We report the implementation of continuous, highly flexible, and transparent graphene films obtained by chemical vapor deposition (CVD) as transparent conductive electrodes (TCE) in organic photovoltaic cells. Graphene films were synthesized by CVD, transferred to transparent substrates, and evaluated in organic solar cell heterojunctions (TCE/poly-3,4-ethylenedioxythiophene:poly styrenesulfonate (PEDOT:PSS)/copper phthalocyanine/fullerene/bathocuproine/aluminum). Key to our success is the continuous nature of the CVD graphene films, which led to minimal surface roughness ( approximately 0.9 nm) and offered sheet resistance down to 230 Omega/sq (at 72% transparency), much lower than stacked graphene flakes at similar transparency. In addition, solar cells with CVD graphene and indium tin oxide (ITO) electrodes were fabricated side-by-side on flexible polyethylene terephthalate (PET) substrates and were confirmed to offer comparable performance, with power conversion efficiencies (eta) of 1.18 and 1.27%, respectively. Furthermore, CVD graphene solar cells demonstrated outstanding capability to operate under bending conditions up to 138 degrees , whereas the ITO-based devices displayed cracks and irreversible failure under bending of 60 degrees . Our work indicates the great potential of CVD graphene films for flexible photovoltaic applications.

In biological complexes, cascade structures promote the spatial separation of photogenerated electrons and holes, preventing their recombination. In contrast, the photogenerated excitons in organic photovoltaic cells are dissociated at a single donor-acceptor heterojunction formed within a de-mixed blend of the donor and acceptor semiconductors. The nanoscale morphology and high charge densities give a high rate of electron-hole encounters, which should in principle result in the formation of spin-triplet excitons, as in organic light-emitting diodes. Although organic photovoltaic cells would have poor quantum efficiencies if every encounter led to recombination, state-of-the-art examples nevertheless demonstrate near-unity quantum efficiency. Here we show that this suppression of recombination arises through the interplay between spin, energetics and delocalization of electronic excitations in organic semiconductors. We use time-resolved spectroscopy to study a series of model high-efficiency polymer-fullerene systems in which the lowest-energy molecular triplet exciton (T1) for the polymer is lower in energy than the intermolecular charge transfer state. We observe the formation of T1 states following bimolecular recombination, indicating that encounters of spin-uncorrelated electrons and holes generate charge transfer states with both spin-singlet ((1)CT) and spin-triplet ((3)CT) characters. We show that the formation of triplet excitons can be the main loss mechanism in organic photovoltaic cells. But we also find that, even when energetically favoured, the relaxation of (3)CT states to T1 states can be strongly suppressed by wavefunction delocalization, allowing for the dissociation of (3)CT states back to free charges, thereby reducing recombination and enhancing device performance. Our results point towards new design rules both for photoconversion systems, enabling the suppression of electron-hole recombination, and for organic light-emitting diodes, avoiding the formation of triplet excitons and enhancing fluorescence efficiency.

According to Hund's rule, the lowest triplet state (T 1 ) is lower in energy than the lowest excited singlet state (S 1 ) in closed-shell molecules. The exchange integral lowers the energy of the triplet state and raises the energy of the singlet state of the same orbital character, leading to a positive singlet−triplet energy gap (Δ ST ). Exceptions are known for biradicals and charge-transfer excited states of large molecules in which the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are spatially separated, resulting in a small exchange integral. In the present work, we discovered with ADC(2), CC2, EOM-CCSD, and CASPT2 calculations that heptazine (1,3,4,6,7,9,9bheptaazaphenalene or tri-s-triazine) exhibits an inverted S 1 /T 1 energy gap (Δ ST ≈ −0.25 eV). This appears to be the first example of a stable closedshell organic molecule exhibiting S 1 /T 1 inversion at its equilibrium geometry. The origins of this phenomenon are the nearly pure HOMO− LUMO excitation character of the S 1 and T 1 states and the lack of spatial overlap of HOMO and LUMO due to a unique structure of these orbitals of heptazine. The S 1 /T 1 inversion is found to be extremely robust, being affected neither by substitution of heptazine nor by oligomerization of heptazine units. Using time-resolved photoluminescence and transient absorption spectroscopy, we investigated the excited-state dynamics of 2,5,8-tris(4-methoxyphenyl)-1,3,4,6,7,9,9bheptaazaphenalene (TAHz), a chemically stable heptazine derivative, in the presence of external heavy atom sources as well as triplet-quenching oxygen. These spectroscopic data are consistent with TAHz singlet excited state decay in the absence of a low-energy triplet loss channel. The absence of intersystem crossing and an exceptionally low radiative rate result in unusually long S 1 lifetimes (of the order of hundreds of nanoseconds in nonaqueous solvents). These features of the heptazine chromophore have profound implications for organic optoelectronics as well as for water-splitting photocatalysis with heptazinebased polymers (e.g., graphitic carbon nitride) which have yet to be systematically explored and exploited.

All-inorganic cesium lead bromide (CsPbBr 3 ) perovskite quantum dots (QDs) have recently emerged as highly promising solution-processed materials for nextgeneration light-emitting applications. They combine the advantages of QD and perovskite materials, which makes them an attractive platform for achieving high optical gain with high stability. Here, we report an ultralow lasing threshold (0.39 μJ/cm 2 ) from a hybrid vertical cavity surface emitting laser (VCSEL) structure consisting of a CsPbBr 3 QD thin film and two highly reflective distributed Bragg reflectors (DBRs). Temperature dependence of the lasing threshold and longterm stability of the device were also characterized. Notably, the CsPbBr 3 QDs provide superior stability and enable stable device operation over 5 h/1.8 × 10 7 optical pulse excitations under ambient conditions. This work demonstrates the significant potential of CsPbBr 3 perovskite QD VCSELs for highly reliable lasers, capable of operating in the short-pulse (femtosecond) and quasi-continuous-wave (nanosecond) regimes.