Identification of the Origin of Ultralow Dark Currents in Organic Photodiodes.

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.

3D Perovskite Passivation with a Benzotriazole-Based 2D Interlayer for High-Efficiency Solar Cells.

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI3) solar cells. In combination with PbI2 and PbBr2, these benzotriazole derivatives form two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) as evidenced by their crystal structures and thin film characteristics. When used to passivate n-i-p FAPbI3 solar cells, the power conversion efficiency improves from 20% to close to 22% by enhancing the open-circuit voltage. Quasi-Fermi level splitting experiments and scanning electron microscopy cathodoluminescence hyperspectral imaging reveal that passivation provides a reduced nonradiative recombination at the interface between the perovskite and hole transport layer. Photoluminescence spectroscopy, angle-resolved grazing-incidence wide-angle X-ray scattering, and depth profiling X-ray photoelectron spectroscopy studies of the 2D/three-dimensional (3D) interface between the benzotriazole RPP and FAPbI3 show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination.

Optical Simulation-Aided Design and Engineering of Monolithic Perovskite/Silicon Tandem Solar Cells.

Monolithic perovskite/c-Si tandem solar cells have attracted enormous research attention and have achieved efficiencies above 30%. This work describes the development of monolithic tandem solar cells based on silicon heterojunction (SHJ) bottom- and perovskite top-cells and highlights light management techniques assisted by optical simulation. We first engineered (i)a-Si:H passivating layers for (100)-oriented flat c-Si surfaces and combined them with various (n)a-Si:H, (n)nc-Si:H, and (n)nc-SiOx:H interfacial layers for SHJ bottom-cells. In a symmetrical configuration, a long minority carrier lifetime of 16.9 ms was achieved when combining (i)a-Si:H bilayers with (n)nc-Si:H (extracted at the minority carrier density of 1015 cm-3). The perovskite sub-cell uses a photostable mixed-halide composition and surface passivation strategies to minimize energetic losses at charge-transport interfaces. This allows tandem efficiencies above 23% (a maximum of 24.6%) to be achieved using all three types of (n)-layers. Observations from experimentally prepared devices and optical simulations indicate that both (n)nc-SiOx:H and (n)nc-Si:H are promising for use in high-efficiency tandem solar cells. This is possible due to minimized reflection at the interfaces between the perovskite and SHJ sub-cells by optimized interference effects, demonstrating the applicability of such light management techniques to various tandem structures.

Revealing defective interfaces in perovskite solar cells from highly sensitive sub-bandgap photocurrent spectroscopy using optical cavities.

Defects in perovskite solar cells are known to affect the performance, but their precise nature, location, and role remain to be firmly established. Here, we present highly sensitive measurements of the sub-bandgap photocurrent to investigate defect states in perovskite solar cells. At least two defect states can be identified in p-i-n perovskite solar cells that employ a polytriarylamine hole transport layer and a fullerene electron transport layer. By comparing devices with opaque and semi-transparent back contacts, we demonstrate the large effect of optical interference on the magnitude and peak position in the sub-bandgap external quantum efficiency (EQE) in perovskite solar cells. Optical simulations reveal that defects localized near the interfaces are responsible for the measured photocurrents. Using optical spacers of different lengths and a mirror on top of a semi-transparent device, allows for the precise manipulation of the optical interference. By comparing experimental and simulated EQE spectra, we show that sub-bandgap defects in p-i-n devices are located near the perovskite-fullerene interface.

Analysis of the Performance of Narrow-Bandgap Organic Solar Cells Based on a Diketopyrrolopyrrole Polymer and a Nonfullerene Acceptor.

The combination of narrow-bandgap diketopyrrolopyrrole (DPP) polymers and nonfullerene acceptors (NFAs) seems well-matched for solar cells that exclusively absorb in the near infrared but they rarely provide high efficiency. One reason is that processing of the active layer is complicated by the fact that DPP-based polymers are generally only sufficiently soluble in chloroform (CF), while NFAs are preferably processed from halogenated aromatic solvents. By using a ternary solvent system consisting of CF, 1,8-diiodooctane (DIO), and chlorobenzene (CB), the short-circuit current density is increased by 50% in solar cells based on a DPP polymer (PDPP5T) and a NFA (IEICO-4F) compared to the use of CF with DIO only. However, the open-circuit voltage and fill factor are reduced. As a result, the efficiency improves from 3.4 to 4.8% only. The use of CB results in stronger aggregation of IEICO-4F as inferred from two-dimensional grazing-incidence wide-angle X-ray diffraction. Photo- and electroluminescence and mobility measurements indicate that the changes in performance can be ascribed to a more aggregated blend film in which charge generation is increased but nonradiative recombination is enhanced because of reduced hole mobility. Hence, while CB is essential to obtain well-ordered domains of IEICO-4F in blends with PDPP5T, the morphology and resulting hole mobility of PDPP5T domains remain suboptimal. The results identify the challenges in processing organic solar cells based on DPP polymers and NFAs as near-infrared absorbing photoactive layers.

Ultralow dark current in near-infrared perovskite photodiodes by reducing charge injection and interfacial charge generation.

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.

Effect of Light-Induced Halide Segregation on the Performance of Mixed-Halide Perovskite Solar Cells.

Light-induced halide segregation hampers obtaining stable wide-band-gap solar cells based on mixed iodide-bromide perovskites. So far, the effect of prolonged illumination on the performance of mixed-halide perovskite solar cells has not been studied in detail. It is often assumed that halide segregation leads to a loss of open-circuit voltage. By simultaneously recording changes in photoluminescence and solar cell performance under prolonged illumination, we demonstrate that cells instead deteriorate by a loss of short-circuit current density and that the open-circuit voltage is less affected. The concurrent red shift, increased lifetime, and higher quantum yield of photoluminescence point to the formation of relatively emissive iodide-rich domains under illumination. Kinetic Monte Carlo simulations provide an atomistic insight into their formation via exchange of bromide and iodide, mediated by halide vacancies. Localization of photogenerated charge carriers in low-energy iodide-rich domains and subsequent recombination cause reduced photocurrent and red-shifted photoluminescence. The loss in photovoltaic performance is diminished by partially replacing organic cations by cesium ions. Ultrasensitive photocurrent spectroscopy shows that cesium ions result in a lower density of sub-band-gap defects and suppress defect growth under illumination. These defects are expected to play a role in the development and recovery of light-induced compositional changes.