Carrier photogeneration, drift and recombination in a semiconducting carbon nanotube network.

Charge carrier photogeneration, drift and recombination in thin film networks of polymer-wrapped (6,5)-single-wall carbon nanotubes (SWNTs) blended with phenyl-C61-butyric acid methyl ester (PCBM) have been investigated by using transient photocurrent and time-delayed collection field (TDCF) techniques. Three distinct transient photocurrent components on the nano- and microsecond timescales have been identified. We attribute the dominant (>50% of total extracted charge) ultrashort photocurrent component with a decay time below our experimental time-resolution of 2 ns to the intratube hole motion. The second component on the few microsecond timescale is attributed to the intertube hole transfer, while the slowest component is assigned to the electron drift within the PCBM phase. The hole drift distance appears to be limited by gaps in the nanotube percolation network rather than by hole trapping or recombination. Photocurrent saturation was observed when excitation densities reached more than one charge pair per nanotube; we attribute this to the local electric field screening.

Role of coherence and delocalization in photo-induced electron transfer at organic interfaces.

Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

Fluorescence relaxation kinetics of poly(methylphenylsilane) film and nanocomposites.

A comparative study of fluorescence relaxation kinetics of σ-conjugated poly(methylphenylsilane) (PMPS) polymer film and nanocomposites has been performed by ultrafast time-gated fluorescence measurements at various temperatures. Investigations have revealed a fine structure of excitonic σ-σ* band. We attribute this structure to emission from two spatially independent states with different ordering of the polymer chain segments, type gauche and trans conformations. In contrary to a more ordered polymer poly(di-n-hexylsilane), no clear thermochromic transition has been detected in PMPS film; however, the trans band intensity increases with temperature and with excitation wavelength, but it is absent when polymer is incorporated into nanopores of small diameter.

Investigation of microstructured chitosans by coherent anti-Stokes Raman microscopy.

This work describes application of coherent anti-Stokes Raman scattering (CARS) microscopy technique for analytical characterization of microstructured materials based on chitosan. We demonstrate that nitrogen-hydrogen vibration band in the high wavenumber region of CARS spectrum prevails over response from oxygen-hydrogen vibrations and can be used as a spectral marker of chitosan. The chemically selective imaging is experimentally demonstrated by applying CARS microscopy to discriminate between chitosan and polystyrene microparticles. CARS microscopy was shown to be a valuable tool for characterization of polluted chitosan fibre from utilized engine filter material. A possibility to observe foreign material pieces on the surface of the polluted chitosan fibre is demonstrated and discussed.

Visualizing charge separation in bulk heterojunction organic solar cells.

Solar cells based on conjugated polymer and fullerene blends have been developed as a low-cost alternative to silicon. For efficient solar cells, electron-hole pairs must separate into free mobile charges that can be extracted in high yield. We still lack good understanding of how, why and when carriers separate against the Coulomb attraction. Here we visualize the charge separation process in bulk heterojunction solar cells by directly measuring charge carrier drift in a polymer:fullerene blend with ultrafast time resolution. We show that initially only closely separated (<1 nm) charge pairs are created and they separate by several nanometres during the first several picoseconds. Charge pairs overcome Coulomb attraction and form free carriers on a subnanosecond time scale. Numerical simulations complementing the experimental data show that fast three-dimensional charge diffusion within an energetically disordered medium, increasing the entropy of the system, is sufficient to drive the charge separation process.

Impact of intramolecular twisting and exciton migration on emission efficiency of multifunctional fluorene-benzothiadiazole-carbazole compounds.

Novel donor-acceptor compounds consisting of singly bonded fluorene (Fl), benzothiadiazole (BT), and carbazole (Cz) functional units in the same molecule were investigated. Analysis of the optical spectra and fluorescence transients of the compounds revealed the domination of intramolecular charge transfer (ICT) states with high fluorescence quantum yield (72%-85%). A similar Cz-Fl-Cz compound exhibiting 100% fluorescence quantum yield and no ICT character was also studied as a reference to reveal the impact of electron-accepting BT groups. Thorough examination of the optical properties of the compounds in different media, i.e., dilute solution and polymer matrix, indicated their twisted conformations due to steric hindrance in the ground state and flattened geometry in the excited state for both reference and ICT compounds. Remarkable fluorescence efficiency losses (amounting to 70%) observed upon casting the molecular solutions into neat films were determined to originate from the low-fluorescent twisted conformers and migration-facilitated exciton quenching. The majority of emission efficiency losses (over 70%) were caused by the twisted conformers, whereas only less than 30% by exciton-migration-induced nonradiative deactivation.

Electric field assisted charge carrier photogeneration in poly(spirobifluorene-co-benzothiadiazole).

The dynamics of charge carrier generation in poly(spirobifluorene-co-benzothiadiazole) was investigated by electric field-induced fluorescence quenching and differential absorption measurements. Three different time domains of carrier generation have been identified: an ultrafast phase, a subnanosecond phase, and an entire lifetime phase. The charge generation efficiencies during the first and second phases were found to be almost independent of temperature, being about 25% and 10%, respectively, at an applied electric field of 1.3×10(6) V/cm, while the generation efficiency during the third phase increases from 2% at 80 K to 10% at room temperature. The results of transient spectroscopy measurements and quantum chemical calculations suggest an intramolecular charge transfer for about 1 ps from the alkoxy-substituted fluorene side group to the benzothiadiazole subunit of the main chain. The formation and evolution of the resulting charge transfer states determine the way of charge carrier generation.

Ultrafast dynamics of carrier mobility in a conjugated polymer probed at molecular and microscopic length scales.

We used time-resolved electric-field-induced second-harmonic generation to probe the charge-carrier-mobility dynamics in amorphous organic materials on an ultrafast time scale. We were able to show that the mobility in poly-spiro-bifluorene-co-benzothiadiazol decreases from 0.1 cm 2/V s at 1 ps to 10-6 cm2/V s within 1 mus. We attribute this dramatic decrease to the relaxation of the charge carriers within the density of states, clearly demonstrating the impact of disorder on the nanoscale charge transport in amorphous semiconductors.

Ultrafast dynamics of the real and imaginary permittivity parts of a photoexcited silver layer revealed by surface plasmon resonance.

Dynamics of the real and imaginary parts of the dielectric permittivity of a photoexcited silver layer has been investigated by means of femtosecond pump-probe spectroscopy in a surface plasmon resonance Kretschmann configuration. Both real and imaginary permittivity parts experience changes in the visible-near-IR regions under silver excitation at 400 nm. The changes are stronger, particularly those of the imaginary part, at longer wavelengths. Three excited states are formed during the relaxation process, which are attributed to the nonequilibrium and equilibrium heated electron distributions and lattice heating. Different time evolutions of the real and imaginary dielectric permittivity parts are explained by different contributions from interband and intraband transitions caused by plasma frequency and electron scattering frequency variations.

Exciton diffusion and relaxation in methyl-substituted polyparaphenylene polymer films.

Exciton diffusion in ladder-type methyl-substituted polyparaphenylene film and solution was investigated by means of femtosecond pump-probe spectroscopy using a combined approach, analyzing exciton-exciton annihilation, and transient absorption depolarization properties. We show that the different views on the exciton dynamics offered by anisotropy decay and annihilation are required in order to obtain a correct picture of the energy transfer dynamics. Comparison of the exciton diffusion coefficient and exciton diffusion radius obtained for polymer film with the two techniques reveals that there is substantial short-range order in the film. Also in isolated chains there is considerable amount of order, as revealed from only partial anisotropy decay, which shows that only a small fraction of the excitons move to differently oriented polymer segments. It is further concluded that interchain energy transfer is faster than intrachain transfer, mainly as a result of shorter interchain distances between chromophoric units.

Dynamics of high repetition rate regenerative amplifiers.

Dynamics features of high repetition rate continuously pumped solid-state regenerative amplifiers were studied numerically. A space independent rate equations and discrete-time dynamical system approach were used for system state evolution analysis. Regular single-energy operation, quasi-periodic pulsing and chaotic behavior regions are distinguished in space of control parameters. Diagrams of dynamical regimes comprehensively exhibiting operation features of the system are presented. Seed energy is shown to be an important parameter determining the stability space. Conditions of stable operation are described quantitatively.

Ultrafast pump-probe surface plasmon resonance spectroscopy of thin gold films.

A time-resolved reflection pump-probe method was combined with a surface plasmon resonance technique in Kretschmann geometry for the investigation of ultrafast light-induced processes in thin films. Transient changes in the gold layer's reflectivity were observed when the layer was excited by 3 ps duration pulses with photon energy exceeding the interband transition and by probing with photon energy close to the interband transition. Comparison of the experimental and modeling results has shown that the imaginary part of the dielectric function of gold increases linearly during excitation, whereas the real part remains unchanged. The decay of the light-induced changes has two components. The first component is faster than the pulse duration, and the second is much longer than 1.5 ns; they are related to cooling of the electron plasma and lattice, respectively.

Singlet-singlet annihilation kinetics in aggregates and trimers of LHCII.

Singlet-singlet annihilation experiments have been performed on trimeric and aggregated light-harvesting complex II (LHCII) using picosecond spectroscopy to study spatial equilibration times in LHCII preparations, complementing the large amount of data on spectral equilibration available in literature. The annihilation kinetics for trimers can well be described by a statistical approach, and an annihilation rate of (24 ps)(-1) is obtained. In contrast, the annihilation kinetics for aggregates can well be described by a kinetic approach over many hundreds of picoseconds, and it is shown that there is no clear distinction between inter- and intratrimer transfer of excitation energy. With this approach, an annihilation rate of (16 ps)(-1) is obtained after normalization of the annihilation rate per trimer. It is shown that the spatial equilibration in trimeric LHCII between chlorophyll a molecules occurs on a time scale that is an order of magnitude longer than in Photosystem I-core, after correcting for the different number of chlorophyll a molecules in both systems. The slow transfer in LHCII is possibly an important factor in determining excitation trapping in Photosystem II, because it contributes significantly to the overall trapping time.

Ultrafast chlorophyll b-chlorophyll a excitation energy transfer in the isolated light harvesting complex, LHC II, of green plants. Implications for the organisation of chlorophylls.

The excitation energy transfer between chlorophyll b (Chl b) and chlorophyll a (Chl a) in the isolated trimeric chlorophyll-a/b-binding protein complex of spinach photosystem 2 (LHC II) has been studied by femtosecond spectroscopy. In the main absorption band of Chl b the ground state recovery consists of two components of 0.5 ps and 2.0 ps, respectively. Also in the Chl a absorption band, at 665 nm, the ground state recovery is essentially bi-exponential. In this case is, however, the fastest relaxation lifetime is a 2.0 ps component followed by a slower component with a lifetime in the order of 10-20 ps. In the Chl b absorption band a more or less constant anisotropy of r = 0.2 was observed during the 3 ps the system was monitored. In the Chl a absorption band there was, however, a relaxation of the anisotropy from r = 0.3 to a quasi steady state level of r = 0.18 in about 1 ps. Since the 0.5 ps component is only seen upon selective excitation of Chl b we assign this component to the energy transfer between Chl b and Chl a. The other components most likely represents redistribution processes of energy among spectrally different forms of Chl a. The energy transfer process between Chl b and Chl a can well be explained by the Förster mechanism which also gives a calculated distance of 13 A between interacting chromophores. The organisation of chlorophylls in LHC II is discussed in view of the recent crystal structure data (1991) Nature 350, 130].