of ultrafast charge separation and recombination kinetics and their effects on steady-state photocatalytic efficiencies of colloidal CdS and CdSe/CdS NRs and related NR-Pt heterostructures. After a brief introduction of their electronic structure, we discuss exciton dynamics of CdS NRs. By transient absorption and time-resolved photoluminescence decay, it is shown that although the conduction band electrons are long-lived, photogenerated holes in CdS NRs are trapped on an ultrafast time scale (∼0.7 ps), which forms localized excitons due to strong Coulomb interaction in 1D NRs. In quasi-type II CdSe/CdS dot-in-rod NRs, a large valence band offset drives the ultrafast localization of holes to the CdSe core, and the competition between this process and ultrafast hole trapping on a CdS rod leads to three types of exciton species with distinct spatial distributions. The effect of the exciton dynamics on photoreduction reactions is illustrated using methyl viologen (MV(2+)) as a model electron acceptor. The steady-state MV(2+) photoreduction quantum yield of CdSe/CdS dot-in-rod NRs approaches unity under rod excitation, much larger than CdSe QDs and CdSe/CdS core/shell QDs. Detailed time-resolved studies show that in quasi-type II CdSe/CdS NRs and type II ZnSe/CdS NRs strong quantum confinement in the radial direction facilitates fast electron transfer and hole removal, whereas the fast carrier mobility along the axial direction enables long distance charge separation and slow charge recombination, which is essential for efficient MV(2+) photoreduction. The NR/MV(2+) relay system can be coupled to Pt nanoparticles in solution for light-driven H2 generation. Alternatively, Pt-tipped CdS and CdSe/CdS NRs provide fully integrated all inorganic systems for light-driven H2 generation. In CdS-Pt and CdSe/CdS-Pt hetero-NRs, ultrafast hole trapping on the CdS rod surface or in CdSe core enables efficient electron transfer from NRs to Pt tips by suppressing hole and energy transfer. It is shown that the quantum yields of photodriven H2 generation using these heterostructures correlate well with measured hole transfer rates from NRs to sacrificial donors, revealing that hole removal is the key efficiency-limiting step. These findings provide important insights for designing more efficient quantum confined NR and NR-Pt based systems for solar-to-fuel conversion.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

PubMed

Bischak, Connor G; Hetherington, Craig L; Wu, Hao; Aloni, Shaul; Ogletree, D Frank; Limmer, David T; Ginsberg, Naomi S

2017-02-08

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

Driving Protein Conformational Changes with Light: Photoinduced Structural Rearrangement in a Heterobimetallic Oxidase.

PubMed

Maugeri, Pearson T; Griese, Julia J; Branca, Rui M; Miller, Effie K; Smith, Zachary R; Eirich, Jürgen; Högbom, Martin; Shafaat, Hannah S

2018-01-31

The heterobimetallic R2lox protein binds both manganese and iron ions in a site-selective fashion and activates oxygen, ultimately performing C-H bond oxidation to generate a tyrosine-valine cross-link near the active site. In this work, we demonstrate that, following assembly, R2lox undergoes photoinduced changes to the active site geometry and metal coordination motif. Through spectroscopic, structural, and mass spectrometric characterization, the photoconverted species is found to consist of a tyrosinate-bound iron center following light-induced decarboxylation of a coordinating glutamate residue and cleavage of the tyrosine-valine cross-link. This process occurs with high quantum efficiencies (Φ = 3%) using violet and near-ultraviolet light, suggesting that the photodecarboxylation is initiated via ligand-to-metal charge transfer excitation. Site-directed mutagenesis and structural analysis suggest that the cross-linked tyrosine-162 is the coordinating residue. One primary product is observed following irradiation, indicating potential use of this class of proteins, which contains a putative substrate channel, for controlled photoinduced decarboxylation processes, with relevance for in vivo functionality of R2lox as well as application in environmental remediation.

Photo-induced halide redistribution in organic–inorganic perovskite films

DOE PAGES

deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; ...

2016-05-24

Organic-inorganic perovskites such as CH 3NH 3PbI 3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH 3NH 3PbI 3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction inmore » trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. In conclusion, our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.« less

Investigations of ultrafast charge dynamics in laser-irradiated targets by a self probing technique employing laser driven protons

NASA Astrophysics Data System (ADS)

Ahmed, H.; Kar, S.; Cantono, G.; Nersisyan, G.; Brauckmann, S.; Doria, D.; Gwynne, D.; Macchi, A.; Naughton, K.; Willi, O.; Lewis, C. L. S.; Borghesi, M.

2016-09-01

The divergent and broadband proton beams produced by the target normal sheath acceleration mechanism provide the unique opportunity to probe, in a point-projection imaging scheme, the dynamics of the transient electric and magnetic fields produced during laser-plasma interactions. Commonly such experimental setup entails two intense laser beams, where the interaction produced by one beam is probed with the protons produced by the second. We present here experimental studies of the ultra-fast charge dynamics along a wire connected to laser irradiated target carried out by employing a 'self' proton probing arrangement - i.e. by connecting the wire to the target generating the probe protons. The experimental data shows that an electromagnetic pulse carrying a significant amount of charge is launched along the wire, which travels as a unified pulse of 10s of ps duration with a velocity close to speed of light. The experimental capabilities and the analysis procedure of this specific type of proton probing technique are discussed.

Charge Transfer Dynamics at Dye-Sensitized ZnO and TiO2 Interfaces Studied by Ultrafast XUV Photoelectron Spectroscopy

PubMed Central

Borgwardt, Mario; Wilke, Martin; Kampen, Thorsten; Mähl, Sven; Xiao, Manda; Spiccia, Leone; Lange, Kathrin M.; Kiyan, Igor Yu.; Aziz, Emad F.

2016-01-01

Interfacial charge transfer from photoexcited ruthenium-based N3 dye molecules into ZnO thin films received controversial interpretations. To identify the physical origin for the delayed electron transfer in ZnO compared to TiO2, we probe directly the electronic structure at both dye-semiconductor interfaces by applying ultrafast XUV photoemission spectroscopy. In the range of pump-probe time delays between 0.5 to 1.0 ps, the transient signal of the intermediate states was compared, revealing a distinct difference in their electron binding energies of 0.4 eV. This finding strongly indicates the nature of the charge injection at the ZnO interface associated with the formation of an interfacial electron-cation complex. It further highlights that the energetic alignment between the dye donor and semiconductor acceptor states appears to be of minor importance for the injection kinetics and that the injection efficiency is dominated by the electronic coupling. PMID:27073060

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

PubMed

Cao, Jun

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

NASA Astrophysics Data System (ADS)

Cao, Jun

2015-06-01

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

Photoinduced relaxation dynamics of nitrogen-capped silicon nanoclusters: a TD-DFT study

NASA Astrophysics Data System (ADS)

Liu, Xiang-Yang; Xie, Xiao-Ying; Fang, Wei-Hai; Cui, Ganglong

2018-04-01

Herein we have developed and implemented a TD-DFT-based surface-hopping dynamics simulation method with a recently proposed numerical algorithm capable of efficiently computing nonadiabatic couplings, a semiclassical spectrum simulation method, and an excited-state character analysis method based on one-electron transition density matrix. With the use of these developed methods, we have studied the spectroscopic properties, excited-state characters, and photoinduced relaxation dynamics of three silicon nanoclusters capped with different chromophores (Cl@SiQD, Car@SiQD, Azo@SiQD). Spectroscopically, the main absorption peak is visibly red-shifted from Cl@SiQD via Car@SiQD to Azo@SiQD. In contrast to Cl@SiQD and Car@SiQD, there are two peaks observed in Azo@SiQD. Mechanistically, the excited-state relaxation to the lowest S1 excited singlet state is ultrafast in Cl@SiQD, which is less than 190 fs and without involving excited-state trapping. In comparison, there are clear excited-state trappings in Car@SiQD and Azo@SiQD. In the former, the S2 state is trapped more than 300 fs; in the latter, the S3 excited-state trapping is more than 615 fs. These results demonstrate that the interfacial interaction has significant influences on the spectroscopic properties and excited-state relaxation dynamics. The knowledge gained in this work could be helpful for the design of silicon nanoclusters with better photoluminescence performance.

Enhanced pairing susceptibility in a photodoped two-orbital Hubbard model

NASA Astrophysics Data System (ADS)

Werner, Philipp; Strand, Hugo U. R.; Hoshino, Shintaro; Murakami, Yuta; Eckstein, Martin

2018-04-01

Local spin fluctuations provide the glue for orbital-singlet spin-triplet pairing in the doped Mott insulating regime of multiorbital Hubbard models. At large Hubbard repulsion U , the pairing susceptibility is nevertheless tiny because the pairing interaction cannot overcome the suppression of charge fluctuations. Using nonequilibrium dynamical mean field simulations of the two-orbital Hubbard model, we show that out of equilibrium the pairing susceptibility in this large-U regime can be strongly enhanced by creating a photoinduced population of the relevant charge states. This enhancement is supported by the long lifetime of photodoped charge carriers and a built-in cooling mechanism in multiorbital Hubbard systems.

The differential algebra based multiple level fast multipole algorithm for 3D space charge field calculation and photoemission simulation

DOE PAGES

None, None

2015-09-28

Coulomb interaction between charged particles inside a bunch is one of the most importance collective effects in beam dynamics, becoming even more significant as the energy of the particle beam is lowered to accommodate analytical and low-Z material imaging purposes such as in the time resolved Ultrafast Electron Microscope (UEM) development currently underway at Michigan State University. In addition, space charge effects are the key limiting factor in the development of ultrafast atomic resolution electron imaging and diffraction technologies and are also correlated with an irreversible growth in rms beam emittance due to fluctuating components of the nonlinear electron dynamics.more » In the short pulse regime used in the UEM, space charge effects also lead to virtual cathode formation in which the negative charge of the electrons emitted at earlier times, combined with the attractive surface field, hinders further emission of particles and causes a degradation of the pulse properties. Space charge and virtual cathode effects and their remediation are core issues for the development of the next generation of high-brightness UEMs. Since the analytical models are only applicable for special cases, numerical simulations, in addition to experiments, are usually necessary to accurately understand the space charge effect. In this paper we will introduce a grid-free differential algebra based multiple level fast multipole algorithm, which calculates the 3D space charge field for n charged particles in arbitrary distribution with an efficiency of O(n), and the implementation of the algorithm to a simulation code for space charge dominated photoemission processes.« less

Photo-induced electronic properties in single quantum well system: effect of excitonic lifetime

NASA Astrophysics Data System (ADS)

Patwari, Jayita; Ghadi, Hemant; Sardar, Samim; Singhal, Jashan; Tongbram, Binita; Shyamal, Sanjib; Bhattacharya, Chinmoy; Chakrabarti, Subhananda; Pal, Samir Kumar

2017-01-01

In the present study, we have established a correlation between the photo-induced electronic phenomena and excited state lifetime of the photo generated carriers in double barrier Al0.3Ga0.7As\\GaAs quantum well (QW) structures. The excited state lifetime was measured experimentally by picosecond time resolved photoluminescence spectroscopy for two samples with different well widths (5.3 nm and 16.5 nm). The faster nonradiative decay time of the narrower well can be attributed to the facile escape of electrons from well to barrier due to lower associated energy compared to that of the thicker well which resembles the simulated results of the energy level distribution. The proposed mechanism of carrier escape is further proven from the higher value of unconventional excitonic capacitance value in the thicker well, measured by impedance spectroscopy. The dependence of photo-induced capacitance on well thickness is explained by the lifetime of the excited carriers in this study. Dependence of the photo-generated capacitance (C) on externally applied bias voltage (V) was also studied to quantitatively establish a proportional relation between the carrier holding capacity of the well and the excitonic lifetime. The higher accumulation of charge and lower ground state energy of the thicker well is evident from the higher tunnelling current found for the same in the photocurrent (I) versus voltage (V) measurement. Thus the escape of electrons from the well to barrier is the key factor affecting the photo generated charge accumulation and its holding capacity which in turn influences the device performances.

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

DOE PAGES

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan; ...

2017-02-21

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Modeling ultrafast exciton migration within the electron donor domains of bulk heterojunction organic photovoltaics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bednarz, Mateusz; Lapin, Joel; McGillicuddy, Ryan

Recent experimental studies revealed that charge carriers harvested by bulk heterojunction organic photovoltaics can be collected on ultrafast time scales. To investigate ultrafast exciton mobility, we construct simple, nonatomistic models of a common polymeric electron donor material. We first explore the relationship between the magnitude of energetic noise in the model Hamiltonian and the spatial extent of resulting eigenstates. We then employ a quantum master equation approach to simulate migration of chromophore-localized initial excited states. Excitons initially localized on a single chromophore at the center of the model delocalize down polymer chains and across pi-stacked chromophores through a coherent, wavelikemore » mechanism during the first few tens of femtoseconds. We explore the dependence of this coherent delocalization on coupling strength and on the magnitude of energetic noise. At longer times we observe continued migration toward a uniform population distribution that proceeds through an incoherent, diffusive mechanism. A series of simulations modeling exciton harvesting in domains of varying size demonstrates that smaller domains enhance ultrafast exciton harvesting yield. Finally, our nonatomistic model falls short of quantitative accuracy but demonstrates that excitons are mobile within electron donor domains on ultrafast time scales and that coherent exciton transport can enhance ultrafast exciton harvesting.« less

Strong negative terahertz photoconductivity in photoexcited graphene

NASA Astrophysics Data System (ADS)

Fu, Maixia; Wang, Xinke; Ye, Jiasheng; Feng, Shengfei; Sun, Wenfeng; Han, Peng; Zhang, Yan

2018-01-01

Terahertz (THz) response of a chemical vapor deposited graphene on a quartz substrate has been investigated by using an ultrafast optical-pump THz-probe spectroscopy. Without photoexcitation, the frequency-dependence optical conductivity shows a strong carrier response owing to the intrinsically doped graphene. Upon photoexcitation, an enhancement in THz transmission is observed and the transmission increases nonlinearly with the increase of pump power, which is rooted in a reduction of intrinsic conductivity arising from the strong enhancement of carrier scattering rather than THz emission occurrence. The modulation depth of 18.8% was experimentally achieved, which is more than four times greater than that of the previous reported. The photoinduced response here highlights the variety of response possible in graphene depending on the sample quality, carrier mobility and doping level. The graphene provides promising applications in high-performance THz modulators and THz photoelectric devices.

Light-Activated Gigahertz Ferroelectric Domain Dynamics

NASA Astrophysics Data System (ADS)

Akamatsu, Hirofumi; Yuan, Yakun; Stoica, Vladimir A.; Stone, Greg; Yang, Tiannan; Hong, Zijian; Lei, Shiming; Zhu, Yi; Haislmaier, Ryan C.; Freeland, John W.; Chen, Long-Qing; Wen, Haidan; Gopalan, Venkatraman

2018-03-01

Using time- and spatially resolved hard x-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO3 are simultaneously captured on subnanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photoinduced electric field of up to 20 ×106 V /m is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling method is developed that reveals the microscopic origin of these dynamics, leading to gigahertz polarization and elastic waves traveling in the crystal with sonic speeds and spatially varying frequencies. The advances in spatiotemporal imaging and dynamical modeling tools open up opportunities for disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains.

Ultrafast Dynamics of a Nucleobase Analogue Illuminated by a Short Intense X-ray Free Electron Laser Pulse

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagaya, K.; Motomura, K.; Kukk, E.

Understanding x-ray radiation damage is a crucial issue for both medical applications of x rays and x-ray free-electron-laser (XFEL) science aimed at molecular imaging. Decrypting the charge and fragmentation dynamics of nucleobases, the smallest units of a macro-biomolecule, contributes to a bottom-up understanding of the damage via cascades of phenomena following x-ray exposure. We investigate experimentally and by numerical simulations the ultrafast radiation damage induced on a nucleobase analogue (5-iodouracil) by an ultrashort (10 fs) high-intensity radiation pulse generated by XFEL at SPring-8 Angstrom Compact free electron Laser (SACLA). The present study elucidates a plausible underlying radiosensitizing mechanism of 5-iodouracil.more » This mechanism is independent of the exact composition of 5-iodouracil and thus relevant to other such radiosensitizers. Furthermore, we found that despite a rapid increase of the net molecular charge in the presence of iodine, and of the ultrafast release of hydrogen, the other atoms are almost frozen within the 10-fs duration of the exposure. Finally, this validates single-shot molecular imaging as a consistent approach, provided the radiation pulse used is brief enough.« less

Ultrafast Dynamics of a Nucleobase Analogue Illuminated by a Short Intense X-ray Free Electron Laser Pulse

DOE PAGES

Nagaya, K.; Motomura, K.; Kukk, E.; ...

2016-06-16

Understanding x-ray radiation damage is a crucial issue for both medical applications of x rays and x-ray free-electron-laser (XFEL) science aimed at molecular imaging. Decrypting the charge and fragmentation dynamics of nucleobases, the smallest units of a macro-biomolecule, contributes to a bottom-up understanding of the damage via cascades of phenomena following x-ray exposure. We investigate experimentally and by numerical simulations the ultrafast radiation damage induced on a nucleobase analogue (5-iodouracil) by an ultrashort (10 fs) high-intensity radiation pulse generated by XFEL at SPring-8 Angstrom Compact free electron Laser (SACLA). The present study elucidates a plausible underlying radiosensitizing mechanism of 5-iodouracil.more » This mechanism is independent of the exact composition of 5-iodouracil and thus relevant to other such radiosensitizers. Furthermore, we found that despite a rapid increase of the net molecular charge in the presence of iodine, and of the ultrafast release of hydrogen, the other atoms are almost frozen within the 10-fs duration of the exposure. Finally, this validates single-shot molecular imaging as a consistent approach, provided the radiation pulse used is brief enough.« less

Ultrafast dynamics of the photo-excited hemes b and cn in the cytochrome b6f complex.

PubMed

Agarwal, Rachna; Chauvet, Adrien A P

2017-01-25

The dynamics of hemes b and c n within the cytochrome b 6 f complex are investigated by means of ultrafast broad-band transient absorption spectroscopy. On the one hand, the data reveal that, subsequent to visible light excitation, part of the b hemes undergoes pulse-limited photo-oxidation, with the liberated electron supposedly being transferred to one of the adjacent aromatic amino acids. Photo-oxidation is followed by charge recombination in about 8.2 ps. Subsequent to charge recombination, heme b is promoted to a vibrationally excited ground state that relaxes in about 4.6 ps. On the other hand, heme c n undergoes ultrafast ground state recovery in about 140 fs. Interestingly, the data also show that, in contrast to previous beliefs, Chl a is involved in the photochemistry of hemes. Indeed, subsequent to heme excitation, Chl a bleaches and recovers to its ground state in 90 fs and 650 fs, respectively. Chl a bleaching allegedly corresponds to the formation of a short lived Chl a anion. Beyond the previously suggested structural role, this study provides unique evidence that Chl a is directly involved in the photochemistry of the hemes.

Battery capacity and recharging needs for electric buses in city transit service

DOE PAGES

Gao, Zhiming; Lin, Zhenhong; LaClair, Tim J.; ...

2017-01-27

Our paper evaluates the energy consumption and battery performance of city transit electric buses operating on real day-to-day routes and standardized bus drive cycles, based on a developed framework tool that links bus electrification feasibility with real-world vehicle performance, city transit bus service reliability, battery sizing and charging infrastructure. The impacts of battery capacity combined with regular and ultrafast charging over different routes have been analyzed in terms of the ability to maintain city transit bus service reliability like conventional buses. These results show that ultrafast charging via frequent short-time boost charging events, for example at a designated bus stopmore » after completing each circuit of an assigned route, can play a significant role in reducing the battery size and can eliminate the need for longer duration charging events that would cause schedule delays. Furthermore, the analysis presented shows that significant benefits can be realized by employing multiple battery configurations and flexible battery swapping practices in electric buses. These flexible design and use options will allow electric buses to service routes of varying city driving patterns and can therefore enable meaningful reductions to the cost of the vehicle and battery while ensuring service that is as reliable as conventional buses.« less

Battery capacity and recharging needs for electric buses in city transit service

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Zhiming; Lin, Zhenhong; LaClair, Tim J.

Our paper evaluates the energy consumption and battery performance of city transit electric buses operating on real day-to-day routes and standardized bus drive cycles, based on a developed framework tool that links bus electrification feasibility with real-world vehicle performance, city transit bus service reliability, battery sizing and charging infrastructure. The impacts of battery capacity combined with regular and ultrafast charging over different routes have been analyzed in terms of the ability to maintain city transit bus service reliability like conventional buses. These results show that ultrafast charging via frequent short-time boost charging events, for example at a designated bus stopmore » after completing each circuit of an assigned route, can play a significant role in reducing the battery size and can eliminate the need for longer duration charging events that would cause schedule delays. Furthermore, the analysis presented shows that significant benefits can be realized by employing multiple battery configurations and flexible battery swapping practices in electric buses. These flexible design and use options will allow electric buses to service routes of varying city driving patterns and can therefore enable meaningful reductions to the cost of the vehicle and battery while ensuring service that is as reliable as conventional buses.« less

Photodetachment process for beam neutralization

DOEpatents

Fink, J.H.; Frank, A.M.

1979-02-20

A process for neutralization of accelerated ions employing photo-induced charge detachment is disclosed. The process involves directing a laser beam across the path of a negative ion beam such as to effect photodetachment of electrons from the beam ions. The frequency of the laser beam employed is selected to provide the maximum cross-section for the photodetachment process. 2 figs.

Triplet exciton dissociation and electron extraction in graphene-templated pentacene observed with ultrafast spectroscopy.

PubMed

McDonough, Thomas J; Zhang, Lushuai; Roy, Susmit Singha; Kearns, Nicholas M; Arnold, Michael S; Zanni, Martin T; Andrew, Trisha L

2017-02-08

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Organic Semiconductor Photovoltaics

NASA Astrophysics Data System (ADS)

Sariciftci, Niyazi Serdar

2005-03-01

Recent developments on organic photovoltaic elements are reviewed. Semiconducting conjugated polymers and molecules as well as nanocrystalline inorganic semiconductors are used in composite thin films. The photophysics of such photoactive devices is based on the photoinduced charge transfer from donor type semiconducting molecules onto acceptor type molecules such as Buckminsterfullerene, C60 and/or nanoparticles. Similar to the first steps in natural photosynthesis, this photoinduced electron transfer leads to a number of potentially interesting applications which include sensitization of the photoconductivity and photovoltaic phenomena. Examples of photovoltaic architectures are discussed with their potential in terrestrial solar energy conversion. Several materials are introduced and discussed for their photovoltaic activities. Furthermore, nanomorphology has been investigated with AFM, SEM and TEM. The morphology/property relationship for a given photoactive system is found to be a major effect.

Scanning ultrafast electron microscopy

PubMed Central

Yang, Ding-Shyue; Mohammed, Omar F.; Zewail, Ahmed H.

2010-01-01

Progress has been made in the development of four-dimensional ultrafast electron microscopy, which enables space-time imaging of structural dynamics in the condensed phase. In ultrafast electron microscopy, the electrons are accelerated, typically to 200 keV, and the microscope operates in the transmission mode. Here, we report the development of scanning ultrafast electron microscopy using a field-emission-source configuration. Scanning of pulses is made in the single-electron mode, for which the pulse contains at most one or a few electrons, thus achieving imaging without the space-charge effect between electrons, and still in ten(s) of seconds. For imaging, the secondary electrons from surface structures are detected, as demonstrated here for material surfaces and biological specimens. By recording backscattered electrons, diffraction patterns from single crystals were also obtained. Scanning pulsed-electron microscopy with the acquired spatiotemporal resolutions, and its efficient heat-dissipation feature, is now poised to provide in situ 4D imaging and with environmental capability. PMID:20696933

Ultrafast terahertz control of extreme tunnel currents through single atoms on a silicon surface

NASA Astrophysics Data System (ADS)

Jelic, Vedran; Iwaszczuk, Krzysztof; Nguyen, Peter H.; Rathje, Christopher; Hornig, Graham J.; Sharum, Haille M.; Hoffman, James R.; Freeman, Mark R.; Hegmann, Frank A.

2017-06-01

Ultrafast control of current on the atomic scale is essential for future innovations in nanoelectronics. Extremely localized transient electric fields on the nanoscale can be achieved by coupling picosecond duration terahertz pulses to metallic nanostructures. Here, we demonstrate terahertz scanning tunnelling microscopy (THz-STM) in ultrahigh vacuum as a new platform for exploring ultrafast non-equilibrium tunnelling dynamics with atomic precision. Extreme terahertz-pulse-driven tunnel currents up to 107 times larger than steady-state currents in conventional STM are used to image individual atoms on a silicon surface with 0.3 nm spatial resolution. At terahertz frequencies, the metallic-like Si(111)-(7 × 7) surface is unable to screen the electric field from the bulk, resulting in a terahertz tunnel conductance that is fundamentally different than that of the steady state. Ultrafast terahertz-induced band bending and non-equilibrium charging of surface states opens new conduction pathways to the bulk, enabling extreme transient tunnel currents to flow between the tip and sample.

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Sung; Rolczynski, Brian S.; Xu, Tao

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast,more » P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.« less

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT.

PubMed

Cho, Sung; Rolczynski, Brian S; Xu, Tao; Yu, Luping; Chen, Lin X

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast, P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.

Impact of charge-transfer excitons in regioregular polythiophene on the charge separation at polythiophene-fullerene heterojunctions

NASA Astrophysics Data System (ADS)

Polkehn, M.; Tamura, H.; Burghardt, I.

2018-01-01

This study addresses the mechanism of ultrafast charge separation in regioregular oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene (P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation of polaronic inter-chain charge separated species in highly ordered oligothiophene has been demonstrated in recent experiments and could have a significant impact on the net charge transfer to the fullerene acceptor. The present approach combines a first-principles parametrized multi-site Hamiltonian, based on time-dependent density functional theory calculations, with accurate quantum dynamics simulations using the multi-layer multi-configuration time-dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this analysis by including the dynamical role of charge transfer excitons. Our investigation highlights the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the oligothiophene domain, and the opening of new transfer channels due the creation of such charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge transfer state can be largely circumvented due to the presence of charge transfer excitons. However, the latter states in turn act as a trap, such that the free carrier yield observed on ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the transfer pathways at P3HT-PCBM type junctions.

Four-dimensional ultrafast electron microscopy of phase transitions

PubMed Central

Grinolds, Michael S.; Lobastov, Vladimir A.; Weissenrieder, Jonas; Zewail, Ahmed H.

2006-01-01

Reported here is direct imaging (and diffraction) by using 4D ultrafast electron microscopy (UEM) with combined spatial and temporal resolutions. In the first phase of UEM, it was possible to obtain snapshot images by using timed, single-electron packets; each packet is free of space–charge effects. Here, we demonstrate the ability to obtain sequences of snapshots (“movies”) with atomic-scale spatial resolution and ultrashort temporal resolution. Specifically, it is shown that ultrafast metal–insulator phase transitions can be studied with these achieved spatial and temporal resolutions. The diffraction (atomic scale) and images (nanometer scale) we obtained manifest the structural phase transition with its characteristic hysteresis, and the time scale involved (100 fs) is now studied by directly monitoring coordinates of the atoms themselves. PMID:17130445

Ultrafast photocurrents in monolayer MoS2

NASA Astrophysics Data System (ADS)

Parzinger, Eric; Wurstbauer, Ursula; Holleitner, Alexander W.

Two-dimensional transition metal dichalcogenides such as MoS2 have emerged as interesting materials for optoelectronic devices. In particular, the ultrafast dynamics and lifetimes of photoexcited charge carriers have attracted great interest during the last years. We investigate the photocurrent response of monolayer MoS2 on a picosecond time scale utilizing a recently developed pump-probe spectroscopy technique based on coplanar striplines. We discuss the ultrafast dynamics within MoS2 including photo-thermoelectric currents and the impact of built-in fields due to Schottky barriers as well as the Fermi level pinning at the contact region. We acknowledge support by the ERC via Project 'NanoREAL', the DFG via excellence cluster 'Nanosystems Initiative Munich' (NIM), and through the TUM International Graduate School of Science and Engineering (IGSSE) and BaCaTeC.

Influence of Nitrogen Doping on Device Operation for TiO₂-Based Solid-State Dye-Sensitized Solar Cells: Photo-Physics from Materials to Devices.

PubMed

Wang, Jin; Tapio, Kosti; Habert, Aurélie; Sorgues, Sebastien; Colbeau-Justin, Christophe; Ratier, Bernard; Scarisoreanu, Monica; Toppari, Jussi; Herlin-Boime, Nathalie; Bouclé, Johann

2016-02-23

Solid-state dye-sensitized solar cells (ssDSSC) constitute a major approach to photovoltaic energy conversion with efficiencies over 8% reported thanks to the rational design of efficient porous metal oxide electrodes, organic chromophores, and hole transporters. Among the various strategies used to push the performance ahead, doping of the nanocrystalline titanium dioxide (TiO₂) electrode is regularly proposed to extend the photo-activity of the materials into the visible range. However, although various beneficial effects for device performance have been observed in the literature, they remain strongly dependent on the method used for the production of the metal oxide, and the influence of nitrogen atoms on charge kinetics remains unclear. To shed light on this open question, we synthesized a set of N-doped TiO₂ nanopowders with various nitrogen contents, and exploited them for the fabrication of ssDSSC. Particularly, we carefully analyzed the localization of the dopants using X-ray photo-electron spectroscopy (XPS) and monitored their influence on the photo-induced charge kinetics probed both at the material and device levels. We demonstrate a strong correlation between the kinetics of photo-induced charge carriers probed both at the level of the nanopowders and at the level of working solar cells, illustrating a direct transposition of the photo-physic properties from materials to devices.

Influence of Nitrogen Doping on Device Operation for TiO2-Based Solid-State Dye-Sensitized Solar Cells: Photo-Physics from Materials to Devices

PubMed Central

Wang, Jin; Tapio, Kosti; Habert, Aurélie; Sorgues, Sebastien; Colbeau-Justin, Christophe; Ratier, Bernard; Scarisoreanu, Monica; Toppari, Jussi; Herlin-Boime, Nathalie; Bouclé, Johann

2016-01-01

Solid-state dye-sensitized solar cells (ssDSSC) constitute a major approach to photovoltaic energy conversion with efficiencies over 8% reported thanks to the rational design of efficient porous metal oxide electrodes, organic chromophores, and hole transporters. Among the various strategies used to push the performance ahead, doping of the nanocrystalline titanium dioxide (TiO2) electrode is regularly proposed to extend the photo-activity of the materials into the visible range. However, although various beneficial effects for device performance have been observed in the literature, they remain strongly dependent on the method used for the production of the metal oxide, and the influence of nitrogen atoms on charge kinetics remains unclear. To shed light on this open question, we synthesized a set of N-doped TiO2 nanopowders with various nitrogen contents, and exploited them for the fabrication of ssDSSC. Particularly, we carefully analyzed the localization of the dopants using X-ray photo-electron spectroscopy (XPS) and monitored their influence on the photo-induced charge kinetics probed both at the material and device levels. We demonstrate a strong correlation between the kinetics of photo-induced charge carriers probed both at the level of the nanopowders and at the level of working solar cells, illustrating a direct transposition of the photo-physic properties from materials to devices. PMID:28344292

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions

NASA Astrophysics Data System (ADS)

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A.; Holleitner, Alexander W.

2016-10-01

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches.

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions

PubMed Central

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A.; Holleitner, Alexander W.

2016-01-01

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches. PMID:27762291

THz-circuits driven by photo-thermoelectric, gate-tunable graphene-junctions.

PubMed

Brenneis, Andreas; Schade, Felix; Drieschner, Simon; Heimbach, Florian; Karl, Helmut; Garrido, Jose A; Holleitner, Alexander W

2016-10-20

For future on-chip communication schemes, it is essential to integrate nanoscale materials with an ultrafast optoelectronic functionality into high-frequency circuits. The atomically thin graphene has been widely demonstrated to be suitable for photovoltaic and optoelectronic devices because of its broadband optical absorption and its high electron mobility. Moreover, the ultrafast relaxation of photogenerated charge carriers has been verified in graphene. Here, we show that dual-gated graphene junctions can be functional parts of THz-circuits. As the underlying optoelectronic process, we exploit ultrafast photo-thermoelectric currents. We describe an immediate photo-thermoelectric current of the unbiased device following a femtosecond laser excitation. For a picosecond time-scale after the optical excitation, an additional photo-thermoelectric contribution shows up, which exhibits the fingerprint of a spatially inverted temperature profile. The latter can be understood by the different time-constants and thermal coupling mechanisms of the electron and phonon baths within graphene to the substrate and the metal contacts. The interplay of the processes gives rise to ultrafast electromagnetic transients in high-frequency circuits, and it is equally important for a fundamental understanding of graphene-based ultrafast photodetectors and switches.

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Photoinduced diffusion molecular transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rozenbaum, Viktor M., E-mail: vik-roz@mail.ru, E-mail: litrakh@gmail.com; Dekhtyar, Marina L.; Lin, Sheng Hsien

2016-08-14

We consider a Brownian photomotor, namely, the directed motion of a nanoparticle in an asymmetric periodic potential under the action of periodic rectangular resonant laser pulses which cause charge redistribution in the particle. Based on the kinetics for the photoinduced electron redistribution between two or three energy levels of the particle, the time dependence of its potential energy is derived and the average directed velocity is calculated in the high-temperature approximation (when the spatial amplitude of potential energy fluctuations is small relative to the thermal energy). The thus developed theory of photoinduced molecular transport appears applicable not only to conventionalmore » dichotomous Brownian motors (with only two possible potential profiles) but also to a much wider variety of molecular nanomachines. The distinction between the realistic time dependence of the potential energy and that for a dichotomous process (a step function) is represented in terms of relaxation times (they can differ on the time intervals of the dichotomous process). As shown, a Brownian photomotor has the maximum average directed velocity at (i) large laser pulse intensities (resulting in short relaxation times on laser-on intervals) and (ii) excited state lifetimes long enough to permit efficient photoexcitation but still much shorter than laser-off intervals. A Brownian photomotor with optimized parameters is exemplified by a cylindrically shaped semiconductor nanocluster which moves directly along a polar substrate due to periodically photoinduced dipole moment (caused by the repetitive excited electron transitions to a non-resonant level of the nanocylinder surface impurity).« less

Effect of Viscosity and Polar Properties of Solvent on Dynamics of Photoinduced Charge Transfer in BTA-1 Cation — Derivative of Thioflavin T

NASA Astrophysics Data System (ADS)

Gogoleva, S. D.; Stsiapura, V. I.

2018-05-01

It was found that the spectral and fluorescent properties of BTA-1C cation in protic and aprotic solvents differ. It was shown that for solutions in long-chain alcohols viscosity is the main factor that determines the dynamics of intramolecular charge transfer in the excited state of the BTA-1C molecule. In the case of aprotic solvents a correlation was found between the rate constant of twisted intramolecular charge transfer (TICT) during rotation of fragments of the molecule in relation to each other in the excited state and the solvent relaxation rate: k TICT 1/τ S .

Femtochemistry of Intramolecular Charge and Proton Transfer Reactions in Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Douhal, Abderrazzak; Sanz, Mikel; Carranza, Maria Angeles

2005-03-17

We report on the first observation of ultrafast intramolecular charge- and proton-transfer reactions in 4'-dimethylaminoflavonol (DAMF) in solution. Upon femtosecond excitation of a non-planar structure of DMAF in apolar medium, the intramolecular charge transfer (ICT) does not occur, and a slow (2 ps) proton motion takes place. However, in polar solvents, the ICT is very fast (100-200 fs) and the produced structure is stabilized that proton motion takes place in few or tens of ps.

Lattice-mediated magnetic order melting in TbMnO 3

DOE PAGES

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.; ...

2018-03-15

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

Anisotropic attosecond charge carrier dynamics and layer decoupling in quasi-2D layered SnS 2

DOE PAGES

Eads, Calley N.; Bandak, Dmytro; Neupane, Mahesh R.; ...

2017-11-08

Strong quantum confinement effects lead to striking new physics in two-dimensional materials such as graphene or transition metal dichalcogenides. While spectroscopic fingerprints of such quantum confinement have been demonstrated widely, the consequences for carrier dynamics are at present less clear, particularly on ultrafast timescales. This is important for tailoring, probing, and understanding spin and electron dynamics in layered and two-dimensional materials even in cases where the desired bandgap engineering has been achieved. Here in this paper we show by means of core–hole clock spectroscopy that SnS 2 exhibits spindependent attosecond charge delocalization times (τ deloc) for carriers confined within amore » layer, τ deloc < 400 as, whereas interlayer charge delocalization is dynamically quenched in excess of a factor of 10, τ deloc > 2.7 fs. These layer decoupling dynamics are a direct consequence of strongly anisotropic screening established within attoseconds, and demonstrate that important two-dimensional characteristics are also present in bulk crystals of van der Waalslayered materials, at least on ultrafast timescales.« less

Domain wall remote pinning in magnetic nano wires

NASA Astrophysics Data System (ADS)

Read, Dan; Miguel, Jorge; Maccherozzi, Francesco; Cavill, Stuart; Dhesi, Sarnjeet; Cardiff University Collaboration; Diamond Light Source Collaboration

2013-03-01

In the current race for information storage media with ever increasing density the position of magnetic domain walls, the region in a magnetic system where the local magnetization continually rotates its direction between adjacent magnetic domains, is one of the most promising routes for future storage media devices. Information storage requires ultrafast read-out and writing operations, but domain walls need to be pinned so that the information is safely stored in the long term. Here we investigate the use of remote magnetostatic charges to trap domain walls. By using X-ray photoelectron emission microscopy we have followed the position of domain walls of opposite charge being pinned or repelled by pinning potentials of increasing strength. Micromagnetic simulations show an excellent agreement with the experimental results. We demonstrate the attractive or repulsive character of the interaction between domain wall and trap depending upon the sign of their magnetic charges. These quasi-static experiments are the antecedent to ultrafast time-resolved XMCD-PEEM experiments where the spin-transfer torque effect will be studied dynamically by applying picosecond-long current pulses across the magnetic nanowire.

Lattice-mediated magnetic order melting in TbMnO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

Utilization of photoinduced charge-separated state of donor-acceptor-linked molecules for regulation of cell membrane potential and ion transport.

PubMed

Numata, Tomohiro; Murakami, Tatsuya; Kawashima, Fumiaki; Morone, Nobuhiro; Heuser, John E; Takano, Yuta; Ohkubo, Kei; Fukuzumi, Shunichi; Mori, Yasuo; Imahori, Hiroshi

2012-04-11

The control of ion transport across cell membranes by light is an attractive strategy that allows targeted, fast control of precisely defined events in the biological membrane. Here we report a novel general strategy for the control of membrane potential and ion transport by using charge-separation molecules and light. Delivery of charge-separation molecules to the plasma membrane of PC12 cells by a membranous nanocarrier and subsequent light irradiation led to depolarization of the membrane potential as well as inhibition of the potassium ion flow across the membrane. Photoregulation of the cell membrane potential and ion transport by using charge-separation molecules is highly promising for control of cell functions. © 2012 American Chemical Society

Ultrafast fragmentation dynamics of triply charged carbon dioxide: Vibrational-mode-dependent molecular bond breakage

NASA Astrophysics Data System (ADS)

Yang, HongJiang; Wang, Enliang; Dong, WenXiu; Gong, Maomao; Shen, Zhenjie; Tang, Yaguo; Shan, Xu; Chen, Xiangjun

2018-05-01

The a b i n i t i o molecular dynamics (MD) simulations using an atom-centered density matrix propagation method have been carried out to investigate the fragmentation of the ground-state triply charged carbon dioxide, CO23 +→C+ + Oa+ + Ob+ . Ten thousands of trajectories have been simulated. By analyzing the momentum correlation of the final fragments, it is demonstrated that the sequential fragmentation dominates in the three-body dissociation, consistent with our experimental observations which were performed by electron collision at impact energy of 1500 eV. Furthermore, the MD simulations allow us to have detailed insight into the ultrafast evolution of the molecular bond breakage at a very early stage, within several tens of femtoseconds, and the result shows that the initial nuclear vibrational mode plays a decisive role in switching the dissociation pathways.

New Avenue for Limiting Degradation in NanoLi4Ti5O12 for Ultrafast-Charge Lithium-Ion Batteries: Hybrid Polymer-Inorganic Particles.

PubMed

Daigle, Jean-Christophe; Asakawa, Yuichiro; Beaupré, Mélanie; Vieillette, René; Laul, Dharminder; Trudeau, Michel; Zaghib, Karim

2017-12-13

Lithium titanium oxide (Li 4 Ti 5 O 12 )-based cells are a very promising battery technology for ultrafast-charge-discharge and long-cycle-life batteries. However, the surface reactivity of lithium titanium oxide in the presence of organic electrolytes continues to be a problem that may cause expansion of pouch cells. In this study, we report on the development of a simple and economical grafting method for forming hybrid polymer-Li 4 Ti 15 O 12 nanoparticles, which can be successfully applied in lithium-ion batteries. This method utilizes a low-cost and scalable hydrophobic polymer that is applicable in industrial processes. The hybrid materials demonstrated exceptional capability for preventing the degradation of cells in accelerated aging and operating over 150 cycles at 1C and 45 °C.

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission.

PubMed

Hart, Stephanie M; Silva, W Ruchira; Frontiera, Renee R

2018-02-07

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes.

Harvesting solar energy by means of charge-separating nanocrystals and their solids.

PubMed

Diederich, Geoffrey; O'Connor, Timothy; Moroz, Pavel; Kinder, Erich; Kohn, Elena; Perera, Dimuthu; Lorek, Ryan; Lambright, Scott; Imboden, Martene; Zamkov, Mikhail

2012-08-23

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials offering a superior control over the spatial distribution of charge carriers across material interfaces. As this study demonstrates, a combination of donor-acceptor nanocrystal (NC) domains in a single nanoparticle can lead to the realization of efficient photocatalytic materials, while a layered assembly of donor- and acceptor-like nanocrystals films gives rise to photovoltaic materials. Initially the paper focuses on the synthesis of composite inorganic nanocrystals, comprising linearly stacked ZnSe, CdS, and Pt domains, which jointly promote photoinduced charge separation. These structures are used in aqueous solutions for the photocatalysis of water under solar radiation, resulting in the production of H2 gas. To enhance the photoinduced separation of charges, a nanorod morphology with a linear gradient originating from an intrinsic electric field is used. The inter-domain energetics are then optimized to drive photogenerated electrons toward the Pt catalytic site while expelling the holes to the surface of ZnSe domains for sacrificial regeneration (via methanol). Here we show that the only efficient way to produce hydrogen is to use electron-donating ligands to passivate the surface states by tuning the energy level alignment at the semiconductor-ligand interface. Stable and efficient reduction of water is allowed by these ligands due to the fact that they fill vacancies in the valence band of the semiconductor domain, preventing energetic holes from degrading it. Specifically, we show that the energy of the hole is transferred to the ligand moiety, leaving the semiconductor domain functional. This enables us to return the entire nanocrystal-ligand system to a functional state, when the ligands are degraded, by simply adding fresh ligands to the system. To promote a photovoltaic charge separation, we use a composite two-layer solid of PbS and TiO2 films. In this configuration, photoinduced electrons are injected into TiO2 and are subsequently picked up by an FTO electrode, while holes are channeled to a Au electrode via PbS layer. To develop the latter we introduce a Semiconductor Matrix Encapsulated Nanocrystal Arrays (SMENA) strategy, which allows bonding PbS NCs into the surrounding matrix of CdS semiconductor. As a result, fabricated solids exhibit excellent thermal stability, attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells.

Femtosecond x rays link melting of charge-density wave correlations and light-enhanced coherent transport in YB a 2 C u 3 O 6.6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Först, M.; Frano, A.; Kaiser, S.

2014-11-17

In this study, we use femtosecond resonant soft x-ray diffraction to measure the optically stimulated ultrafast changes of charge density wave correlations in underdoped YBa₂Cu₃O₆.₆. We find that when coherent interlayer transport is enhanced by optical excitation of the apical oxygen distortions, at least 50% of the in-plane charge density wave order is melted. These results indicate that charge ordering and superconductivity may be competing up to the charge ordering transition temperature, with the latter becoming a hidden phase that is accessible only by nonlinear phonon excitation.

Ultrafast optical switching of infrared plasmon polaritons in high-mobility graphene

NASA Astrophysics Data System (ADS)

Ni, G. X.; Wang, L.; Goldflam, M. D.; Wagner, M.; Fei, Z.; McLeod, A. S.; Liu, M. K.; Keilmann, F.; Özyilmaz, B.; Castro Neto, A. H.; Hone, J.; Fogler, M. M.; Basov, D. N.

2016-04-01

The success of metal-based plasmonics for manipulating light at the nanoscale has been empowered by imaginative designs and advanced nano-fabrication. However, the fundamental optical and electronic properties of elemental metals, the prevailing plasmonic media, are difficult to alter using external stimuli. This limitation is particularly restrictive in applications that require modification of the plasmonic response at sub-picosecond timescales. This handicap has prompted the search for alternative plasmonic media, with graphene emerging as one of the most capable candidates for infrared wavelengths. Here we visualize and elucidate the properties of non-equilibrium photo-induced plasmons in a high-mobility graphene monolayer. We activate plasmons with femtosecond optical pulses in a specimen of graphene that otherwise lacks infrared plasmonic response at equilibrium. In combination with static nano-imaging results on plasmon propagation, our infrared pump-probe nano-spectroscopy investigation reveals new aspects of carrier relaxation in heterostructures based on high-purity graphene.

Evidence for photo-induced monoclinic metallic VO{sub 2} under high pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hsieh, Wen-Pin, E-mail: wphsieh@stanford.edu; Mao, Wendy L.; Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305

2014-01-13

We combine ultrafast pump-probe spectroscopy with a diamond-anvil cell to decouple the insulator-metal electronic transition from the lattice symmetry changing structural transition in the archetypal strongly correlated material vanadium dioxide. Coherent phonon spectroscopy enables tracking of the photo-excited phonon vibrational frequencies of the low temperature, monoclinic (M{sub 1})-insulating phase that transforms into the metallic, tetragonal rutile structured phase at high temperature or via non-thermal photo-excitations. We find that in contrast with ambient pressure experiments where strong photo-excitation promptly induces the electronic transition along with changes in the lattice symmetry, at high pressure, the coherent phonons of the monoclinic (M{sub 1})more » phase are still clearly observed upon the photo-driven phase transition to a metallic state. These results demonstrate the possibility of synthesizing and studying transient phases under extreme conditions.« less

Light-activated Gigahertz Ferroelectric Domain Dynamics

DOE PAGES

Akamatsu, Hirofumii; Yuan, Yakun; Stoica, Vladimir A.; ...

2018-02-26

Using time- and spatially-resolved hard X-ray diffraction microscopy, the striking structural and electrical dynamics upon optical excitation of a single crystal of BaTiO 3 are simultaneously captured on sub-nanoseconds and nanoscale within individual ferroelectric domains and across walls. A large emergent photo-induced electric field of up to 20 million volts per meter is discovered in a surface layer of the crystal, which then drives polarization and lattice dynamics that are dramatically distinct in a surface layer versus bulk regions. A dynamical phase-field modeling (DPFM) method is developed that reveals the microscopic origin of these dynamics, leading to GHz polarization andmore » elastic waves travelling in the crystal with sonic speeds and spatially varying frequencies. The advance of spatiotemporal imaging and dynamical modeling tools open opportunities of disentangling ultrafast processes in complex mesoscale structures such as ferroelectric domains« less

PF-AR NW14, a new time-resolved diffraction/scattering beamline

NASA Astrophysics Data System (ADS)

Nozawa, Shunsuke; Adachi, Shin-ichi; Tazaki, Ryoko; Takahashi, Jun-ichi; Itatani, Jiro; Daimon, Masahiro; Mori, Takeharu; Sawa, Hiroshi; Kawata, Hiroshi; Koshihara, Shin-ya

2005-01-01

NW14 is a new insertion device beamline at the Photon Factory Advanced Ring (PF-AR), which is a unique ring with full-time single-bunched operation, aiming for timeresolved x-ray diffraction/scattering and XAFS experiments. The primary scientific goal of this beamline is to observe the ultrafast dynamics of condensed matter systems such as organic and inorganic crystals, biological systems and liquids triggered by optical pulses. With the large photon fluxes derived from the undulator, it should become possible to take a snapshoot an atomic-scale image of the electron density distribution. By combining a series of images it is possible to produce a movie of the photo-induced dynamics with 50-ps resolution. The construction of the beamline is being funded by the ERATO Koshihara Non-equilibrium Dynamics Project of the Japan Science and Technology Agency (JST), and the beamline will be operational from autumn 2005.

Simultaneous observation of the quantization and the interference pattern of a plasmonic near-field

PubMed Central

Piazza, L; Lummen, T.T.A.; Quiñonez, E; Murooka, Y; Reed, B.W.; Barwick, B; Carbone, F

2015-01-01

Surface plasmon polaritons can confine electromagnetic fields in subwavelength spaces and are of interest for photonics, optical data storage devices and biosensing applications. In analogy to photons, they exhibit wave–particle duality, whose different aspects have recently been observed in separate tailored experiments. Here we demonstrate the ability of ultrafast transmission electron microscopy to simultaneously image both the spatial interference and the quantization of such confined plasmonic fields. Our experiments are accomplished by spatiotemporally overlapping electron and light pulses on a single nanowire suspended on a graphene film. The resulting energy exchange between single electrons and the quanta of the photoinduced near-field is imaged synchronously with its spatial interference pattern. This methodology enables the control and visualization of plasmonic fields at the nanoscale, providing a promising tool for understanding the fundamental properties of confined electromagnetic fields and the development of advanced photonic circuits. PMID:25728197

Ultrafast photo-induced dynamics across the metal-insulator transition of VO2

NASA Astrophysics Data System (ADS)

Wang, Siming; Ramírez, Juan Gabriel; Jeffet, Jonathan; Bar-Ad, Shimshon; Huppert, Dan; Schuller, Ivan K.

2017-04-01

The transient reflectivity of VO2 films across the metal-insulator transition clearly shows that with low-fluence excitation, when insulating domains are dominant, energy transfer from the optically excited electrons to the lattice is not instantaneous, but precedes the superheating-driven expansion of the metallic domains. This implies that the phase transition in the coexistence regime is lattice-, not electronically-driven, at weak laser excitation. The superheated phonons provide the latent heat required for the propagation of the optically-induced phase transition. For VO2 this transition path is significantly different from what has been reported in the strong-excitation regime. We also observe a slow-down of the superheating-driven expansion of the metallic domains around the metal-insulator transition, which is possibly due to the competition among several co-existing phases, or an emergent critical-like behavior.

Time-resolved measurement of intramolecular photoinduced electron transfer processes in perylene diimides (Conference Presentation)

NASA Astrophysics Data System (ADS)

Döring, Robin Carl; Baal, Eduard; Sundermeyer, Jörg; Chatterjee, Sangam

2017-02-01

Perylene-3,4,9,10-tetracarboxylic acid (PTCDA) and respective derivatives (e.g. perylene diimide - PDI) are widely used as dyes but also for device applications such as organic field effect transistors or in organic photovoltaics. Due to their intrinsically high quantum efficiencies they are also used as spectroscopic standards. One major drawback of these materials is their low solubility in organic solvents which can be addressed by long alkyl substitutions. When introducing a tertiary amine into the molecule a mechanism known as photoinduced electron transfer (PET) can occur. Here, following an optically excited HOMO-LUMO transition of the core, an electron from the electron lone pair of the amine is transferred to the HOMO of the perylene core. Hence, radiative recombination is disallowed and photoluminescence effectively quenched. Here, we perform a systematic study of the distance dependence of the PET by introducing alkyle groups as spacer units between PDI core and the tertiary amine. Dynamics of the PET are extracted from ultrafast time-resolved photoluminescence measurement data. A rate equation model, simulating a three level system, reveals rate constant of the back electron transfer, otherwise not accessible with our experimental methods. Assuming a Marcus model of electron transfer, electronic coupling strength between the electronic states involved in the respective transitions can be calculated. In addition to the distance dependence, the effects of protonation and methylation of the the tertiary amine units are studied.

Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Jun, E-mail: caojunbnu@mail.bnu.edu.cn

2015-06-28

In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed intomore » 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.« less

Quantum Femtosecond Magnetism: Phase Transition in Step with Light in a Strongly Correlated Manganese Oxide

NASA Astrophysics Data System (ADS)

Wang, Jigang

2014-03-01

Research of non-equilibrium phase transitions of strongly correlated electrons is built around addressing an outstanding challenge: how to achieve ultrafast manipulation of competing magnetic/electronic phases and reveal thermodynamically hidden orders at highly non-thermal, femtosecond timescales? Recently we reveal a new paradigm called quantum femtosecond magnetism-photoinduced femtosecond magnetic phase transitions driven by quantum spin flip fluctuations correlated with laser-excited inter-atomic coherent bonding. We demonstrate an antiferromagnetic (AFM) to ferromagnetic (FM) switching during about 100 fs laser pulses in a colossal magneto-resistive manganese oxide. Our results show a huge photoinduced femtosecond spin generation, measured by magnetic circular dichroism, with photo-excitation threshold behavior absent in the picosecond dynamics. This reveals an initial quantum coherent regime of magnetism, while the optical polarization/coherence still interacts with the spins to initiate local FM correlations that compete with the surrounding AFM matrix. Our results thus provide a framework that explores quantum non-equilibrium kinetics to drive phase transitions between exotic ground states in strongly correlated elecrons, and raise fundamental questions regarding some accepted rules, such as free energy and adiabatic potential surface. This work is in collaboration with Tianqi Li, Aaron Patz, Leonidas Mouchliadis, Jiaqiang Yan, Thomas A. Lograsso, Ilias E. Perakis. This work was supported by the National Science Foundation (contract no. DMR-1055352). Material synthesis at the Ames Laboratory was supported by the US Department of Energy-Basic Energy Sciences (contract no. DE-AC02-7CH11358).

Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites.

PubMed

Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena; Almora, Osbel; Garcia-Belmonte, Germà; Campoy-Quiles, Mariano; Bisquert, Juan

2015-04-16

We investigate the ferroelectric properties of photovoltaic methylammonium lead halide CH3NH3PbI3 perovskite using piezoelectric force microscopy (PFM) and macroscopic polarization methods. The electric polarization is clearly observed by amplitude and phase hysteresis loops. However, the polarization loop decreases as the frequency is lowered, persisting for a short time only, in the one second regime, indicating that CH3NH3PbI3 does not exhibit permanent polarization at room temperature. This result is confirmed by macroscopic polarization measurement based on a standard capacitive method. We have observed a strong increase of piezoelectric response under illumination, consistent with the previously reported giant photoinduced dielectric constant at low frequencies. We speculate that an intrinsic charge transfer photoinduced dipole in the perovskite cage may lie at the origin of this effect.

Protonation-induced ultrafast torsional dynamics in 9-anthrylbenzimidazole: a pH activated molecular rotor.

PubMed

Nandi, Amitabha; Kushwaha, Archana; Das, Dipanwita; Ghosh, Rajib

2018-03-07

We report the photophysical properties and excited state dynamics of 9-anthrylbenzimidazole (ANBI) which exhibits protonation-induced molecular rotor properties. In contrast to the highly emissive behavior of neutral ANBI, protonation of the benzimidazole group of ANBI induces efficient nonradiative deactivation by ultrafast torsional motion around the bond connecting the anthracene and benzimidazole units, as revealed by ultrafast transient absorption and fluorescence spectroscopy. Contrary to viscosity-independent fluorescence of neutral dyes, protonated ANBI is shown to display linear variation of emission yield and lifetime with solvent viscosity. The protonation-induced molecular rotor properties in the studied system are shown to be driven by enhanced charge transfer and are corroborated by quantum chemical calculations. Potential application as a microviscosity sensor of acidic regions in a heterogeneous environment by these proton-activated molecular rotor properties of ANBI is discussed.

Ultrafast spectroscopic investigation of a fullerene poly(3-hexylthiophene) dyad

NASA Astrophysics Data System (ADS)

Banerji, Natalie; Seifter, Jason; Wang, Mingfeng; Vauthey, Eric; Wudl, Fred; Heeger, Alan J.

2011-08-01

We present the femtosecond spectroscopic investigation of a covalently linked dyad, PCB-P3HT, formed by a segment of the conjugated polymer P3HT (regioregular poly(3-hexylthiophene)) that is end capped with the fullerene derivative PCB ([6,6]-phenyl-C61-butyric acid ester), adapted from PCBM. The fluorescence of the P3HT segment in tetrahydrofuran (THF) solution is reduced by 64% in the dyad compared to a control compound without attached fullerene (P3HT-OH). Fluorescence upconversion measurements reveal that the partial fluorescence quenching of PCB-P3HT in THF is multiphasic and occurs on an average time scale of 100 ps, in parallel to excited-state relaxation processes. Judging from ultrafast transient absorption experiments, the origin of the quenching is excitation energy transfer from the P3HT donor to the PCB acceptor. Due to the much higher solubility of P3HT compared to PCB in THF, the PCB-P3HT dyad molecules self-assemble into micelles. When pure C60 is added to the solution, it is incorporated into the fullerene-rich center of the micelles. This dramatically increases the solubility of C60 but does not lead to significant additional quenching of the P3HT fluorescence by the C60 contained in the micelles. In PCB-P3HT thin films drop-cast from THF, the micelle structure is conserved. In contrast to solution, quantitative and ultrafast (<150 fs) charge separation occurs in the solid-state films and leads to the formation of long-lived mobile charge carriers with characteristic transient absorption signatures similar to those that have been observed in P3HT:PCBM bulk heterojunction blends. While π-stacking interactions between neighboring P3HT chains are weak in the micelles, they are strong in thin films drop-cast from ortho-dichlorobenzene. Here, PCB-P3HT self-assembles into a network of long fibers, clearly seen in atomic force microscopy images. Ultrafast charge separation occurs also for the fibrous morphology, but the transient absorption experiments show fast loss of part of the charge carriers due to intensity-induced recombination and annihilation processes and monomolecular interfacial trap-mediated or geminate recombination. The yield of the long-lived charge carriers in the highly organized fibers is however comparable to that obtained with annealed P3HT:PCBM blends. PCB-P3HT can therefore be considered as an active material in organic photovoltaic devices.

Effect of Molecular Coupling on Ultrafast Electron-Transfer and Charge-Recombination Dynamics in a Wide-Gap ZnS Nanoaggregate Sensitized by Triphenyl Methane Dyes.

PubMed

Debnath, Tushar; Maity, Partha; Dana, Jayanta; Ghosh, Hirendra N

2016-03-03

Wide-band-gap ZnS nanocrystals (NCs) were synthesized, and after sensitizing the NCs with series of triphenyl methane (TPM) dyes, ultrafast charge-transfer dynamics was demonstrated. HRTEM images of ZnS NCs show the formation of aggregate crystals with a flower-like structure. Exciton absorption and lumimescence, due to quantum confinement of the ZnS NCs, appear at approximately 310 and 340 nm, respectively. Interestingly, all the TPM dyes (pyrogallol red, bromopyrogallol red, and aurin tricarboxylic acid) form charge-transfer complexes with the ZnS NCs, with the appearance of a red-shifted band. Electron injection from the photoexcited TPM dyes into the conduction band of the ZnS NCs is shown to be a thermodynamically viable process, as confirmed by steady-state and time-resolved emission studies. To unravel charge-transfer (both electron injection and charge recombination) dynamics and the effect of molecular coupling, femtosecond transient absorption studies were carried out in TPM-sensitized ZnS NCs. The electron-injection dynamics is pulse-width-limited in all the ZnS/TPM dye systems, however, the back electron transfer differs, depending on the molecular coupling of the sensitizers (TPM dyes). The detailed mechanisms for the above-mentioned processes are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene-MoS2 van der Waals Heterojunction.

PubMed

Bettis Homan, Stephanie; Sangwan, Vinod K; Balla, Itamar; Bergeron, Hadallia; Weiss, Emily A; Hersam, Mark C

2017-01-11

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS 2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS 2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS 2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS 2 decay processes, the hole transfer yield from MoS 2 to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS 2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

Ultrafast and Ultrasensitive Gas Sensors Derived from a Large Fermi-Level Shift in the Schottky Junction with Sieve-Layer Modulation.

PubMed

Cheng, Ching-Cheng; Wu, Chia-Lin; Liao, Yu-Ming; Chen, Yang-Fang

2016-07-13

Gas sensors play an important role in numerous fields, covering a wide range of applications, including intelligent systems and detection of harmful and toxic gases. Even though they have attracted much attention, the response time on the order of seconds to minutes is still very slow. To circumvent the existing problems, here, we provide a seminal attempt with the integration of graphene, semiconductor, and an addition sieve layer forming a nanocomposite gas sensor with ultrahigh sensitivity and ultrafast response. The designed sieve layer has a suitable band structure that can serve as a blocking layer to prevent transfer of the charges induced by adsorbed gas molecules into the underlying semiconductor layer. We found that the sensitivity can be reduced to the parts per million level, and the ultrafast response of around 60 ms is unprecedented compared with published graphene-based gas sensors. The achieved high performance can be interpreted well by the large change of the Fermi level of graphene due to its inherent nature of the low density of states and blocking of the sieve layer to prevent charge transfer from graphene to the underlying semiconductor layer. Accordingly, our work is very useful and timely for the development of gas sensors with high performance for practical applications.

GPU.proton.DOCK: Genuine Protein Ultrafast proton equilibria consistent DOCKing.

PubMed

Kantardjiev, Alexander A

2011-07-01

GPU.proton.DOCK (Genuine Protein Ultrafast proton equilibria consistent DOCKing) is a state of the art service for in silico prediction of protein-protein interactions via rigorous and ultrafast docking code. It is unique in providing stringent account of electrostatic interactions self-consistency and proton equilibria mutual effects of docking partners. GPU.proton.DOCK is the first server offering such a crucial supplement to protein docking algorithms--a step toward more reliable and high accuracy docking results. The code (especially the Fast Fourier Transform bottleneck and electrostatic fields computation) is parallelized to run on a GPU supercomputer. The high performance will be of use for large-scale structural bioinformatics and systems biology projects, thus bridging physics of the interactions with analysis of molecular networks. We propose workflows for exploring in silico charge mutagenesis effects. Special emphasis is given to the interface-intuitive and user-friendly. The input is comprised of the atomic coordinate files in PDB format. The advanced user is provided with a special input section for addition of non-polypeptide charges, extra ionogenic groups with intrinsic pK(a) values or fixed ions. The output is comprised of docked complexes in PDB format as well as interactive visualization in a molecular viewer. GPU.proton.DOCK server can be accessed at http://gpudock.orgchm.bas.bg/.

Measurement of charge transport through organic semiconducting devices

NASA Astrophysics Data System (ADS)

Klenkler, Richard A.

2007-12-01

In this thesis, two important and unexplored areas of organic semiconductor device physics are investigated: The first area involves determining the effect of energy barriers and intermixing at the interfaces between hole transport layers (HTLs). This effect was discerned by first establishing a method of pressure-laminating successive solution coated HTLs to gether. It was found that in the range of 0.8--3.0 MPa a pressure-laminated interface between two identical HTLs causes no measurable perturbation to charge transport. By this method, 2 different HTLs can be sandwiched together to create a discrete interface, and by inserting a mixed HTL in the middle an intermixed interface between the 2 HTLs can be simulated. With these sandwiched devices, charge injection across discrete versus intermixed interfaces were compared using time-of-flight measurements. For the hole transport materials investigated, no perturbation to the overall charge transport was observed with the discrete interface, however in contrast the rate of charge transport was clearly reduced through the intermixed interface. The second area that was investigated pertains to the development of a bulk mobility measurement technique that has a higher resolution than existing methods. The approach that was used involved decoupling the charge carrier transient signal from the device charging circuit. With this approach, the RC time constant constraint that limits the resolution of existing methods is eliminated. The resulting method, termed the photoinduced electroluminescence (EL) mobility measurement technique, was then used to compare the electron mobility of the metal chelate, AlQ3 to that of the novel triazine material, BTB. Results showed that BTB demonstrated an order of magnitude higher mobility than AlQ3. Overall, these findings have broad implications regarding device design. The pressure-lamination method could be used, e.g., as a diagnostic tool to help in the design of multilayer xerographic photoreceptors, such as those that include an abrasion resistant overcoat. Further, the photoinduced EL technique could be use as a tool to help characterize charge flow and balance in organic light emitting devices amongst others.

Ultrafast electron diffraction optimized for studying structural dynamics in thin films and monolayers

PubMed Central

Badali, D. S.; Gengler, R. Y. N.; Miller, R. J. D.

2016-01-01

A compact electron source specifically designed for time-resolved diffraction studies of free-standing thin films and monolayers is presented here. The sensitivity to thin samples is achieved by extending the established technique of ultrafast electron diffraction to the “medium” energy regime (1–10 kV). An extremely compact design, in combination with low bunch charges, allows for high quality diffraction in a lensless geometry. The measured and simulated characteristics of the experimental system reveal sub-picosecond temporal resolution, while demonstrating the ability to produce high quality diffraction patterns from atomically thin samples. PMID:27226978

Ultrafast relaxation dynamics of nitric oxide synthase studied by visible broadband transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S.

2017-09-01

Ultrafast dynamics of endothelial nitric oxide synthase (eNOS) oxygenase domain was studied by transient absorption spectroscopy pumping at Soret band. The broadband visible probe spectrum has visualized the relaxation dynamics from the Soret band to Q-band and charge transfer (CT) band. Supported by two-dimensional correlation spectroscopy, global fitting analysis has successfully concluded the relaxation dynamics from the Soret band to be (1) electronic transition to Q-band (0.16 ps), (2) ligand dissociation and CT (0.94 ps), (3) relaxation of the CT state (4.0 ps), and (4) ligand rebinding (59 ps).

Ultrafast carrier dynamics in GaN/InGaN multiple quantum wells nanorods

NASA Astrophysics Data System (ADS)

Chen, Weijian; Wen, Xiaoming; Latzel, Michael; Yang, Jianfeng; Huang, Shujuan; Shrestha, Santosh; Patterson, Robert; Christiansen, Silke; Conibeer, Gavin

2018-01-01

GaN/InGaN multiple quantum wells (MQW) is a promising material for high-efficiency solid-state lighting. Ultrafast optical pump-probe spectroscopy is an important characterization technique for examining fundamental phenomena in semiconductor nanostructure with sub-picosecond resolution. In this study, ultrafast exciton and charge carrier dynamics in GaN/InGaN MQW planar layer and nanorod are investigated using femtosecond transient absorption (TA) techniques at room temperature. Here nanorods are fabricated by etching the GaN/InGaN MQW planar layers using nanosphere lithography and reactive ion etching. Photoluminescence efficiency of the nanorods have been proved to be much higher than that of the planar layers, but the mechanism of the nanorod structure improvement of PL efficiency is not adequately studied. By comparing the TA profile of the GaN/InGaN MQW planar layers and nanorods, the impact of surface states and nanorods lateral confinement in the ultrafast carrier dynamics of GaN/InGaN MQW is revealed. The nanorod sidewall surface states have a strong influence on the InGaN quantum well carrier dynamics. The ultrafast relaxation processes studied in this GaN/InGaN MQW nanostructure is essential for further optimization of device application.

Influence of Processing Additives on Charge-Transfer Time Scales and Sound Velocity in Organic Bulk Heterojunction Films.

PubMed

Kaake, Loren G; Welch, Gregory C; Moses, Daniel; Bazan, Guillermo C; Heeger, Alan J

2012-05-17

The role of processing additives in organic bulk heterojunction thin films was investigated by means of transient absorption spectroscopy. The rate of ultrafast charge transfer was found to increase when a small amount of diiodooctane was used during film formation. In addition, coherent acoustic phonons were observed, and their velocity was determined. A strong correlation between the sound velocity and the charge-transfer time scale was observed, both of which could be explained by a subtle increase in thin film density.

Plasmon enhanced heterogeneous electron transfer with continuous band energy model

NASA Astrophysics Data System (ADS)

Zhao, Dandan; Niu, Lu; Wang, Luxia

2017-08-01

Photoinduced charge injection from a perylene dye molecule into the conduction band of a TiO2 system decorated by a metal nanoparticles (MNP) is studied theoretically. Utilizing the density matrix theory the charge transfer dynamics is analyzed. The continuous behavior of the TiO2 conduction band is accounted for by a Legendre polynomials expansion. The simulations consider optical excitation of the dye molecule coupled to the MNP and the subsequent electron injection into the TiO2 semiconductor. Due to the energy transfer coupling between the molecule and the MNP optical excitation and subsequent charge injection into semiconductor is strongly enhanced. The respective enhancement factor can reach values larger than 103. Effects of pulse duration, coupling strength and energetic resonances are also analyzed. The whole approach offers an efficient way to increase charge injection in dye-sensitized solar cells.

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Dynamic diffraction effects and coherent breathing oscillations in ultrafast electron diffraction in layered 1T-TaSeTe

PubMed Central

Wei, Linlin; Sun, Shuaishuai; Guo, Cong; Li, Zhongwen; Sun, Kai; Liu, Yu; Lu, Wenjian; Sun, Yuping; Tian, Huanfang; Yang, Huaixin; Li, Jianqi

2017-01-01

Anisotropic lattice movements due to the difference between intralayer and interlayer bonding are observed in the layered transition-metal dichalcogenide 1T-TaSeTe following femtosecond laser pulse excitation. Our ultrafast electron diffraction investigations using 4D-transmission electron microscopy (4D-TEM) clearly reveal that the intensity of Bragg reflection spots often changes remarkably due to the dynamic diffraction effects and anisotropic lattice movement. Importantly, the temporal diffracted intensity from a specific crystallographic plane depends on the deviation parameter s, which is commonly used in the theoretical study of diffraction intensity. Herein, we report on lattice thermalization and structural oscillations in layered 1T-TaSeTe, analyzed by dynamic diffraction theory. Ultrafast alterations of satellite spots arising from the charge density wave in the present system are also briefly discussed. PMID:28470025

Ultrafast electron microscopy in materials science, biology, and chemistry

NASA Astrophysics Data System (ADS)

King, Wayne E.; Campbell, Geoffrey H.; Frank, Alan; Reed, Bryan; Schmerge, John F.; Siwick, Bradley J.; Stuart, Brent C.; Weber, Peter M.

2005-06-01

The use of pump-probe experiments to study complex transient events has been an area of significant interest in materials science, biology, and chemistry. While the emphasis has been on laser pump with laser probe and laser pump with x-ray probe experiments, there is a significant and growing interest in using electrons as probes. Early experiments used electrons for gas-phase diffraction of photostimulated chemical reactions. More recently, scientists are beginning to explore phenomena in the solid state such as phase transformations, twinning, solid-state chemical reactions, radiation damage, and shock propagation. This review focuses on the emerging area of ultrafast electron microscopy (UEM), which comprises ultrafast electron diffraction (UED) and dynamic transmission electron microscopy (DTEM). The topics that are treated include the following: (1) The physics of electrons as an ultrafast probe. This encompasses the propagation dynamics of the electrons (space-charge effect, Child's law, Boersch effect) and extends to relativistic effects. (2) The anatomy of UED and DTEM instruments. This includes discussions of the photoactivated electron gun (also known as photogun or photoelectron gun) at conventional energies (60-200 keV) and extends to MeV beams generated by rf guns. Another critical aspect of the systems is the electron detector. Charge-coupled device cameras and microchannel-plate-based cameras are compared and contrasted. The effect of various physical phenomena on detective quantum efficiency is discussed. (3) Practical aspects of operation. This includes determination of time zero, measurement of pulse-length, and strategies for pulse compression. (4) Current and potential applications in materials science, biology, and chemistry. UEM has the potential to make a significant impact in future science and technology. Understanding of reaction pathways of complex transient phenomena in materials science, biology, and chemistry will provide fundamental knowledge for discovery-class science.

Hole Transfer from Low Band Gap Quantum Dots to Conjugated Polymers in Organic/Inorganic Hybrid Photovoltaics.

PubMed

Colbert, Adam E; Janke, Eric M; Hsieh, Stephen T; Subramaniyan, Selvam; Schlenker, Cody W; Jenekhe, Samson A; Ginger, David S

2013-01-17

We use photoinduced absorption (PIA) spectroscopy to investigate pathways for photocurrent generation in hybrid organic/inorganic quantum dot bulk heterojunction solar cells. We study blends of the conjugated polymer poly(2,3-bis(2-(hexyldecyl)quinoxaline-5,8-diyl-alt-N-(2-hexyldecyl)dithieno[3,2-b:2',3'-d]pyrrole) (PDTPQx-HD) with PbS quantum dots and find that positively charged polarons are formed on the conjugated polymer following selective photoexcitation of the PbS quantum dots. This result provides a direct spectroscopic fingerprint demonstrating that photoinduced hole transfer occurs from the photoexcited quantum dots to the host polymer. We compute the relative yields of long-lived holes following photoexcitation of both the polymer and quantum dot phases and estimate that more long-lived polarons are produced per photon absorbed by the polymer phase than by the quantum dot phase.

Photo-Induced Room-Temperature Gas Sensing with a-IGZO Based Thin-Film Transistors Fabricated on Flexible Plastic Foil.

PubMed

Knobelspies, Stefan; Bierer, Benedikt; Daus, Alwin; Takabayashi, Alain; Salvatore, Giovanni Antonio; Cantarella, Giuseppe; Ortiz Perez, Alvaro; Wöllenstein, Jürgen; Palzer, Stefan; Tröster, Gerhard

2018-01-26

We present a gas sensitive thin-film transistor (TFT) based on an amorphous Indium-Gallium-Zinc-Oxide (a-IGZO) semiconductor as the sensing layer, which is fabricated on a free-standing flexible polyimide foil. The photo-induced sensor response to NO₂ gas at room temperature and the cross-sensitivity to humidity are investigated. We combine the advantages of a transistor based sensor with flexible electronics technology to demonstrate the first flexible a-IGZO based gas sensitive TFT. Since flexible plastic substrates prohibit the use of high operating temperatures, the charge generation is promoted with the help of UV-light absorption, which ultimately triggers the reversible chemical reaction with the trace gas. Furthermore, the device fabrication process flow can be directly implemented in standard TFT technology, allowing for the parallel integration of the sensor and analog or logical circuits.

Fluoride anion sensing mechanism of 2-ureido-4[1H]-pyrimidinone quadruple hydrogen-bonded supramolecular assembly: photoinduced electron transfer and partial configuration change.

PubMed

Chen, Jun-Sheng; Zhou, Pan-Wang; Li, Guang-Yue; Chu, Tian-Shu; He, Guo-Zhong

2013-05-02

The fluoride anion sensing mechanism of 6-methyl-5-(9-methylene-anthracene)-(2-butylureido-4[1H]-pyrimidinone) (AnUP) has been investigated using the DFT/TDDFT method. The theoretical results indicate that the proton of the N3-H3 group in pyrimidine moiety is captured by the added fluoride anion and then deprotonated. The calculated vertical excitation energies of AnUP-dimer and its deprotonated form agree well with the experimental results. The molecular orbital analysis demonstrates that the first excited state (S1) of AnUP-dimer is a local excited state with a π-π* transition, whereas for the deprotonated form, S1 is a completely charge-separation state and is responsible for the photoinduced electron transfer (PET) process. The PET process from anthracene to the pyrimidine moiety leads to the fluorescence quenching.

Photo-Induced Room-Temperature Gas Sensing with a-IGZO Based Thin-Film Transistors Fabricated on Flexible Plastic Foil

PubMed Central

Bierer, Benedikt; Takabayashi, Alain; Ortiz Perez, Alvaro; Wöllenstein, Jürgen

2018-01-01

We present a gas sensitive thin-film transistor (TFT) based on an amorphous Indium–Gallium–Zinc–Oxide (a-IGZO) semiconductor as the sensing layer, which is fabricated on a free-standing flexible polyimide foil. The photo-induced sensor response to NO2 gas at room temperature and the cross-sensitivity to humidity are investigated. We combine the advantages of a transistor based sensor with flexible electronics technology to demonstrate the first flexible a-IGZO based gas sensitive TFT. Since flexible plastic substrates prohibit the use of high operating temperatures, the charge generation is promoted with the help of UV-light absorption, which ultimately triggers the reversible chemical reaction with the trace gas. Furthermore, the device fabrication process flow can be directly implemented in standard TFT technology, allowing for the parallel integration of the sensor and analog or logical circuits. PMID:29373524

Ultrafast-Charging Supercapacitors Based on Corn-Like Titanium Nitride Nanostructures.

PubMed

Yang, Peihua; Chao, Dongliang; Zhu, Changrong; Xia, Xinhui; Zhang, Yongqi; Wang, Xingli; Sun, Peng; Tay, Beng Kang; Shen, Ze Xiang; Mai, Wenjie; Fan, Hong Jin

2016-06-01

Ultrahigh rates realized by ALD-made TiN . The symmetric full-cell supercapacitors deliver a typical capacitance of 20.7 F cm -3 at a scan rate of 1 V s -1 , and retain 4.3 F cm -3 at high rate of 100 V s -1 . The devices can be charged and discharged for 20 000 cycles with negligible capacitance loss and with an ultralow self-discharge current (≈1 μA).

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution.

PubMed

Wernet, Ph; Kunnus, K; Josefsson, I; Rajkovic, I; Quevedo, W; Beye, M; Schreck, S; Grübel, S; Scholz, M; Nordlund, D; Zhang, W; Hartsock, R W; Schlotter, W F; Turner, J J; Kennedy, B; Hennies, F; de Groot, F M F; Gaffney, K J; Techert, S; Odelius, M; Föhlisch, A

2015-04-02

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16 - 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

Orbital-specific mapping of the ligand exchange dynamics of Fe(CO)5 in solution

NASA Astrophysics Data System (ADS)

Wernet, Ph.; Kunnus, K.; Josefsson, I.; Rajkovic, I.; Quevedo, W.; Beye, M.; Schreck, S.; Grübel, S.; Scholz, M.; Nordlund, D.; Zhang, W.; Hartsock, R. W.; Schlotter, W. F.; Turner, J. J.; Kennedy, B.; Hennies, F.; de Groot, F. M. F.; Gaffney, K. J.; Techert, S.; Odelius, M.; Föhlisch, A.

2015-04-01

Transition-metal complexes have long attracted interest for fundamental chemical reactivity studies and possible use in solar energy conversion. Electronic excitation, ligand loss from the metal centre, or a combination of both, creates changes in charge and spin density at the metal site that need to be controlled to optimize complexes for photocatalytic hydrogen production and selective carbon-hydrogen bond activation. An understanding at the molecular level of how transition-metal complexes catalyse reactions, and in particular of the role of the short-lived and reactive intermediate states involved, will be critical for such optimization. However, suitable methods for detailed characterization of electronic excited states have been lacking. Here we show, with the use of X-ray laser-based femtosecond-resolution spectroscopy and advanced quantum chemical theory to probe the reaction dynamics of the benchmark transition-metal complex Fe(CO)5 in solution, that the photo-induced removal of CO generates the 16-electron Fe(CO)4 species, a homogeneous catalyst with an electron deficiency at the Fe centre, in a hitherto unreported excited singlet state that either converts to the triplet ground state or combines with a CO or solvent molecule to regenerate a penta-coordinated Fe species on a sub-picosecond timescale. This finding, which resolves the debate about the relative importance of different spin channels in the photochemistry of Fe(CO)5 (refs 4, 16,17,18,19 and 20), was made possible by the ability of femtosecond X-ray spectroscopy to probe frontier-orbital interactions with atom specificity. We expect the method to be broadly applicable in the chemical sciences, and to complement approaches that probe structural dynamics in ultrafast processes.

An Efficient, "Burn in" Free Organic Solar Cell Employing a Nonfullerene Electron Acceptor.

PubMed

Cha, Hyojung; Wu, Jiaying; Wadsworth, Andrew; Nagitta, Jade; Limbu, Saurav; Pont, Sebastian; Li, Zhe; Searle, Justin; Wyatt, Mark F; Baran, Derya; Kim, Ji-Seon; McCulloch, Iain; Durrant, James R

2017-09-01

A comparison of the efficiency, stability, and photophysics of organic solar cells employing poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3'″-di(2-octyldodecyl)-2,2';5',2″;5″,2'″-quaterthiophen-5,5'″-diyl)] (PffBT4T-2OD) as a donor polymer blended with either the nonfullerene acceptor EH-IDTBR or the fullerene derivative, [6,6]-phenyl C 71 butyric acid methyl ester (PC 71 BM) as electron acceptors is reported. Inverted PffBT4T-2OD:EH-IDTBR blend solar cell fabricated without any processing additive achieves power conversion efficiencies (PCEs) of 9.5 ± 0.2%. The devices exhibit a high open circuit voltage of 1.08 ± 0.01 V, attributed to the high lowest unoccupied molecular orbital (LUMO) level of EH-IDTBR. Photoluminescence quenching and transient absorption data are employed to elucidate the ultrafast kinetics and efficiencies of charge separation in both blends, with PffBT4T-2OD exciton diffusion kinetics within polymer domains, and geminate recombination losses following exciton separation being identified as key factors determining the efficiency of photocurrent generation. Remarkably, while encapsulated PffBT4T-2OD:PC 71 BM solar cells show significant efficiency loss under simulated solar irradiation ("burn in" degradation) due to the trap-assisted recombination through increased photoinduced trap states, PffBT4T-2OD:EH-IDTBR solar cell shows negligible burn in efficiency loss. Furthermore, PffBT4T-2OD:EH-IDTBR solar cells are found to be substantially more stable under 85 °C thermal stress than PffBT4T-2OD:PC 71 BM devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoinduced Dynamics of Charge Separation: From Photosynthesis to Polymer–Fullerene Bulk Heterojunctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niklas, Jens; Beaupré, Serge; Leclerc, Mario

2015-06-18

Understanding charge separation and charge transport is crucial for improving the efficiency of organic solar cells. Their active media are based on organic molecules and polymers, serving as both light-absorbing and transport layers. The charge-transfer (CT) states play an important role, being intermediate for free carrier generation and charge recombination. Here, we use light-induced electron paramagnetic resonance spectroscopy to study the CT dynamics in blends of the polymers P3HT, PCDTBT, and PTB7 with the fullerene derivative C-60-PCBM. Time-resolved EPR measurements show strong spin-polarization patterns for all polymer-fullerene blends, confirming predominant generation of singlet CT states and partial orientation ordering nearmore » the donor-acceptor interface. These observations allow a comparison with charge separation processes in molecular donor-acceptor systems and in natural and artificial photosynthetic assemblies, and thus the elucidation of the initial steps of sequential CT in organic photovoltaic materials.« less

Photoinduced electron transfer (PET) versus excimer formation in supramolecular p/n-heterojunctions of perylene bisimide dyes and implications for organic photovoltaics.

PubMed

Nowak-Król, Agnieszka; Fimmel, Benjamin; Son, Minjung; Kim, Dongho; Würthner, Frank

2015-01-01

Foldamer systems comprised of two perylene bisimide (PBI) dyes attached to the conjugated backbones of 1,2-bis(phenylethynyl)benzene and phenylethynyl-bis(phenylene)indane, respectively, were synthesized and investigated with regard to their solvent-dependent properties. UV/Vis absorption and steady-state fluorescence spectra show that both foldamers exist predominantly in a folded H-aggregated state consisting of π-π-stacked PBIs in THF and in more random conformations with weaker excitonic coupling between the PBIs in chloroform. Time-resolved fluorescence spectroscopy and transient absorption spectroscopy reveal entirely different relaxation pathways for the photoexcited molecules in the given solvents, i.e. photoinduced electron transfer leading to charge separated states for the open conformations (in chloroform) and relaxation into excimer states with red-shifted emission for the stacked conformations (in THF). Supported by redox data from cyclic voltammetry and Rehm-Weller analysis we could relate the processes occurring in these solution-phase model systems to the elementary processes in organic solar cells. Accordingly, only if relaxation pathways such as excimer formation are strictly avoided in molecular semiconductor materials, excitons may diffuse over larger distances to the heterojunction interface and produce photocurrent via the formation of electron/hole pairs by photoinduced electron transfer.

Ultrafast Carrier dynamics of InxGa1-xN nanostructures grown directly on Si(111)

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Devi, Pooja; Rodriguez⁠, P. E. D. S.; Kumar, Manish; Shivling, V. D.; Noetzel, Richard; Sharma, Chhavi; Sinha, R. K.; Kumar, Mahesh

2018-05-01

We show a flux dependence changes in structural, optical and electronic properties of InxGa1-xN nanostructures (NSs) namely nanocolumns (NCs), nanoflakes (NFs) and nanowall network (NWN) grown directly on Si(111) surface. Field emission scanning electron microscopy (FESEM) images were recorded to see morphological changes from NFs to NCs and NWNc etc, while high-resolution X-ray diffraction (HRXRD) ω-2θ scans were used to determine In incorporation. The maximum In incorporation was observed to be 20, 33 and 38% for the sharp transition from NFs to NCs and NWNs, respectively. The charge carrier dynamics of these grown NSs were probed using Ultrafast Femtosecond Transient Absorption Spectroscopy (UFTAS) with excitation at 350 nm pump wavelength. The UFTAS studies show the comparative charge carriers dynamics of the NWS, NCs and NFs. The charge carrier studies show a higher lifetime in NWNs as compare to NCs and NFs. Further, to examine electronic structure and level of degeneracy of these NSs, core-level and valence band spectra were analyzed by X-ray photoelectron spectroscopy (XPS), which manifest the upward band bending ranging from 0.2 eV to 0.4 eV.

Modeling of silicon in femtosecond laser-induced modification regimes: accounting for ambipolar diffusion

NASA Astrophysics Data System (ADS)

Derrien, Thibault J.-Y.; Bulgakova, Nadezhda M.

2017-05-01

During the last decades, femtosecond laser irradiation of materials has led to the emergence of various applications based on functionalization of surfaces at the nano- and microscale. Via inducing a periodic modification on material surfaces (band gap modification, nanostructure formation, crystallization or amorphization), optical and mechanical properties can be tailored, thus turning femtosecond laser to a key technology for development of nanophotonics, bionanoengineering, and nanomechanics. Although modification of semiconductor surfaces with femtosecond laser pulses has been studied for more than two decades, the dynamics of coupling of intense laser light with excited matter remains incompletely understood. In particular, swift formation of a transient overdense electron-hole plasma dynamically modifies optical properties in the material surface layer and induces large gradients of hot charge carriers, resulting in ultrafast charge-transport phenomena. In this work, the dynamics of ultrafast laser excitation of a semiconductor material is studied theoretically on the example of silicon. A special attention is paid to the electron-hole pair dynamics, taking into account ambipolar diffusion effects. The results are compared with previously developed simulation models, and a discussion of the role of charge-carrier dynamics in localization of material modification is provided.

Ultrafast Primary Reactions in the Photosystems of Oxygen-Evolving Organisms

NASA Astrophysics Data System (ADS)

Holzwarth, A. R.

In oxygen-evolving photosynthetic organisms (plants, green algae, cyanobacteria), the primary steps of photosynthesis occur in two membrane-bound protein supercomplexes, Photosystem I (PS I) and Photosystem II (PS II), located in the thylakoid membrane (c.f. Fig. 7.1) along with two other important protein complexes, the cytochrome b6/f complex and the ATP-synthase [1]. Each of the photosystems consists of a reaction center (RC) where the photoinduced early electron transfer processes occur, of a so-called core antenna consisting of chlorophyll (Chl) protein complexes responsible for light absorption and ultrafast energy transfer to the RC pigments, and additional peripheral antenna complexes of various kinds that increase the absorption cross-section. The peripheral complexes are Chl a/b-protein complexes in higher plants and green algae (LHC I or LHC II for PS I or PS II, respectively) and so-called phycobilisomes in cyanobacteria and red algae [2-4]. The structures and light-harvesting functions of these antenna systems have been extensively reviewed [2, 5-9]. Recently, X-ray structures of both PS I and PS II antenna/RC complexes have been determined, some to atomic resolution. Although many details of the pigment content and organization of the RCs and antenna systems of PS I and PS II have been known before, the high resolution structures of the integral complexes allow us for the first time to try to understand structure/function relationships in detail. This article covers our present understanding of the ultrafast energy transfer and early electron transfer processes occurring in the photosystems of oxygen-evolving organisms. The main emphasis will be on the electron transfer processes. However, in both photosystems the kinetics of the energy transfer processes in the core antennae is intimately interwoven with the kinetics of the electron transfer steps. Since both types of processes occur on a similar time scale, their kinetics cannot be considered separately in any experiment and consequently they have to be discussed together.

Design of a laser scanner for a digital mammography system.

PubMed

Rowlands, J A; Taylor, J E

1996-05-01

We have developed a digital readout system for radiographic images using a scanning laser beam. In this system, electrostatic charge images on amorphous selenium (alpha-Se) plates are read out using photo-induced discharge (PID). We discuss the design requirements of a laser scanner for the PID system and describe its construction from commercially available components. The principles demonstrated can be adapted to a variety of digital imaging systems.

Ultrafast charge transfer between MoTe2 and MoS2 monolayers

NASA Astrophysics Data System (ADS)

Pan, Shudi; Ceballos, Frank; Bellus, Matthew Z.; Zereshki, Peymon; Zhao, Hui

2017-03-01

High quality and stable electrical contact between metal and two-dimensional materials, such as transition metal dichalcogenides, is a necessary requirement that has yet to be achieved in order to successfully exploit the advantages that these materials offer to electronics and optoelectronics. MoTe2, owing to its phase changing property, can potentially offer a solution. A recent study demonstrated that metallic phase of MoTe2 connects its semiconducting phase with very low resistance. To utilize this property to connect other two-dimensional materials, it is important to achieve efficient charge transfer between MoTe2 and other semiconducting materials. Using MoS2 as an example, we report ultrafast and efficient charge transfer between MoTe2 and MoS2 monolayers. In the transient absorption measurements, an ultrashort pump pulse is used to selectively excite electrons in MoTe2. The appearance of the excited electrons in the conduction band of MoS2 is monitored by using a probe pulse that is tuned to the resonance of MoS2. We found that electrons transfer to MoS2 on a time scale of at most 0.3 ps. The transferred electrons give rise to a large transient absorption signal at both A-exciton and B-exciton resonances due to the screening effect. We also observed ultrafast transfer of holes from MoS2 to MoTe2. Our results suggest the feasibility of using MoTe2 as a bridge material to connect MoS2 and other transition metal dichalcogenides, and demonstrate a new transition metal dichalcogenide heterostructure involving MoTe2, which extends the spectral range of such structures to infrared.

The synthesis and properties of linear A-π-D-π-A type organic small molecule containing diketopyrrolopyrrole terminal units.

PubMed

Zhang, Shanshan; Niu, Qingfen; Sun, Tao; Li, Yang; Li, Tianduo; Liu, Haixia

2017-08-05

A novel linear A-π-D-π-A-type organic small molecule Ph2(PDPP) 2 consisting diketopyrrolopyrrole (DPP) as acceptor unit, biphenylene as donor unit and acetylene unit as π-linkage has been successfully designed and synthesized. Its corresponding thermal, photophysical and electrochemical properties as well as the photoinduced charge-separation process were investigated. Ph2(PDPP) 2 exhibits high thermal stability and it can be soluble in common organic solvents such as chloroform and tetrahydrofuran. The photophysical properties show that DPP 2 Ph 2 harvests sunlight over the entire visible spectrum range in the thin-film state (300-800nm). DPP 2 Ph 2 has lower band gaps and appropriate energy levels to satisfy the requirement of solution-processable organic solar cells. The efficient photoinduced charge separation process was clearly observed between DPP 2 Ph 2 with PC 61 BM and the K sv value was found to be as high as 2.13×10 4 M -1 . Therefore, these excellent properties demonstrate that the designed A-π-D-π-A-type small molecule Ph2(PDPP) 2 is the prospective candidate as donor material for organic photovoltaic material. Copyright © 2017 Elsevier B.V. All rights reserved.

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

PubMed

Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

2013-08-15

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Observation of ultrafast temporal evolution of symmetry in short-pulsed laser induced transient states of matter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Garnett, Joy; Krzyzanowska, Halina; Baydin, Andrey; Tolk, Norman H.

2017-02-01

In condensed matter physics, ultrafast photoexcitation has been shown to result in modification of macroscopic material properties, sometimes involving phase changes, on a subpicosecond time scale. In semiconductors, irreversible non-thermal solid-to-liquid structural transitions have been demonstrated at high laser fluences. In the pump-probe experiments reported here, we observe a striking continuously varying low-fluence pump-induced time-dependent structural symmetry modification in intrinsic gallium arsenide (GaAs) using a probe that produces femtosecond polarization-resolved second harmonic generation (f-PRSHG) data. SHG spectroscopy is particularly suited to monitor symmetry changes since its magnitude is governed by the nonlinear optical susceptibility tensor whose elements are determined by the underlying material symmetry. Conceptually, these experiments seek to provide insight into the details of the time evolution of symmetry arising from laser induced transient states of matter in GaAs. Overall, the basic explanation of these experimental observations is that as a result of the photoinduced electronic excitation, many electrons, including bond electrons are excited to higher states. This results in subpicosecond changes in the local anharmonic potential and produces a changing nonlinear polarization response thus accounting for the nonthermal time dependent symmetry changes. Clearly, our approach may be easily extended to many different crystalline materials with different levels of defects, dopants and stresses to fully characterize the time dependent behavior of laser induced transient states in material systems.

Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

NASA Astrophysics Data System (ADS)

Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

2017-06-01

Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

High-yield, ultrafast, surface plasmon-enhanced, Au nanorod optical field electron emitter arrays.

PubMed

Hobbs, Richard G; Yang, Yujia; Fallahi, Arya; Keathley, Philip D; De Leo, Eva; Kärtner, Franz X; Graves, William S; Berggren, Karl K

2014-11-25

Here we demonstrate the design, fabrication, and characterization of ultrafast, surface-plasmon enhanced Au nanorod optical field emitter arrays. We present a quantitative study of electron emission from Au nanorod arrays fabricated by high-resolution electron-beam lithography and excited by 35 fs pulses of 800 nm light. We present accurate models for both the optical field enhancement of Au nanorods within high-density arrays, and electron emission from those nanorods. We have also studied the effects of surface plasmon damping induced by metallic interface layers at the substrate/nanorod interface on near-field enhancement and electron emission. We have identified the peak optical field at which the electron emission mechanism transitions from a 3-photon absorption mechanism to strong-field tunneling emission. Moreover, we have investigated the effects of nanorod array density on nanorod charge yield, including measurement of space-charge effects. The Au nanorod photocathodes presented in this work display 100-1000 times higher conversion efficiency relative to previously reported UV triggered emission from planar Au photocathodes. Consequently, the Au nanorod arrays triggered by ultrafast pulses of 800 nm light in this work may outperform equivalent UV-triggered Au photocathodes, while also offering nanostructuring of the electron pulse produced from such a cathode, which is of interest for X-ray free-electron laser (XFEL) development where nanostructured electron pulses may facilitate more efficient and brighter XFEL radiation.

Control of Terahertz Emission by Ultrafast Spin-Charge Current Conversion at Rashba Interfaces

NASA Astrophysics Data System (ADS)

Jungfleisch, Matthias B.; Zhang, Qi; Zhang, Wei; Pearson, John E.; Schaller, Richard D.; Wen, Haidan; Hoffmann, Axel

2018-05-01

We show that a femtosecond spin-current pulse can generate terahertz (THz) transients at Rashba interfaces between two nonmagnetic materials. Our results unambiguously demonstrate the importance of the interface in this conversion process that we interpret in terms of the inverse Rashba Edelstein effect, in contrast to the THz emission in the bulk conversion process via the inverse spin-Hall effect. Furthermore, we show that at Rashba interfaces the THz-field amplitude can be controlled by the helicity of the light. The optical generation of electric photocurrents by these interfacial effects in the femtosecond regime will open up new opportunities in ultrafast spintronics.

Control of Terahertz Emission by Ultrafast Spin-Charge Current Conversion at Rashba Interfaces.

PubMed

Jungfleisch, Matthias B; Zhang, Qi; Zhang, Wei; Pearson, John E; Schaller, Richard D; Wen, Haidan; Hoffmann, Axel

2018-05-18

We show that a femtosecond spin-current pulse can generate terahertz (THz) transients at Rashba interfaces between two nonmagnetic materials. Our results unambiguously demonstrate the importance of the interface in this conversion process that we interpret in terms of the inverse Rashba Edelstein effect, in contrast to the THz emission in the bulk conversion process via the inverse spin-Hall effect. Furthermore, we show that at Rashba interfaces the THz-field amplitude can be controlled by the helicity of the light. The optical generation of electric photocurrents by these interfacial effects in the femtosecond regime will open up new opportunities in ultrafast spintronics.

Ultrafast photocurrents at the surface of the three-dimensional topological insulator Bi2Se3

PubMed Central

Braun, Lukas; Mussler, Gregor; Hruban, Andrzej; Konczykowski, Marcin; Schumann, Thomas; Wolf, Martin; Münzenberg, Markus; Perfetti, Luca; Kampfrath, Tobias

2016-01-01

Three-dimensional topological insulators are fascinating materials with insulating bulk yet metallic surfaces that host highly mobile charge carriers with locked spin and momentum. Remarkably, surface currents with tunable direction and magnitude can be launched with tailored light beams. To better understand the underlying mechanisms, the current dynamics need to be resolved on the timescale of elementary scattering events (∼10 fs). Here, we excite and measure photocurrents in the model topological insulator Bi2Se3 with a time resolution of 20 fs by sampling the concomitantly emitted broadband terahertz (THz) electromagnetic field from 0.3 to 40 THz. Strikingly, the surface current response is dominated by an ultrafast charge transfer along the Se–Bi bonds. In contrast, photon-helicity-dependent photocurrents are found to be orders of magnitude smaller than expected from generation scenarios based on asymmetric depopulation of the Dirac cone. Our findings are of direct relevance for broadband optoelectronic devices based on topological-insulator surface currents. PMID:27796297

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eads, Calley N.; Bandak, Dmytro; Neupane, Mahesh R.

Strong quantum confinement effects lead to striking new physics in two-dimensional materials such as graphene or transition metal dichalcogenides. While spectroscopic fingerprints of such quantum confinement have been demonstrated widely, the consequences for carrier dynamics are at present less clear, particularly on ultrafast timescales. This is important for tailoring, probing, and understanding spin and electron dynamics in layered and two-dimensional materials even in cases where the desired bandgap engineering has been achieved. Here in this paper we show by means of core–hole clock spectroscopy that SnS 2 exhibits spindependent attosecond charge delocalization times (τ deloc) for carriers confined within amore » layer, τ deloc < 400 as, whereas interlayer charge delocalization is dynamically quenched in excess of a factor of 10, τ deloc > 2.7 fs. These layer decoupling dynamics are a direct consequence of strongly anisotropic screening established within attoseconds, and demonstrate that important two-dimensional characteristics are also present in bulk crystals of van der Waalslayered materials, at least on ultrafast timescales.« less

The mechanism of charge carrier generation at the TiO2—n-Si heterojunction activated by gold nanoparticles

NASA Astrophysics Data System (ADS)

Mishin, Maxim V.; Vorobyev, Alexander A.; Kondrateva, Anastasia S.; Koroleva, Ekaterina Y.; Karaseov, Platon A.; Bespalova, Polina G.; Shakhmin, Alexander L.; Glukhovskoy, Anatoly V.; Wurz, Marc Christopher; Filimonov, Alexey V.

2018-07-01

Photo-induced current through nanocomposite heterojunction structures consisting of a TiO2 coating activated with embedded gold nanoparticles on top of Si, SiO2, and columnar structured SiO2 is studied. The highest photo-activity in the visible part of the spectrum is found in the composite containing pillar-like silicon dioxide nanostructures. Experimental results were qualitatively explained on the basis of Franz-Keldysh effect taking into account the effects of electrical inhomogeneities appearing at charged nanoparticles. It is established that processes at the interface between silicon and noble metal nanoparticles play an important role in charge carrier photo-generation which opens a new opportunity to tune the photo-response of a nanocomposite via changing heterostructure topology.

Reversible Strain-Induced Electron-Hole Recombination in Silicon Nanowires Observed with Femtosecond Pump-Probe Microscopy

DTIC Science & Technology

2014-01-01

devices with indirect-bandgap materials such as silicon . KEYWORDS: Ultrafast imaging , strained nanomaterials, spectroscopy Lattice strain produced by...photogenerated charge cloud as a result of carrier diffusion . Normalized carrier profiles, generated by integrating the images along the direction normal to the...To test this idea, Figure 2. Charge carrier diffusion in a Si NW locally strained by a bending deformation (A) SEM image of a bent Si nanowire ∼100

Coherent control of D2/H2 dissociative ionization by a mid-infrared two-color laser field

NASA Astrophysics Data System (ADS)

Wanie, Vincent; Ibrahim, Heide; Beaulieu, Samuel; Thiré, Nicolas; Schmidt, Bruno E.; Deng, Yunpei; Alnaser, Ali S.; Litvinyuk, Igor V.; Tong, Xiao-Min; Légaré, François

2016-01-01

Steering the electrons during an ultrafast photo-induced process in a molecule influences the chemical behavior of the system, opening the door to the control of photochemical reactions and photobiological processes. Electrons can be efficiently localized using a strong laser field with a well-designed temporal shape of the electric component. Consequently, many experiments have been performed with laser sources in the near-infrared region (800 nm) in the interest of studying and enhancing the electron localization. However, due to its limited accessibility, the mid-infrared (MIR) range has barely been investigated, although it allows to efficiently control small molecules and even more complex systems. To push further the manipulation of basic chemical mechanisms, we used a MIR two-color (1800 and 900 nm) laser field to ionize H2 and D2 molecules and to steer the remaining electron during the photo-induced dissociation. The study of this prototype reaction led to the simultaneous control of four fragmentation channels. The results are well reproduced by a theoretical model solving the time-dependent Schrödinger equation for the molecular ion, identifying the involved dissociation mechanisms. By varying the relative phase between the two colors, asymmetries (i.e., electron localization selectivity) of up to 65% were obtained, corresponding to enhanced or equivalent levels of control compared to previous experiments. Experimentally easier to implement, the use of a two-color laser field leads to a better electron localization than carrier-envelope phase stabilized pulses and applying the technique in the MIR range reveals more dissociation channels than at 800 nm.

Mechanism of photoexcited precession of magnetization in (Ga,Mn)As on the basis of time-resolved spectroscopy

NASA Astrophysics Data System (ADS)

Matsuda, T.; Munekata, H.

2016-02-01

In order to investigate the mechanism of photoexcited precession of magnetization in ferromagnetic G a1 -xM nxAs , magneto-optical (MO) and differential reflectivity (Δ R /R ; DR) temporal profiles are studied at relatively long (picosecond to nanosecond) and ultrashort (1 ps or less) time scales for samples with different Mn content (x =0.01 -0.11 ) . As to the oscillatory MO profiles observed in the long time scale, simulation based on the Landau-Lifshitz-Gilbert equation combined with two different MO effects confirms photoinducement of the perpendicular anisotropy component Δ Heff ,⊥ . As for the profiles observed in the ultrashort time scale, they are consistently explained in terms of the dynamics of photogenerated carriers, but not by the sudden reduction in magnetization (the ultrafast demagnetization). In light of these experimental results and analyses, a mechanism that accounts for the photoinduced Δ Heff ,⊥ is addressed: namely, photoionizationlike excitation of M n2 + , M n2 ++h ν →M n2 +,*=M n3++e- . That such excitation tips magnetic anisotropy toward the out-of-plane direction through the inducement of orbital angular momentum and the gradient ∂ (M n2 +,* )/∂ z is discussed. The validity of the proposed mechanism is examined by estimating the efficiency of excitation on the basis of the Lambert-Beer law and the experimental Δ Heff ,⊥ values, through which an efficiency of 1-10 ppm with a nominal optical cross section of around 5 ×10-12m2 is obtained.

New Aspects of Photocurrent Generation at Graphene pn Junctions Revealed by Ultrafast Optical Measurements

NASA Astrophysics Data System (ADS)

Aivazian, Grant; Sun, Dong; Jones, Aaron; Ross, Jason; Yao, Wang; Cobden, David; Xu, Xiaodong

2012-02-01

The remarkable electrical and optical properties of graphene make it a promising material for new optoelectronic applications. However, one important, but so far unexplored, property is the role of hot carriers in charge and energy transport at graphene interfaces. Here we investigate the photocurrent (PC) dynamics at a tunable graphene pn junction using ultrafast scanning PC microscopy. Pump-probe measurements show a temperature dependent relaxation time of photogenerated carriers that increases from 1.5ps at 290K to 4ps at 20K; while the amplitude of the PC is independent of the lattice temperature. These observations imply that it is hot carriers, not phonons, which dominate ultrafast energy transport. Gate dependent measurements show many interesting features such as pump induced saturation, enhancement, and sign reversal of probe generated PC. These observations reveal that the underlying PC mechanism is a combination of the thermoelectric and built-in electric field effects. Our results enhance the understanding of non-equilibrium electron dynamics, electron-electron interactions, and electron-phonon interactions in graphene. They also determine fundamental limits on ultrafast device operation speeds (˜500 GHz) for graphene-based photodetectors.

Change of electric dipole moment in charge transfer transitions of ferrocene oligomers studied by ultrafast two-photon absorption

NASA Astrophysics Data System (ADS)

Mikhaylov, Alexander; Arias, Eduardo; Moggio, Ivana; Ziolo, Ronald; Uudsemaa, Merle; Trummal, Aleksander; Cooper, Thomas; Rebane, Aleksander

2017-02-01

Change of permanent electric dipole moment in the lower-energy charge transfer transitions for a series of symmetrical and non-symmetrical ferrocene-phenyleneethynylene oligomers were studied by measuring the corresponding femtosecond two-photon absorption cross section spectra, and were determined to be in the range Δμ = 3 - 10 D. Quantum-chemical calculations of Δμ for the non-symmetrical oligomers show good quantitative agreement with the experimental results, thus validating two-photon absorption spectroscopy as a viable experimental approach to study electrostatic properties of organometallics and other charge transfer systems.

Ballistic and resonant negative photocurrents in semiconducting carbon nanotubes

NASA Astrophysics Data System (ADS)

Karnetzky, Christoph; Sponfeldner, Lukas; Engl, Max; Holleitner, Alexander W.

2017-04-01

Ultrafast photocurrent experiments are performed on semiconducting, single-walled carbon nanotubes under a resonant optical excitation of their subbands. The photogenerated excitons are dissociated at large electric fields and the resulting transport of the charge carriers turns out to be ballistic. Thermionic emission processes to the contacts dominate the photocurrent amplitude. The charge current without laser excitation is well described by a Fowler-Nordheim tunneling. The time-averaged photocurrent changes polarity as soon as sufficient charge carriers are injected from the contacts, which can be explained by an effective population inversion in the optically pumped subbands.

Ballistic and resonant negative photocurrents in single carbon nanotubes

NASA Astrophysics Data System (ADS)

Karnetzky, Christoph; Sponfeldner, Lukas; Engl, Max; Holleitner, Alexander W.

We present ultrafast photocurrent experiments on semiconducting, single-walled carbon nanotubes under a resonant optical excitation of their subbands. We demonstrate that a ballistic transport of the photogenerated charge carriers can be achieved. Moreover, thermionic emission processes to the contacts dominate the photocurrent. In contrast, the charge current without laser excitation is well described by a Fowler-Nordheim tunneling. The time-averaged photocurrent changes polarity as soon as sufficient charge carriers are injected from the contacts, which can be explained by an effective population inversion in the optically pumped subbands. We acknowledge the ERC via the project NanoREAL.

Ultrafast far-infrared studies of vanadates &mdash Multiple routes for an insulator to metal transition

NASA Astrophysics Data System (ADS)

Liu, Mengkun

The metal insulator transition in vanadates has been studied for decades and yet new discoveries still spring up revealing new physics, especially among two of the most studied members: Vanadium sesquioxide (V20 3) and Vanadium dioxide (VO2). Although subtleties abound, both of the materials have first order insulator to metal phase transitions that are considered to be related to strong electron-electron (e-e) correlation. Further, ultrafast spectroscopy of strongly correlated materials has generated great interest in the field given the potential to dynamically distinguish the difference between electronic (spin) response versus lattice responses due to the associated characteristic energy and time scales. In this thesis, I mainly focus on utilizing ultrafast optical and THz spectroscopy to study phase transition dynamics in high quality V20 3 and VO2 thin films epitaxially grown on different substrates. The main findings of the thesis are: (1) Despite the fact that the insulator to metal transition (IMT) in V203 is electron-correlation driven, lattice distortion plays an important role. Coherent oscillations in the far-infrared conductivity are observed resulting from coherent acoustic phonon modulation of the bandwidth W. The same order of lattice distortion induces less of an effect on the electron transport in VO2 in comparison to V203. This is directly related to the difference in latent heat of the phase transitions in VO2 and V203. (2) It is possible for the IMT to occur with very little structural change in epitaxial strained VO2 films, like in the case of Cr doped or strained V203. However, in V02, this necessitates a large strain which is only possible by clamping to a substrate with larger c axis parameter through epitaxial growth. This is demonstrated for VO 2 films on TiO2 substrates. (3) Initiating an ultrafast photo-induced insulator-to-metal transition (IMT) is not only possible with above bandgap excitation, but also possible with high-field far-infrared excitation. With the help of the field enhancement in metamaterial split ring resonator gaps, we obtain picosecond THz electric field transients of several MV/cm which is sufficient to drive the insulator to metal transition in V02.

Photoinduced Charge Transfer and Electrochemical Properties of Triphenylamine Ih-Sc3N@C80 Donor-Acceptor Conjugates

PubMed Central

Pinzón, Julio R.; Gasca, Diana C.; Shankara, Gayathri. S; Bottari, Giovanni; Torres, Tomás; Guldi, Dirk M.; Echegoyen, Luis

2009-01-01

Two isomeric [5,6]-pyrrolidine-Ih-Sc3N@C80 electron donor acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C60 analogues, in order to determine i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, ii) the thermal stability towards the retro-cycloaddition reaction and iii) the effect of changing C60 for Ih-Sc3N@C80 as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C60 and Ih-Sc3N@C80 dyads. In addition to that, the N-substituted TPA-Ih-Sc3N@C80 dyad has much better thermal stability than the 2-subtituted one. Finally, the Ih-Sc3N@C80 dyads have considerably longer lived charge separated states than their C60 analogues, thus approving the advantage of using Ih-Sc3N@C80 instead of C60 as the acceptor for the construction of fullerene based donor acceptor conjugates. These findings are important for the design and future application of Ih-Sc3N@C80 dyads as materials for the construction of plastic organic solar cells. PMID:19445462

Ultrafast Intramolecular Electron and Proton Transfer in Bis(imino)isoindole Derivatives.

PubMed

Driscoll, Eric; Sorenson, Shayne; Dawlaty, Jahan M

2015-06-04

Concerted motion of electrons and protons in the excited state is pertinent to a wide range of chemical phenomena, including those relevant for solar-to-fuel light harvesting. The excited state dynamics of small proton-bearing molecules are expected to serve as models for better understanding such phenomena. In particular, for designing the next generation of multielectron and multiproton redox catalysts, understanding the dynamics of more than one proton in the excited state is important. Toward this goal, we have measured the ultrafast dynamics of intramolecular excited state proton transfer in a recently synthesized dye with two equivalent transferable protons. We have used a visible ultrafast pump to initiate the proton transfer in the excited state, and have probed the transient absorption of the molecule over a wide bandwidth in the visible range. The measurement shows that the signal which is characteristic of proton transfer emerges within ∼710 fs. To identify whether both protons were transferred in the excited state, we have measured the ultrafast dynamics of a related derivative, where only a single proton was available for transfer. The measured proton transfer time in that molecule was ∼427 fs. The observed dynamics in both cases were reasonably fit with single exponentials. Supported by the ultrafast observations, steady-state fluorescence, and preliminary computations of the relaxed excited states, we argue that the doubly protonated derivative most likely transfers only one of its two protons in the excited state. We have performed calculations of the frontier molecular orbitals in the Franck-Condon region. The calculations show that in both derivatives, the excitation is primarily from the HOMO to LUMO causing a large rearrangement of the electronic charge density immediately after photoexcitation. In particular, charge density is shifted away from the phenolic protons and toward the proton acceptor nitrogens. The proton transfer is hypothesized to occur both due to enhanced acidity of the phenolic proton and enhanced basicity of the nitrogen in the excited state. We hope this study can provide insight for better understanding of the general class of excited state concerted electron-proton dynamics.

Enhanced coherent oscillations in the superconducting state of underdoped YB a 2 C u 3 O 6 + x induced via ultrafast terahertz excitation

DOE PAGES

Dakovski, Georgi L.; Lee, Wei -Sheng; Hawthorn, David G.; ...

2015-06-24

We utilize intense, single-cycle terahertz pulses to induce collective excitations in the charge-density-wave-ordered underdoped cuprate YBa 2Cu 3O 6+x. These excitations manifest themselves as pronounced coherent oscillations of the optical reflectivity in the transient state, accompanied by minimal incoherent quasiparticle relaxation dynamics. The oscillations occur at frequencies consistent with soft phonon energies associated with the charge-density-wave, but vanish above the superconducting transition temperature rather than that at the charge-density-wave transition. These results indicate an intimate relationship of the terahertz excitation with the underlying charge-density-wave and the superconducting condensate itself.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

PubMed Central

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-01-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level. PMID:28272396

Ultrafast surface carrier dynamics in the topological insulator Bi₂Te₃.

PubMed

Hajlaoui, M; Papalazarou, E; Mauchain, J; Lantz, G; Moisan, N; Boschetto, D; Jiang, Z; Miotkowski, I; Chen, Y P; Taleb-Ibrahimi, A; Perfetti, L; Marsi, M

2012-07-11

We discuss the ultrafast evolution of the surface electronic structure of the topological insulator Bi(2)Te(3) following a femtosecond laser excitation. Using time and angle-resolved photoelectron spectroscopy, we provide a direct real-time visualization of the transient carrier population of both the surface states and the bulk conduction band. We find that the thermalization of the surface states is initially determined by interband scattering from the bulk conduction band, lasting for about 0.5 ps; subsequently, few picoseconds are necessary for the Dirac cone nonequilibrium electrons to recover a Fermi-Dirac distribution, while their relaxation extends over more than 10 ps. The surface sensitivity of our measurements makes it possible to estimate the range of the bulk-surface interband scattering channel, indicating that the process is effective over a distance of 5 nm or less. This establishes a correlation between the nanoscale thickness of the bulk charge reservoir and the evolution of the ultrafast carrier dynamics in the surface Dirac cone.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery

NASA Astrophysics Data System (ADS)

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-01

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion...carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Light, Molecules, Action: Using Ultrafast Uv-Visible and X-Ray Spectroscopy to Probe Excited State Dynamics in Photoactive Molecules

NASA Astrophysics Data System (ADS)

Sension, R. J.

2017-06-01

Light provides a versatile energy source capable of precise manipulation of material systems on size scales ranging from molecular to macroscopic. Photochemistry provides the means for transforming light energy from photon to process via movement of charge, a change in shape, a change in size, or the cleavage of a bond. Photochemistry produces action. In the work to be presented here ultrafast UV-Visible pump-probe, and pump-repump-probe methods have been used to probe the excited state dynamics of stilbene-based molecular motors, cyclohexadiene-based switches, and polyene-based photoacids. Both ultrafast UV-Visible and X-ray absorption spectroscopies have been applied to the study of cobalamin (vitamin B_{12}) based compounds. Optical measurements provide precise characterization of spectroscopic signatures of the intermediate species on the S_{1} surface, while time-resolved XANES spectra at the Co K-edge probe the structural changes that accompany these transformations.

Realizing Ultrafast Electron Pulse Self-Compression by Femtosecond Pulse Shaping Technique.

PubMed

Qi, Yingpeng; Pei, Minjie; Qi, Dalong; Yang, Yan; Jia, Tianqing; Zhang, Shian; Sun, Zhenrong

2015-10-01

Uncorrelated position and velocity distribution of the electron bunch at the photocathode from the residual energy greatly limit the transverse coherent length and the recompression ability. Here we first propose a femtosecond pulse-shaping method to realize the electron pulse self-compression in ultrafast electron diffraction system based on a point-to-point space-charge model. The positively chirped femtosecond laser pulse can correspondingly create the positively chirped electron bunch at the photocathode (such as metal-insulator heterojunction), and such a shaped electron pulse can realize the self-compression in the subsequent propagation process. The greatest advantage for our proposed scheme is that no additional components are introduced into the ultrafast electron diffraction system, which therefore does not affect the electron bunch shape. More importantly, this scheme can break the limitation that the electron pulse via postphotocathode static compression schemes is not shorter than the excitation laser pulse due to the uncorrelated position and velocity distribution of the initial electron bunch.

Organic photovoltaics: elucidating the ultra-fast exciton dissociation mechanism in disordered materials.

PubMed

Heitzer, Henry M; Savoie, Brett M; Marks, Tobin J; Ratner, Mark A

2014-07-14

Organic photovoltaics (OPVs) offer the opportunity for cheap, lightweight and mass-producible devices. However, an incomplete understanding of the charge generation process, in particular the timescale of dynamics and role of exciton diffusion, has slowed further progress in the field. We report a new Kinetic Monte Carlo model for the exciton dissociation mechanism in OPVs that addresses the origin of ultra-fast (<1 ps) dissociation by incorporating exciton delocalization. The model reproduces experimental results, such as the diminished rapid dissociation with increasing domain size, and also lends insight into the interplay between mixed domains, domain geometry, and exciton delocalization. Additionally, the model addresses the recent dispute on the origin of ultra-fast exciton dissociation by comparing the effects of exciton delocalization and impure domains on the photo-dynamics.This model provides insight into exciton dynamics that can advance our understanding of OPV structure-function relationships. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast fluxional exchange dynamics in electrolyte solvation sheath of lithium ion battery.

PubMed

Lee, Kyung-Koo; Park, Kwanghee; Lee, Hochan; Noh, Yohan; Kossowska, Dorota; Kwak, Kyungwon; Cho, Minhaeng

2017-03-08

Lithium cation is the charge carrier in lithium-ion battery. Electrolyte solution in lithium-ion battery is usually based on mixed solvents consisting of polar carbonates with different aliphatic chains. Despite various experimental evidences indicating that lithium ion forms a rigid and stable solvation sheath through electrostatic interactions with polar carbonates, both the lithium solvation structure and more importantly fluctuation dynamics and functional role of carbonate solvent molecules have not been fully elucidated yet with femtosecond vibrational spectroscopic methods. Here we investigate the ultrafast carbonate solvent exchange dynamics around lithium ions in electrolyte solutions with coherent two-dimensional infrared spectroscopy and find that the time constants of the formation and dissociation of lithium-ion···carbonate complex in solvation sheaths are on a picosecond timescale. We anticipate that such ultrafast microscopic fluxional processes in lithium-solvent complexes could provide an important clue to understanding macroscopic mobility of lithium cation in lithium-ion battery on a molecular level.

Direct determination of resonance energy transfer in photolyase: structural alignment for the functional state.

PubMed

Tan, Chuang; Guo, Lijun; Ai, Yuejie; Li, Jiang; Wang, Lijuan; Sancar, Aziz; Luo, Yi; Zhong, Dongping

2014-11-13

Photoantenna is essential to energy transduction in photoinduced biological machinery. A photoenzyme, photolyase, has a light-harvesting pigment of methenyltetrahydrofolate (MTHF) that transfers its excitation energy to the catalytic flavin cofactor FADH¯ to enhance DNA-repair efficiency. Here we report our systematic characterization and direct determination of the ultrafast dynamics of resonance energy transfer from excited MTHF to three flavin redox states in E. coli photolyase by capturing the intermediates formed through the energy transfer and thus excluding the electron-transfer quenching pathway. We observed 170 ps for excitation energy transferring to the fully reduced hydroquinone FADH¯, 20 ps to the fully oxidized FAD, and 18 ps to the neutral semiquinone FADH(•), and the corresponding orientation factors (κ(2)) were determined to be 2.84, 1.53 and 1.26, respectively, perfectly matching with our calculated theoretical values. Thus, under physiological conditions and over the course of evolution, photolyase has adopted the optimized orientation of its photopigment to efficiently convert solar energy for repair of damaged DNA.

Ultrafast carrier dynamics in bimetallic nanostructure-enhanced methylammonium lead bromide perovskites.

PubMed

Zarick, Holly F; Boulesbaa, Abdelaziz; Puretzky, Alexander A; Talbert, Eric M; DeBra, Zachary R; Soetan, Naiya; Geohegan, David B; Bardhan, Rizia

2017-01-26

In this work, we examine the impact of hybrid bimetallic Au/Ag core/shell nanostructures on the carrier dynamics of methylammonium lead tribromide (MAPbBr 3 ) mesoporous perovskite solar cells (PSCs). Plasmon-enhanced PSCs incorporated with Au/Ag nanostructures demonstrated improved light harvesting and increased power conversion efficiency by 26% relative to reference devices. Two complementary spectral techniques, transient absorption spectroscopy (TAS) and time-resolved photoluminescence (trPL), were employed to gain a mechanistic understanding of plasmonic enhancement processes. TAS revealed a decrease in the photobleach formation time, which suggests that the nanostructures improve hot carrier thermalization to an equilibrium distribution, relieving hot phonon bottleneck in MAPbBr 3 perovskites. TAS also showed a decrease in carrier decay lifetimes, indicating that nanostructures enhance photoinduced carrier generation and promote efficient electron injection into TiO 2 prior to bulk recombination. Furthermore, nanostructure-incorporated perovskite films demonstrated quenching in steady-state PL and decreases in trPL carrier lifetimes, providing further evidence of improved carrier injection in plasmon-enhanced mesoporous PSCs.

Understanding Phase-Change Memory Alloys from a Chemical Perspective

NASA Astrophysics Data System (ADS)

Kolobov, A. V.; Fons, P.; Tominaga, J.

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Understanding Phase-Change Memory Alloys from a Chemical Perspective.

PubMed

Kolobov, A V; Fons, P; Tominaga, J

2015-09-01

Phase-change memories (PCM) are associated with reversible ultra-fast low-energy crystal-to-amorphous switching in GeTe-based alloys co-existing with the high stability of the two phases at ambient temperature, a unique property that has been recently explained by the high fragility of the glass-forming liquid phase, where the activation barrier for crystallisation drastically increases as the temperature decreases from the glass-transition to room temperature. At the same time the atomistic dynamics of the phase-change process and the associated changes in the nature of bonding have remained unknown. In this work we demonstrate that key to this behavior is the formation of transient three-center bonds in the excited state that is enabled due to the presence of lone-pair electrons. Our findings additionally reveal previously ignored fundamental similarities between the mechanisms of reversible photoinduced structural changes in chalcogenide glasses and phase-change alloys and offer new insights into the development of efficient PCM materials.

Time-resolved measurements with streaked diffraction patterns from electrons generated in laser plasma wakefield

NASA Astrophysics Data System (ADS)

He, Zhaohan; Nees, John; Hou, Bixue; Krushelnick, Karl; Thomas, Alec; Beaurepaire, Benoît; Malka, Victor; Faure, Jérôme

2013-10-01

Femtosecond bunches of electrons with relativistic to ultra-relativistic energies can be robustly produced in laser plasma wakefield accelerators (LWFA). Scaling the electron energy down to sub-relativistic and MeV level using a millijoule laser system will make such electron source a promising candidate for ultrafast electron diffraction (UED) applications due to the intrinsic short bunch duration and perfect synchronization with the optical pump. Recent results of electron diffraction from a single crystal gold foil, using LWFA electrons driven by 8-mJ, 35-fs laser pulses at 500 Hz, will be presented. The accelerated electrons were collimated with a solenoid magnetic lens. By applying a small-angle tilt to the magnetic lens, the diffraction pattern can be streaked such that the temporal evolution is separated spatially on the detector screen after propagation. The observable time window and achievable temporal resolution are studied in pump-probe measurements of photo-induced heating on the gold foil.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

DOE PAGES

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; ...

2017-05-24

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born–Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersionmore » of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.« less

Broadband photocarrier dynamics and nonlinear absorption of PLD-grown WTe2 semimetal films

NASA Astrophysics Data System (ADS)

Gao, Wenbin; Huang, Lei; Xu, Jinlong; Chen, Yequan; Zhu, Chunhui; Nie, Zhonghui; Li, Yao; Wang, Xuefeng; Xie, Zhenda; Zhu, Shining; Xu, Jun; Wan, Xiangang; Zhang, Chao; Xu, Yongbing; Shi, Yi; Wang, Fengqiu

2018-04-01

WTe2 is a unique material in the family of transition metal dichalcogenides and it has been proposed as a candidate for type-II Weyl semimetals. However, thus far, studies on the optical properties of this emerging material have been significantly hindered by the lack of large-area, high-quality WTe2 materials. Here, we grow a centimeter-scale, highly crystalline WTe2 ultrathin film (˜35 nm) by a pulsed laser deposition technique. Broadband pump-probe spectroscopy (1.2-2.5 μm) reveals a peculiar ultrafast optical response where an initial photo-bleaching signal (lasting ˜3 ps) is followed by a long-lived photoinduced absorption signature. Nonlinear absorption characterization using femtosecond pulses confirms the saturable absorption response of the WTe2 ultrathin films, and we further demonstrated a mode-locked Thulium fiber laser using a WTe2 absorber. Our work provides important insights into linear and nonlinear optical responses of WTe2 thin films.

Tunable near- to mid-infrared pump terahertz probe spectroscopy in reflection geometry

NASA Astrophysics Data System (ADS)

Zhang, S. J.; Wang, Z. X.; Dong, T.; Wang, N. L.

2017-10-01

Strong-field mid-infrared pump-terahertz (THz) probe spectroscopy has been proven as a powerful tool for light control of different orders in strongly correlated materials. We report the construction of an ultrafast broadband infrared pump-THz probe system in reflection geometry. A two-output optical parametric amplifier is used for generating mid-infrared pulses with GaSe as the nonlinear crystal. The setup is capable of pumping bulk materials at wavelengths ranging from 1.2 μm to 15 μm and beyond, and detecting the subtle, transient photoinduced changes in the reflected electric field of the THz probe at different temperatures. As a demonstration, we present 15 μm pump-THz probe measurements of a bulk EuSbTe3 single crystal. A 0:5% transient change in the reflected THz electric field can be clearly resolved. The widely tuned pumping energy could be used in mode-selective excitation experiments and applied to many strongly correlated electron systems.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

NASA Astrophysics Data System (ADS)

Lemke, Henrik T.; Kjær, Kasper S.; Hartsock, Robert; van Driel, Tim B.; Chollet, Matthieu; Glownia, James M.; Song, Sanghoon; Zhu, Diling; Pace, Elisabetta; Matar, Samir F.; Nielsen, Martin M.; Benfatto, Maurizio; Gaffney, Kelly J.; Collet, Eric; Cammarata, Marco

2017-05-01

The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3]2+ compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

NASA Astrophysics Data System (ADS)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Ultrafast Extreme Ultraviolet Spectroscopy of Methylammonium Lead Iodide Perovskite for Carrier Specific Photophysics

NASA Astrophysics Data System (ADS)

Verkamp, Max A.; Lin, Ming-Fu; Ryland, Elizabeth S.; Benke, Kristin; Vura-Weis, Josh

2017-06-01

Methyl ammonium lead iodide (perovskite) is a leading candidate for next-generation solar cell devices. However, the fundamental photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) spectroscopy was used to investigate relaxation dynamics in perovskite with carrier specific signals arising from transitions from the common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation in a broad spectrum (40-70 eV) were obtained using high-harmonic generation in a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the dynamics of charge carriers after above-band and band-edge excitation.

Communication: Charge-transfer rate constants in zinc-porphyrin-porphyrin-derived dyads: A Fermi golden rule first-principles-based study

NASA Astrophysics Data System (ADS)

Manna, Arun K.; Dunietz, Barry D.

2014-09-01

We investigate photoinduced charge transfer (CT) processes within dyads consisting of porphyrin derivatives in which one ring ligates a Zn metal center and where the rings vary by their degree of conjugation. Using a first-principles approach, we show that molecular-scale means can tune CT rates through stabilization affected by the polar environment. Such means of CT tuning are important for achieving high efficiency optoelectronic applications using organic semiconducting materials. Our fully quantum mechanical scheme is necessary for reliably modeling the CT process across different regimes, in contrast to the pervading semi-classical Marcus picture that grossly underestimates transfer in the far-inverted regime.

Photoinduced charge-carrier modulation of inkjet-printed carbon nanotubes via poly(vinyl acetate) doping and dedoping for thermoelectric generators

NASA Astrophysics Data System (ADS)

Horike, Shohei; Fukushima, Tatsuya; Saito, Takeshi; Koshiba, Yasuko; Ishida, Kenji

2018-01-01

Here, we studied the charge-carrier modulation of single-walled carbon nanotubes (SWCNTs) via poly(vinyl acetate) (PVAc) doping and dedoping under ultraviolet (UV) light irradiation with the aim of pairing several p- and n-type SWCNTs as thermoelectric (TE) elements. The Seebeck coefficient of the SWCNTs was first made negative by doping with PVAc and then made positive again through UV-induced PVAc dedoping. A possible TE module configuration and the process for its fabrication are proposed, wherein prints and photopatterns can be obtained without the use of additional electrodes. Our findings enable the fabrication of fine TE modules using simple materials and techniques.

Perovskites for Photovoltaics in the Spotlight: Photoinduced Physical Changes and Their Implications.

PubMed

Gottesman, Ronen; Zaban, Arie

2016-02-16

Organic-inorganic halide perovskites are in consensus to revolutionize the field of photovoltaics and optoelectronic devices due to their superior optical and electronic properties which are unprecedented in comparison to those of other solution processed semiconductors. These hybrid materials are used as light absorbers and also as charge carriers which makes them very versatile to be implemented and studied in a multitude of fields. Traditionally, the working paradigm in solar cells and optoelectronic devices' characterization has been that the properties of photovoltaic materials remain stable following illumination of varying times and intensities. However, recently there has been a growing number of reports on prolonged illumination-dependent physical changes in perovskite films and perovskite based devices. The changes are reversible and range from structural transformations and differences in optical characteristics, to an increase in optoelectronic properties and physical parameters. In this Account, we review the physical changes in three reported model systems which display changes under prolonged illumination of light intensities of ∼0.01-1 sun. The three systems are (i) a free-standing perovskite film on a glass substrate, (ii) a symmetrical system with nonselective electrical contacts, and (iii) a working perovskite solar cell (either a planar or a porous structure). We examine each model system and discuss its photoinduced physical changes and conclude with the implications on future experimentation design, data analysis, and characterization that involve organic-inorganic halide perovskites illumination. Since hybrid perovskites are considered to be mixed ionic-electronic conductors in nature, ions that migrate in the perovskite under electrical fields can influence its properties. Therefore, an important distinction is made between photoinduced effects and photo and electric field induced effects. Thus, photoinduced effects are designated as observed effects in illuminated free-standing films or symmetrical devices without selective contacts. In contrast, photo- and electric field induced effects are designated as observed effects under open-circuit potential or during voltage scanning (internal electrical field exists across the device). In the latter case, the two effects are superimposed and it is difficult to evaluate the relative influence of each one (light or electric field). However, we show that the magnitude and the importance of the photoinduced effect are substantial.