Electron-donating amine-interlayer induced n-type doping of polymer:nonfullerene blends for efficient narrowband near-infrared photo-detection.

Inherently narrowband near-infrared organic photodetectors are highly desired for many applications, including biological imaging and surveillance. However, they suffer from a low photon-to-charge conversion efficiencies and utilize spectral narrowing techniques which strongly rely on the used material or on a nano-photonic device architecture. Here, we demonstrate a general and facile approach towards wavelength-selective near-infrared phtotodetection through intentionally n-doping 500-600 nm-thick nonfullerene blends. We show that an electron-donating amine-interlayer can induce n-doping, resulting in a localized electric field near the anode and selective collection of photo-generated carriers in this region. As only weakly absorbed photons reach this region, the devices have a narrowband response at wavelengths close to the absorption onset of the blends with a high spectral rejection ratio. These spectrally selective photodetectors exhibit zero-bias external quantum efficiencies of ~20-30% at wavelengths of 900-1100 nm, with a full-width-at-half-maximum of ≤50 nm, as well as detectivities of >1012 Jones.

Efficient and Stable Perovskite Solar Cells with a High Open-Circuit Voltage Over 1.2 V Achieved by a Dual-Side Passivation Layer.

Suppressing nonradiative recombination at the interface between the organometal halide perovskite (PVK) and the charge-transport layer (CTL) is crucial for improving the efficiency and stability of PVK-based solar cells (PSCs). Here, a new bathocuproine (BCP)-based nonconjugated polyelectrolyte (poly-BCP) is synthesized and this is introduced as a "dual-side passivation layer" between the tin oxide (SnO2 ) CTL and the PVK absorber. Poly-BCP significantly suppresses both bulk and interfacial nonradiative recombination by passivating oxygen-vacancy defects from the SnO2 side and simultaneously scavenges ionic defects from the other (PVK) side. Therefore, PSCs with poly-BCP exhibits a high power conversion efficiency (PCE) of 24.4% and a high open-circuit voltage of 1.21 V with a reduced voltage loss (PVK bandgap of 1.56 eV). The non-encapsulated PSCs also show excellent long-term stability by retaining 93% of the initial PCE after 700 h under continuous 1-sun irradiation in nitrogen atmosphere conditions.

Static Disorder in Lead Halide Perovskites.

In crystalline and amorphous semiconductors, the temperature-dependent Urbach energy can be determined from the inverse slope of the logarithm of the absorption spectrum and reflects the static and dynamic energetic disorder. Using recent advances in the sensitivity of photocurrent spectroscopy methods, we elucidate the temperature-dependent Urbach energy in lead halide perovskites containing different numbers of cation components. We find Urbach energies at room temperature to be 13.0 ± 1.0, 13.2 ± 1.0, and 13.5 ± 1.0 meV for single, double, and triple cation perovskite. Static, temperature-independent contributions to the Urbach energy are found to be as low as 5.1 ± 0.5, 4.7 ± 0.3, and 3.3 ± 0.9 meV for the same systems. Our results suggest that, at a low temperature, the dominant static disorder in perovskites is derived from zero-point phonon energy rather than structural disorder. This is unusual for solution-processed semiconductors but broadens the potential application of perovskites further to quantum electronics and devices.

Probing Charge Generation Efficiency in Thin-Film Solar Cells by Integral-Mode Transient Charge Extraction.

The photogeneration of free charges in light-harvesting devices is a multistep process, which can be challenging to probe due to the complexity of contributing energetic states and the competitive character of different driving mechanisms. In this contribution, we advance a technique, integral-mode transient charge extraction (ITCE), to probe these processes in thin-film solar cells. ITCE combines capacitance measurements with the integral-mode time-of-flight method in the low intensity regime of sandwich-type thin-film devices and allows for the sensitive determination of photogenerated charge-carrier densities. We verify the theoretical framework of our method by drift-diffusion simulations and demonstrate the applicability of ITCE to organic and perovskite semiconductor-based thin-film solar cells. Furthermore, we examine the field dependence of charge generation efficiency and find our ITCE results to be in excellent agreement with those obtained via time-delayed collection field measurements conducted on the same devices.

Direct observation of trap-assisted recombination in organic photovoltaic devices.

Trap-assisted recombination caused by localised sub-gap states is one of the most important first-order loss mechanism limiting the power-conversion efficiency of all solar cells. The presence and relevance of trap-assisted recombination in organic photovoltaic devices is still a matter of some considerable ambiguity and debate, hindering the field as it seeks to deliver ever higher efficiencies and ultimately a viable new solar photovoltaic technology. In this work, we show that trap-assisted recombination loss of photocurrent is universally present under operational conditions in a wide variety of organic solar cell materials including the new non-fullerene electron acceptor systems currently breaking all efficiency records. The trap-assisted recombination is found to be induced by states lying 0.35-0.6 eV below the transport edge, acting as deep trap states at light intensities equivalent to 1 sun. Apart from limiting the photocurrent, we show that the associated trap-assisted recombination via these comparatively deep traps is also responsible for ideality factors between 1 and 2, shedding further light on another open and important question as to the fundamental working principles of organic solar cells. Our results also provide insights for avoiding trap-induced losses in related indoor photovoltaic and photodetector applications.

Charge-generating mid-gap trap states define the thermodynamic limit of organic photovoltaic devices.

Detailed balance is a cornerstone of our understanding of artificial light-harvesting systems. For next generation organic solar cells, this involves intermolecular charge-transfer (CT) states whose energies set the maximum open circuit voltage VOC. We have directly observed sub-gap states significantly lower in energy than the CT states in the external quantum efficiency spectra of a significant number of organic semiconductor blends. Taking these states into account and using the principle of reciprocity between emission and absorption results in non-physical radiative limits for the VOC. We propose and provide compelling evidence for these states being non-equilibrium mid-gap traps which contribute to photocurrent by a non-linear process of optical release, upconverting them to the CT state. This motivates the implementation of a two-diode model which is often used in emissive inorganic semiconductors. The model accurately describes the dark current, VOC and the long-debated ideality factor in organic solar cells. Additionally, the charge-generating mid-gap traps have important consequences for our current understanding of both solar cells and photodiodes - in the latter case defining a detectivity limit several orders of magnitude lower than previously thought.

Charge Carrier Transport and Generation via Trap-Mediated Optical Release in Organic Semiconductor Devices.

The impact of intermixed donor-acceptor domains in organic bulk heterojunction (BHJ) solar cells, using low-donor-content devices as model systems, is clarified. At low donor contents, the devices are found to exhibit anomalously high open-circuit voltages independent of the donor-acceptor energetics. These observations can be consistently explained by a theoretical model based on optical release of trapped holes, assuming the donors behave as trap sites in the gap of the acceptor. Our findings provide guidelines for reducing the large open-circuit voltage losses in organic solar cells and avoiding morphology-induced losses in state-of-the-art BHJ solar cells and photodetectors.