Dimali A. Vithanage

Towards longer-lived metal-to-ligand charge transfer states of iron(ii) complexes: an N-heterocyclic carbene approach.

A 9 ps (3)MLCT lifetime was achieved by a Fe(II) complex based on C(NHC)^N(py)^C(NHC) pincer ligands. This is the longest known so far for any kind of complexes of this abundant metal, and increased by almost two orders of magnitude compared to the reference Fe(II) bis-terpyridine complex.

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

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.

Ultrafast Terahertz Photoconductivity of Bulk Heterojunction Materials Reveals High Carrier Mobility up to Nanosecond Time Scale.

The few-picosecond (ps) decay of terahertz (THz) photoconductivity typically observed for conjugated polymer:fullerene blends (at excitation fluencies ~10(15) photons/cm(2) per pulse) is shown to be a result of charge pair annihilation for two polymer:PCBM blends. At a factor of 100 lower excitation density, the THz decay is in the hundreds of ps time scale, implying that very high carrier mobility (~0.1 cm(2) V(-1) s(-1)) prevails for long time after charge formation, of importance for free charge formation in organic solar cells.

Charge Carrier Generation and Transport in Different Stoichiometry APFO3:PC61BM Solar Cells

In this paper we studied carrier drift dynamics in APFO3:PC61BM solar cells of varied stoichiometry (2:1, 1:1, and 1:4 APFO3:PC61BM) over a wide time range, from subpicoseconds to microseconds with a combination of ultrafast optical electric field probing and conventional transient integrated photocurrent techniques. Carrier drift and extraction dynamics are strongly stoichiometry dependent: the speed of electron or hole drift increases with higher concentration of PC61BM or polymer, respectively. The electron extraction from a sample with 80% PC61BM takes place during hundreds of picoseconds, but slows down to sub-microseconds in a sample with 33% PC61BM. The hole extraction is less stoichiometry dependent: it varies form sub-nanoseconds to tens of nanoseconds when the PC61BM concentration changes from 33% to 80%. The electron extraction rate correlates with the conversion efficiency of solar cells, leading to the conclusion that fast electron motion is essential for efficient charge carrier separation preventing their geminate recombination.

Carrier motion in as-spun and annealed P3HT:PCBM blends revealed by ultrafast optical electric field probing and Monte Carlo simulations

Charge transport dynamics in solar cell devices based on as-spun and annealed P3HT:PCBM films are compared using ultrafast time-resolved optical probing of the electric field by means of field-induced second harmonic generation. The results show that charge carriers drift about twice as far during the first 3 ns after photogeneration in a device where the active layer has been thermally annealed. The carrier dynamics were modelled using Monte-Carlo simulations and good agreement between experimental and simulated drift dynamics was obtained using identical model parameters for both cells, but with different average PCBM and polymer domain sizes. The calculations suggest that small domain sizes in as-spun samples limit the carrier separation distance disabling their escape from geminate recombination.

Influence of Blend Ratio and Processing Additive on Free Carrier Yield and Mobility in PTB7:PC71BM Photovoltaic Solar Cells

Charge separation and extraction dynamics were investigated in high-performance bulk heterojunction solar cells made from the polymer PTB7 and the soluble fullerene PC71BM on a broad time scale from subpicosecond to microseconds using ultrafast optical probing of carrier drift and the integral-mode photocurrent measurements. We show that the short circuit current is determined by the separation of charge pairs into free carriers, which is strongly influenced by blend composition. This separation is found to be efficient in fullerene-rich blends where a high electron mobility of >0.1 cm2 V–1 s–1 is observed in the first 10 ps after excitation. Morphology optimization using the solvent additive 1,8-diiodooctane (DIO) doubles the charge pair separation efficiency and the short-circuit current. Carrier extraction at low internal electric field is slightly faster from the cells prepared with DIO, which can reduce recombination losses and enhance a fill factor.

Wide field-of-view fluorescent antenna for visible light communications beyond the étendue limit

Visible light communications (VLC) is an important emerging field aiming to use optical communications to supplement Wi-Fi. This will greatly increase the available bandwidth so that demands for ever-higher data rates can be met. In this vision, solid-state lighting will provide illumination while being modulated to transmit data. An important obstacle to realizing this vision are receivers, which need to be inexpensive, sensitive, fast, and have a large field of view (FoV). One approach to increasing the sensitivity of a VLC receiver is to increase the area of the receiver’s photodetector, but this makes them expensive and slow. An alternative approach is to use optical elements to concentrate light, but conservation of etendue in these elements limits their FoV. In this paper, we demonstrate novel antennas that overcome these limitations, giving fast receivers with large collection areas and large FoV. Our results exceed the limit of etendue, giving an enhancement of light collection by a factor of 12, with FoV semi-angle of 60°, and we show a threefold increase in data rate.

Demonstration of 2.3 Gb/s RGB white-light VLC using polymer based colour-converters and GaN micro-LEDs

This paper presents a demonstration of polymer based colour-converters and GaN micro-LEDs for red-green-blue based white-light visible-light-communication. By applying an optimised orthogonal-frequency-division-multiplexing scheme, an aggregate-rate of 2.3 Gb/s is demonstrated.

A simple wide field of view concentrator for free space visible light communications

The optical gain of a simple new type of wide field of view optical concentrator is predicted and easy modifications that will significantly increase its gain without changing its field of view are identified.

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

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.