Organic photodetectors (OPDs) have gained increasing interest as they offer cost-effective fabrication methods using low temperature processes, making them particularly attractive for large area image detectors on lightweight flexible plastic substrates. Moreover, their photophysical and optoelectronic properties can be tuned both at a material and device level. Visible-light OPDs are proposed for use in indirect-conversion X-ray detectors, fingerprint scanners, and intelligent surfaces for gesture recognition. Near-infrared OPDs find applications in biomedical imaging and optical communications. For most applications, minimizing the OPD dark current density (J d ) is crucial to improve important figures of merits such as the signal-to-noise ratio, the linear dynamic range, and the specific detectivity (D*). Here, a quantitative analysis of the intrinsic dark current processes shows that charge injection from the electrodes is the dominant contribution to J d in OPDs. J d reduction is typically addressed by fine-tuning the active layer energetics and stratification or by using charge blocking layers. Yet, most experimental J d values are higher than the calculated intrinsic limit. Possible reasons for this deviation are discussed, including extrinsic defects in the photoactive layer and the presence of trap states. This provides the reader with guidelines to improve the OPD performances in view of imaging applications.

Building efficient triplet-harvesting layers for photovoltaic applications requires a deep understanding of the microscopic properties of the components involved and their dynamics. Singlet fission is a particularly appealing mechanism as it generates two excitons from a single photon. However, the pathways of the coupled triplets into free species, and their dependence on the intermolecular geometry, has not been fully explored. In this work, we produce highly ordered dilute pentacene films with distinct parallel and herringbone dimers and aggregates. Using electron paramagnetic resonance spectroscopy, we provide compelling evidence for the formation of distinct quintet excitons in ambient conditions, with intrinsically distinctive electronic and kinetic properties. We find that the ability of quintets to separate into free triplets is promoted in the parallel dimers and this provides molecular design rules to control the triplets, favouring either enhanced photovoltaic efficiency (parallel) or strongly bound pairs that could be exploited for logic applications (herringbone).

Minimizing the reverse bias dark current while retaining external quantum efficiency is crucial if the light detection sensitivity of organic photodiodes (OPDs) is to compete with inorganic photodetectors. However, a quantitative relationship between the magnitude of the dark current density under reverse bias (  Jd) and the properties of the bulk heterojunction (BHJ) active layer has so far not been established. Here, a systematic analysis of Jd in state‐of‐the‐art BHJ OPDs using five polymers with a range of energy levels and charge transport characteristics is presented. The magnitude and activation energy of Jd are explained using a model that assumes charge injection from the metal contacts into an energetically disordered semiconductor. By relating Jd to material parameters, insights into the origin of Jd are obtained that enable the future selection of successful OPD materials.

Metal halide perovskite photodiodes (PPDs) offer high responsivity and broad spectral sensitivity, making them attractive for low-cost visible and near-infrared sensing. A significant challenge in achieving high detectivity in PPDs is lowering the dark current density (JD) and noise current (in). This is commonly accomplished using charge-blocking layers to reduce charge injection. By analyzing the temperature dependence of JD for lead-tin based PPDs with different bandgaps and electron-blocking layers (EBL), we demonstrate that while EBLs eliminate electron injection, they facilitate undesired thermal charge generation at the EBL-perovskite interface. The interfacial energy offset between the EBL and the perovskite determines the magnitude and activation energy of JD. By increasing this offset we realized a PPD with ultralow JD and in of 5 × 10−8 mA cm−2 and 2 × 10−14 A Hz−1/2, respectively, and wavelength sensitivity up to 1050 nm, establishing a new design principle to maximize detectivity in perovskite photodiodes.

The synthesis of a highly twisted chrysene derivative incorporating two electron deficient o‐carboranyl groups is reported. The molecule exhibits a complex, excitation‐dependent photoluminescence, including aggregation‐induced emission (AIE) with good quantum efficiency and an exceptionally long singlet excited state lifetime. Through a combination of detailed optical studies and theoretical calculations, the excited state species are identified, including an unusual excimer induced by the presence of o‐carborane. This is the first time that o‐carborane has been shown to induce excimer formation ab initio, as well as the first observation of excimer emission by a chrysene‐based small molecule in solution. Bis‐o‐carboranyl chrysene is thus an initial member of a new family of o‐carboranyl phenacenes exhibiting a novel architecture for highly‐efficient multi‐luminescent fluorophores.

Side chain engineering of conjugated donor–acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)‐terthiophene‐based conjugated polymers PDPP3T‐1 and PDPP3T‐2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin‐film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T‐1 in which TEG chains are uniformly distributed can self‐assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T‐1 exhibits high saturated hole mobility up to 2.6 cm2 V−1 s−1 without any post‐treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T‐2. Moreover, the respective field effect transistors made of PDPP3T‐1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.

Compared to conjugated polymers, small‐molecule organic semiconductors present negligible batch‐to‐batch variations, but presently provide comparatively low power conversion efficiencies (PCEs) in small‐molecular organic solar cells (SM‐OSCs), mainly due to suboptimal nanomorphology. Achieving precise control of the nanomorphology remains challenging. Here, two new small‐molecular donors H13 and H14, created by fluorine and chlorine substitution of the original donor molecule H11, are presented that exhibit a similar or higher degree of crystallinity/aggregation and improved open‐circuit voltage with IDIC‐4F as acceptor. Due to kinetic and thermodynamic reasons, H13‐based blend films possess relatively unfavorable molecular packing and morphology. In contrast, annealed H14‐based blends exhibit favorable characteristics, i.e., the highest degree of aggregation with the smallest paracrystalline π–π distortions and a nanomorphology with relatively pure domains, all of which enable generating and collecting charges more efficiently. As a result, blends with H13 give a similar PCE (10.3%) as those made with H11 (10.4%), while annealed H14‐based SM‐OSCs have a significantly higher PCE (12.1%). Presently this represents the highest efficiency for SM‐OSCs using IDIC‐4F as acceptor. The results demonstrate that precise control of phase separation can be achieved by fine‐tuning the molecular structure and film formation conditions, improving PCE and providing guidance for morphology design.

Organic bulk heterojunction photodiodes (OPDs) attract attention for sensing and imaging. Their detectivity is typically limited by a substantial reverse bias dark current density (Jd). Recently, using thermal admittance or spectral photocurrent measurements, Jd has been attributed to thermal charge generation mediated by mid‐gap states. Here, the temperature dependence of Jd in state‐of‐the‐art OPDs is reported with Jd down to 10−9 mA cm−2 at −0.5 V bias. For a variety of donor‐acceptor bulk‐heterojunction blends it is found that the thermal activation energy of Jd is lower than the effective bandgap of the blends, by ca. 0.3 to 0.5 eV, but higher than expected for mid‐gap states. Ultra‐sensitive sub‐bandgap photocurrent spectroscopy reveals that the minimum photon energy for optical charge generation in OPDs correlates with the dark current thermal activation energy. The dark current in OPDs is attributed to thermal charge generation at the donor‐acceptor interface mediated by intra‐gap states near the band edges.