Maxim S. Pshenichnikov

The Role of Driving Energy and Delocalized States for Charge Separation in Organic Semiconductors

Bands That Separate In organic photovoltaic devices, the charge carriers that form at the interface between donor and acceptor layers—the electrons and holes—form bound states called excitons. Efficient current generation requires some mechanism for their separation and for the movement of free carriers to the electrodes. Bakulin et al. (p. 1340, published online 23 February) studied a process in which the excitons created with an optical pulse were also subjected to infrared pulses. In polymer-blend devices, a three-step process was observed: The boundstate excitons diffused toward the donor-acceptor interface, formed a charge-transfer state, and then dissociated into free carriers. Bound excited charge carriers achieve long-range separation by promotion to delocalized band states. The electron-hole pair created via photon absorption in organic photoconversion systems must overcome the Coulomb attraction to achieve long-range charge separation. We show that this process is facilitated through the formation of excited, delocalized band states. In our experiments on organic photovoltaic cells, these states were accessed for a short time (<1 picosecond) via infrared (IR) optical excitation of electron-hole pairs bound at the heterojunction. Atomistic modeling showed that the IR photons promote bound charge pairs to delocalized band states, similar to those formed just after singlet exciton dissociation, which indicates that such states act as the gateway for charge separation. Our results suggest that charge separation in efficient organic photoconversion systems occurs through hot-state charge delocalization rather than energy-gradient–driven intermolecular hopping.

Optical pulse compression to 5 fs at a 1-MHz repetition rate

We report on the characterization and compression of the white-light continuum produced by injection of a 13-fs pulse from a cavity-dumped self-mode-locked Ti:sapphire laser into a single-mode fiber. Pulses as short as 5 fs were generated at repetition rates up to 1 MHz.

Autocorrelation measurement of 6-fs pulses based on the two-photon-induced photocurrent in a GaAsP photodiode

We experimentally characterize the two-photon response of a GaAsP photodiode by use of a femtosecond Ti:sapphire laser tuned below the diode bandgap. The photodiode is shown to be highly suitable for real-time second-order autocorrelation measurements of pulses as short as 6fs in duration and with energies as small as a few picojoules.

Hydrogen-bond dynamics in water explored by heterodyne-detected photon echo

Results of heterodyne-detected photon echo experiments on the OH stretching mode of water are reported and discussed. Two vibrational dynamical processes with time constants of 130 and 900 fs were identified. The former is attributed to bond breaking dynamics of a single hydrogen bond, the latter to rearrangement of the hydrogen-bond network.

Generation of 13-fs, 5-MW pulses from a cavity-dumped Ti : sapphire laser

We report on a cavity-dumped self-mode-locked Ti:sapphire laser operating on a 10-fs time scale. Pulses with energies exceeding 60 nJ and peak powers of 5 MW were generated at repetition rates as high as 200 kHz. On injection of the output of this laser into a fiber, a white-light continuum is produced that shows great potential for compression.

Second-harmonic generation frequency-resolved optical gating in the single-cycle regime

The problem of measuring broad-band femtosecond pulses by the technique of second-harmonic generation frequency-resolved optical gating (SHG FROG) is addressed. We derive the full equation for the FROG signal, which is valid even for single-optical-cycle pulses. The effect of the phase mismatch in the second-harmonic crystal, the implications of the beam geometry, and the frequency-dependent variation of the nonlinearity are discussed in detail. Our numerical simulations show that, under carefully chosen experimental conditions and with a proper spectral correction of the data, the traditional FROG inversion routines work well even in the single-cycle regime. The developed description of the SHG FROG signal was applied to measure the white-light continuum pulses in the spectral region of 500-1100 nm. The obtained spectral phase of these pulses served as a target function for the pulse compressor design. The pulses produced by compression around 800 nm were also characterized by SHG FROG. The resulting pulse duration measures 4.5 fs which corresponds to /spl sim/2.5 optical cycles.

On the relation between the echo-peak shift and Brownian-oscillator correlation function

We show that for systems that exhibit bimodal dynamics in their system-bath correlation function the shift of the stimulated photon-echo maximum as a function of waiting time reflects fairly well the long time part of the correlation function. For early times this correspondence breaks down due to a fundamentally different behaviour of the echo-peak shift in this time domain and because of the effect of finite pulse duration on the echo-peak shift. The method is used to characterize the solvation dynamics in various dye solutions.

PHASE-LOCKED HETERODYNE-DETECTED STIMULATED PHOTON-ECHO - A UNIQUE TOOL TO STUDY SOLUTE-SOLVENT INTERACTIONS

Abstract Heterodyne-detected phase-locked femtosecond stimulated photon echo (HSPE) and pump—probe (PLPP) experiments were accomplished on a dye dissolved in ethylene glycol. It is shown that all four Liouville pathways are needed in a proper description of the observed phenomena. By measurement of the real and imaginary part of the PLPP signal the short-time (⩽ 60 fs) solvation dynamics can be probed, but none was found in ethylene glycol. Time-resolved and conventional stimulated photon echo experiments were also performed. The fastest solvation step in ethylene glycol seems to occur on a time scale of 300 fs.

Amplitude and phase characterization of 4.5-fs pulses by frequency-resolved optical gating

The technique of second-harmonic generation frequency-resolved optical gating is applied to measure the intensity and the phase of 4.5-fs pulses resulting from the fiber-compressed output of a cavity-dumped Ti:sapphire laser. Characterization of even shorter optical pulses by this method should also be feasible.

Hydrophobic Molecules Slow Down the Hydrogen-Bond Dynamics of Water

We study the spectral and orientational dynamics of HDO molecules in solutions of tertiary-butyl-alcohol (TBA), trimethyl-amine-oxide (TMAO), and tetramethylurea (TMU) in isotopically diluted water (HDO:D(2)O and HDO:H(2)O). The spectral dynamics are studied with femtosecond two-dimensional infrared spectroscopy and the orientational dynamics with femtosecond polarization-resolved vibrational pump-probe spectroscopy. We observe a strong slowing down of the spectral diffusion around the central part of the absorption line that increases with increasing solute concentration. At low concentrations, the fraction of water showing slow spectral dynamics is observed to scale with the number of methyl groups, indicating that this effect is due to slow hydrogen-bond dynamics in the hydration shell of the methyl groups of the solute molecules. The slowing down of the vibrational frequency dynamics is strongly correlated with the slowing down of the orientational mobility of the water molecules. This correlation indicates that these effects have a common origin in the effect of hydrophobic molecular groups on the hydrogen-bond dynamics of water.