Exciton Regeneration at Polymeric Semiconductor Heterojunctions

Control of the band-edge offsets at heterojunctions between organic semiconductors allows efficient operation of either photovoltaic or light-emitting diodes. We investigate systems where the exciton is marginally stable against charge separation, and show via E-field-dependent time-resolved photoluminescence spectroscopy that excitons that have undergone charge separation at a heterojunction can be efficiently regenerated. This is because the charge transfer produces a geminate electron-hole pair (separation 2.2-3.1nm) which may collapse into an exciplex and then endothermically (E=100-200meV) back-transfer towards the exciton.Comment: 10 pages, 4 figures. Manuscript in press in Phys. Rev. Let

Mesoscopic order and the dimentionality of long-range resonance energy transfer in supramolecular semiconductors

We present time-resolved photoluminescence measurements on two series of oligo-p-phenylenevinylene materials that self-assemble into supramolecular nanostructures with thermotropic reversibility in dodecane. One set of derivatives form chiral, helical stacks while the second set form less organised, frustrated stacks. Here we study the effects of supramolecular organisation on the resonance energy transfer rates. We measure these rates in nanoassemblies formed with mixed blends of oligomers and compare them with the rates predicted by Foerster theory. Our results and analysis show that control of supramolecular order in the nanometre lengthscale has a dominant effect on the efficiency and dimentionality of resonance energy transfer.Comment: 17 Pages, 5 Figures, Submitted to J. Chem. Phy

Chromophores in molecular nanorings : when is a ring a ring?

The topology of a conjugated molecule plays a significant role in controlling both the electronic properties and the conformational manifold that the molecule may explore. Fully π-conjugated molecular nanorings are of particular interest, as their lowest electronic transition may be strongly suppressed as a result of symmetry constraints. In contrast, the simple Kasha model predicts an enhancement in the radiative rate for corresponding linear oligomers. Here we investigate such effects in linear and cyclic conjugated molecules containing between 6 and 42 butadiyne-linked porphyrin units (corresponding to 600 C–C bonds) as pure monodisperse oligomers. We demonstrate that as the diameter of the nanorings increases beyond ∼10 nm, its electronic properties tend toward those of a similarly sized linear molecule as a result of excitation localization on a subsegment of the ring. However, significant differences persist in the nature of the emitting dipole polarization even beyond this limit, arising from variations in molecular curvature and conformation

Cation-disorder engineering promotes efficient charge-carrier transport in AgBiS2 nanocrystal films

Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS2 nanocrystals (NCs) are explored where Ag and Bi cation-ordering can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation engineering results in a six-fold increase in the charge-carrier mobility, reaching ∼2.7 cm2V−1s−1 in AgBiS2 NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localisation, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localisation of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications

Raman Spectrum of the Organic-Inorganic Halide Perovskite CH3NH3PbI3 from First Principles and High-Resolution Low-Temperature Raman Measurements

We investigate the Raman spectrum of the low-temperature orthorhombic phase of the organic-inorganic halide perovskite CH3NH3PbI3, by combining first-principles calculations with high-resolution low-temperature Raman measurements. We find good agreement between theory and experiment, and successfully assign each of the Raman peaks to the underlying vibrational modes. In the low-frequency spectral range (below 60 cm1) we assign the prominent Raman signals at 26, 32, 42 and 49 cm1 to the Pb-I-Pb bending modes with either Ag or B2g symmetry, and the signal at 58 cm1 to the librational mode of the organic cation. Owing to their significant intensity, we propose that these peaks can serve as clear markers of the vibrations of the [PbI3] network and of the CH3NH+ 3 cations in this perovskite, respectively. In particular, the ratios of the intensities of these peaks might be used to monitor possible deviations from the ideal stoichiometry of CH3NH3PbI3

Charge-Carrier Dynamics in 2D Hybrid Metal–Halide Perovskites

Hybrid metal–halide perovskites are promising new materials for use in solar cells; however, their chemical stability in the presence of moisture remains a significant drawback. Quasi two-dimensional (2D) perovskites that incorporate hydrophobic organic interlayers offer improved resistance to degradation by moisture, currently still at the cost of overall cell efficiency. To elucidate the factors affecting the optoelectronic properties of these materials, we have investigated the charge transport properties and crystallographic orientation of mixed methylammonium (MA)–phenylethylammonium (PEA) lead iodide thin films as a function of the MA-to-PEA ratio and, thus, the thickness of the “encapsulated” MA lead–halide layers. We find that monomolecular charge-carrier recombination rates first decrease with increasing PEA fraction, most likely as a result of trap passivation, but then increase significantly as excitonic effects begin to dominate for thin confined layers. Bimolecular and Auger recombination rate constants are found to be sensitive to changes in electronic confinement, which alters the density of states for electronic transitions. We demonstrate that effective charge-carrier mobilities remain remarkably high (near 10 cm2V−1s−1) for intermediate PEA content and are enhanced for preferential orientation of the conducting lead iodide layers along the probing electric field. The trade-off between trap reduction, electronic confinement, and layer orientation leads to calculated charge-carrier diffusion lengths reaching a maximum of 2.5 μm for intermediate PEA content (50%)

Unraveling loss mechanisms arising from energy-level misalignment between metal halide perovskites and hole transport layers

Metal halide perovskites are promising light absorbers for multijunction photovoltaic applications because of their remarkable bandgap tunability, achieved through compositional mixing on the halide site. However, poor energy-level alignment at the interface between wide-bandgap mixed-halide perovskites and charge-extraction layers still causes significant losses in solar-cell performance. Here, the origin of such losses is investigated, focusing on the energy-level misalignment between the valence band maximum and the highest occupied molecular orbital (HOMO) for a commonly employed combination, FA0.83Cs0.17Pb(I1-xBrx)3 with bromide content x ranging from 0 to 1, and poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). A combination of time-resolved photoluminescence spectroscopy and numerical modeling of charge-carrier dynamics reveals that open-circuit voltage (VOC) losses associated with a rising energy-level misalignment derive from increasing accumulation of holes in the HOMO of PTAA, which then subsequently recombine non-radiatively across the interface via interfacial defects. Simulations assuming an ideal choice of hole-transport material to pair with FA0.83Cs0.17Pb(I1-xBrx)3 show that such VOC losses originating from energy-level misalignment can be reduced by up to 70 mV. These findings highlight the urgent need for tailored charge-extraction materials exhibiting improved energy-level alignment with wide-bandgap mixed-halide perovskites to enable solar cells with improved power conversion efficiencies

Photovoltaic Performance of FAPbI3 Perovskite Is Hampered by Intrinsic Quantum Confinement

Formamidinium lead trioiodide (FAPbI3) is a promising perovskite for single-junction solar cells. However, FAPbI3 is metastable at room temperature and can cause intrinsic quantum confinement effects apparent through a series of above-bandgap absorption peaks. Here, we explore three common solution-based film-fabrication methods, neat N,N-dimethylformamide (DMF)–dimethyl sulfoxide (DMSO) solvent, DMF-DMSO with methylammonium chloride, and a sequential deposition approach. The latter two offer enhanced nucleation and crystallization control and suppress such quantum confinement effects. We show that elimination of these absorption features yields increased power conversion efficiencies (PCEs) and short-circuit currents, suggesting that quantum confinement hinders charge extraction. A meta-analysis of literature reports, covering 244 articles and 825 photovoltaic devices incorporating FAPbI3 films corroborates our findings, indicating that PCEs rarely exceed a 20% threshold when such absorption features are present. Accordingly, ensuring the absence of these absorption features should be the first assessment when designing fabrication approaches for high-efficiency FAPbI3 solar cells

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

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.H.L.S was supported by the Winton Programme for the Physics of Sustainability and A.J.M received funding from the Engineering and Physical Sciences Research Council.This is the accepted manuscript. The final version is available at http://www.pnas.org/content/112/25/7656.abstract