Patrick Parkinson

Carrier lifetime and mobility enhancement in nearly defect-free core-shell nanowires measured using time-resolved terahertz spectroscopy

We have used transient terahertz photoconductivity measurements to assess the efficacy of two-temperature growth and core-shell encapsulation techniques on the electronic properties of GaAs nanowires. We demonstrate that two-temperature growth of the GaAs core leads to an almost doubling in charge-carrier mobility and a tripling of carrier lifetime. In addition, overcoating the GaAs core with a larger-bandgap material is shown to reduce the density of surface traps by 82%, thereby enhancing the charge conductivity.

Role of Ultrafast Torsional Relaxation in the Emission from Polythiophene Aggregates

An understanding of aggregation effects in organic semiconductors is essential for their effective use in optoelectronic devices. Typically, the electronic dynamics in such systems are heavily dependant upon the aggregation state, and dynamics often occur on sub-nanosecond timescales.

Ultrafast Transient Terahertz Conductivity of Monolayer MoS2 and WSe2 Grown by Chemical Vapor Deposition

We have measured ultrafast charge carrier dynamics in monolayers and trilayers of the transition metal dichalcogenides MoS2 and WSe2 using a combination of time-resolved photoluminescence and terahertz spectroscopy. We recorded a photoconductivity and photoluminescence response time of just 350 fs from CVD-grown monolayer MoS2, and 1 ps from trilayer MoS2 and monolayer WSe2. Our results indicate the potential of these materials as high-speed optoelectronic materials.

Ultrafast Charge Separation at a Polymer-Single-Walled Carbon Nanotube Molecular Junction

We have investigated the charge photogeneration dynamics at the interface formed between single-walled carbon nanotubes (SWNTs) and poly(3-hexylthiophene) (P3HT) using a combination of femtosecond spectroscopic techniques. We demonstrate that photoexcitation of P3HT forming a single molecular layer around a SWNT leads to an ultrafast (∼430 fs) charge transfer between the materials. The addition of excess P3HT leads to long-term charge separation in which free polarons remain separated at room temperature. Our results suggest that SWNT-P3HT blends incorporating only small fractions (1%) of SWNTs allow photon-to-charge conversion with efficiencies comparable to those for conventional (60:40) P3HT-fullerene blends, provided that small-diameter tubes are individually embedded in the P3HT matrix.

Enhanced minority carrier lifetimes in GaAs/AlGaAs core-shell Nanowires through shell growth optimization

The effects of AlGaAs shell thickness and growth time on the minority carrier lifetime in the GaAs core of GaAs/AlGaAs core-shell nanowires grown by metal-organic chemical vapor deposition are investigated. The carrier lifetime increases with increasing AlGaAs shell thickness up to a certain value as a result of reducing tunneling probability of carriers through the AlGaAs shell, beyond which the carrier lifetime reduces due to the diffusion of Ga-Al and/or impurities across the GaAs/AlGaAs heterointerface. Interdiffusion at the heterointerface is observed directly using high-angle annular dark field scanning transmission electron microscopy. We achieve room temperature minority carrier lifetimes of 1.9 ns by optimizing the shell growth with the intention of reducing the effect of interdiffusion.

Distinct Photocurrent Response of Individual GaAs Nanowires Induced by n-Type Doping

The doping-dependent photoconductive properties of individual GaAs nanowires have been studied by conductive atomic force microscopy. Linear responsivity against the bias voltage is observed for moderate n-doped GaAs wires with a Schottky contact under illumination, while that of the undoped ones exhibits a saturated response. The carrier lifetime of a single nanowire can be obtained by simulating the characteristic photoelectric behavior. Consistent with the photoluminescence results, the significant drop of minority hole lifetime, from several hundred to subpicoseconds induced by n-type doping, leads to the distinct photoconductive features. Moreover, by comparing with the photoelectric behavior of AlGaAs shelled nanowires, the equivalent recombination rate of carriers at the surface is assessed to be >1 × 10(12) s(-1) for 2 × 10(17)cm(-3) n-doped bare nanowires, nearly 30 times higher than that of the doping-related bulk effects. This work suggests that intentional doping in nanowires could change the charge status of the surface states and impose significant impact on the electrical and photoelectrical performances of semiconductor nanostructures.

Long minority carrier lifetime in Au-catalyzed GaAs/AlxGa1−xAs core-shell nanowires

The Australian Research Council is acknowledged for the financial support and the authors acknowledge the use of facilities in the Centre for Advanced Microscopy (AMMRF node) and the ACT node of the Australian National Fabrication Facility for this work.

Identification of a triplet pair intermediate in singlet exciton fission in solution

Significance We use transient spectroscopy to investigate the mechanism of singlet exciton fission, a quantum mechanical phenomenon in some organic molecules in which a spin-singlet excited state can split into two spin-triplet states. This process may be harnessed to boost solar cell efficiencies, but the underlying mechanism remains poorly understood. Central to most models is a triplet pair state, consisting of two triplets entangled into an overall spin-singlet configuration, but it has never before been optically detected. In a solution-based system, we detect a state with simultaneous singlet and triplet exciton character that dissociates to form triplet excitons in 120% yield. We consider that this intermediate constitutes a triplet pair state, and its observation allows important insight into the nature of triplet exciton coupling. Singlet exciton fission is the spin-conserving transformation of one spin-singlet exciton into two spin-triplet excitons. This exciton multiplication mechanism offers an attractive route to solar cells that circumvent the single-junction Shockley–Queisser limit. Most theoretical descriptions of singlet fission invoke an intermediate state of a pair of spin-triplet excitons coupled into an overall spin-singlet configuration, but such a state has never been optically observed. In solution, we show that the dynamics of fission are diffusion limited and enable the isolation of an intermediate species. In concentrated solutions of bis(triisopropylsilylethynyl)[TIPS]—tetracene we find rapid (<100 ps) formation of excimers and a slower (∼10 ns) break up of the excimer to two triplet exciton-bearing free molecules. These excimers are spectroscopically distinct from singlet and triplet excitons, yet possess both singlet and triplet characteristics, enabling identification as a triplet pair state. We find that this triplet pair state is significantly stabilized relative to free triplet excitons, and that it plays a critical role in the efficient endothermic singlet fission process.

Ultrafast energy transfer in biomimetic multistrand nanorings.

We report the synthesis of LH2-like supramolecular double- and triple-stranded complexes based upon porphyrin nanorings. Energy transfer from the antenna dimers to the π-conjugated nanoring occurs on a subpicosecond time scale, rivaling transfer rates in natural light-harvesting systems. The presence of a second nanoring acceptor doubles the transfer rate, providing strong evidence for multidirectional energy funneling. The behavior of these systems is particularly intriguing because the local nature of the interaction may allow energy transfer into states that are, for cyclic nanorings, symmetry-forbidden in the far field. These complexes are versatile synthetic models for natural light-harvesting systems.

Ultrafast energy transfer in biomimetic multistrand nanorings

We report the synthesis of LH2-like supramolecular double- and triple-stranded complexes based upon porphyrin nanorings. Energy transfer from the antenna dimers to the π-conjugated nanoring occurs on a subpicosecond time scale, rivaling transfer rates in natural light-harvesting systems. The presence of a second nanoring acceptor doubles the transfer rate, providing strong evidence for multidirectional energy funneling. The behavior of these systems is particularly intriguing because the local nature of the interaction may allow energy transfer into states that are, for cyclic nanorings, symmetry-forbidden in the far field. These complexes are versatile synthetic models for natural light-harvesting systems.