Decreasing exciton dissociation rates for reduced voltage losses in organic solar cells.

Enhancing the device electroluminescence quantum efficiency (EQEEL) is a critical factor in mitigating non-radiative voltage losses (VNR) and further improving the performance of organic solar cells (OSCs). While the common understanding attributes EQEEL in OSCs to the dynamics of charge transfer (CT) states, persistent efforts to manipulate these decay dynamics have yielded limited results, with the EQEEL of high-efficiency OSCs typically remaining below 10-2%. This value is considerably lower than that observed in high efficiency inorganic photovoltaic devices. Here, we report that EQEEL is also influenced by the dissociation rate constant of singlet states (kDS). Importantly, in contrast to the traditional belief that advocates maximizing kDS for superior photovoltaic quantum efficiency (EQEPV), a controlled reduction in kDS is shown to enhance EQEEL without compromising EQEPV. Consequently, a promising experimental approach to address the VNR challenge is proposed, resulting in a significant improvement in the performance of OSCs.

Molecularly induced order promotes charge separation through delocalized charge-transfer states at donor-acceptor heterojunctions.

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors above 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher structural order of B4PYMPM molecules leads to more delocalized CT states. Furthermore, we find no correlation between the quantum efficiency of FCC radiative recombination and the bound or unbound nature of the CT states. This work highlights the importance of structural ordering at donor-acceptor interfaces for efficient FCC generation and shows that less bound CT states do not preclude efficient radiative recombination.

A tetrathienopyrrole-based ladder-type donor polymer for high-performance organic near-infrared cavity detectors.

Organic semiconductors can afford detection at wavelengths beyond commercial silicon photodetectors. However, for each targeted near-infrared wavelength range, this requires individually optimized materials, which adds to the complexity and costs. Moreover, finding molecules with strong absorption beyond 1 µm that perform well in organic photodetectors remains a challenge. In microcavity devices, the detection window can be extended to wavelengths inaccessible for silicon without the need for new materials by adopting an intelligent design. Previous work has demonstrated the applicability of a dithienopyrrole-based donor polymer (PDTPQx) in such a cavity photodetector device, with a photoresponse up to 1200 nm. In this work, the π-conjugated backbone of the polymer is extended, affording higher hole mobility and better donor:acceptor intermixing. This leads to enhanced peak external quantum efficiencies up to 1450 nm. The (thermal noise limited) detectivities achieved with the PTTPQx polymer (1.07 × 1012 to 1.82 × 1010 Jones) are among the very best in the 900-1400 nm wavelength regime.

Balanced Energy Gaps as a Key Design Rule for Solution-Phase Organic Room Temperature Phosphorescence.

Metal-free organic emitters that display solution-phase room temperature phosphorescence (sRTP) remain exceedingly rare. Here, we investigate the structural and photophysical properties that support sRTP by comparing a recently reported sRTP compound (BTaz-Th-PXZ) to two novel analogous materials, replacing the donor group by either acridine or phenothiazine. The emissive triplet excited state remains fixed in all three cases, while the emissive charge-transfer singlet states (and the calculated paired charge-transfer T2 state) vary with the donor unit. While all three materials show dominant RTP in film, in solution different singlet-triplet and triplet-triplet energy gaps give rise to triplet-triplet annihilation followed by weak sRTP for the new compounds, compared to dominant sRTP throughout for the original PXZ material. Engineering both the sRTP state and higher charge-transfer states therefore emerges as a crucial element in designing emitters capable of sRTP.

Understanding and Suppressing Non-Radiative Recombination Losses in Non-Fullerene Organic Solar Cells.

Organic solar cells benefit from non-fullerene acceptors (NFA) due to their high absorption coefficients, tunable frontier energy levels, and optical gaps, as well as their relatively high luminescence quantum efficiencies as compared to fullerenes. Those merits result in high yields of charge generation at a low or negligible energetic offset at the donor/NFA heterojunction, with efficiencies over 19% achieved for single-junction devices. Pushing this value significantly over 20% requires an increase in open-circuit voltage, which is currently still well below the thermodynamic limit. This can only be achieved by reducing non-radiative recombination, and hereby increasing the electroluminescence quantum efficiency of the photo-active layer. Here, current understanding of the origin of non-radiative decay, as well as an accurate quantification of the associated voltage losses are summarized. Promising strategies for suppressing these losses are highlighted, with focus on new material design, optimization of donor-acceptor combination, and blend morphology. This review aims at guiding researchers in their quest to find future solar harvesting donor-acceptor blends, which combine a high yield of exciton dissociation with a high yield of radiative free carrier recombination and low voltage losses, hereby closing the efficiency gap with inorganic and perovskite photovoltaics.

RAINBOW Organic Solar Cells: Implementing Spectral Splitting in Lateral Multi-Junction Architectures.

While multi-junction geometries have the potential to boost the efficiency of organic solar cells, the experimental gains yet obtained are still very modest. This work proposes an alternative spectral splitting device concept in which various individual semiconducting junctions with cascading bandgaps are laid side by side, thus the name RAINBOW. Each lateral sub-cell receives a fraction of the spectrum that closely matches the main absorption band of the given semiconductor. Here, simulations are used to identify the important material and device properties of each RAINBOW sub-cell. Using the resulting design rules, three systems are selected, with narrow, medium, and wide effective bandgaps, and their potential as sub-cells in this geometry is experimentally investigated. With the aid of a custom-built setup that generates spectrally spread sunlight on demand, the simulations are experimentally validated, showing that this geometry can lead to a reduction in thermalization losses and an improvement in light harvesting, which results in a relative improvement in efficiency of 46.6% with respect to the best sub-cell. Finally, a working proof-of-concept monolithic device consisting of two sub-cells deposited from solution on the same substrate is fabricated, thus demonstrating the feasibility and the potential of the RAINBOW solar cell concept.

Ultra-precise photothermal measurements reveal near unity photoluminescence quantum yields of molecular emitters in solution.

Molecules with a photoluminescence quantum yield (PLQY) approaching unity enable new applications such as efficient luminescent solar concentrators and spectral redistributors. Moreover, they have the potential for thermally assisted photon upconversion and optical refrigeration, for which the slightest amount of non-radiative loss is detrimental. However, when the PLQY is within a few percent of 100%, it cannot be precisely determined using standard techniques. Here, we combine spectroscopic measurements with photothermal techniques to determine the photothermal threshold energy, i.e. the minimum photon energy at which the chromophores produce heat upon excitation. The PLQY is directly related to this energy and is determined for six fluorescent molecules in low concentration solutions with an unprecedented precision down to ±0.003 within 95% confidence intervals. Independent measurements based on photothermal-deflection spectroscopy and thermal lensing spectroscopy generally provide values within the margin of error, demonstrating the reliability of this measurement concept. Solutions of perylene red in carbon tetrachloride are found to have the highest PLQY of the measured series, being 0.994 ± 0.003. In addition, we observe phonon-assisted, optical upconversion when exciting perylene red within its optical gap at photon energies below its photothermal threshold. Similar measurements on perylene orange in chloroform reveal the presence of low energy sub-gap impurities, preventing upconversion when exciting at the photothermal threshold.

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.

Increasing donor-acceptor spacing for reduced voltage loss in organic solar cells.

The high voltage losses ([Formula: see text]), originating from inevitable electron-phonon coupling in organic materials, limit the power conversion efficiency of organic solar cells to lower values than that of inorganic or perovskite solar cells. In this work, we demonstrate that this [Formula: see text] can in fact be suppressed by controlling the spacing between the donor (D) and the acceptor (A) materials (DA spacing). We show that in typical organic solar cells, the DA spacing is generally too small, being the origin of the too-fast non-radiative decay of charge carriers ([Formula: see text]), and it can be increased by engineering the non-conjugated groups, i.e., alkyl chain spacers in single component DA systems and side chains in high-efficiency bulk-heterojunction systems. Increasing DA spacing allows us to realize significantly reduced [Formula: see text] and improved device voltage. This points out a new research direction for breaking the performance bottleneck of organic solar cells.

Miniaturized VIS-NIR Spectrometers Based on Narrowband and Tunable Transmission Cavity Organic Photodetectors with Ultrahigh Specific Detectivity above 1014 Jones.

Spectroscopic photodetection plays a key role in many emerging applications such as context-aware optical sensing, wearable biometric monitoring, and biomedical imaging. Photodetectors based on organic semiconductors open many new possibilities in this field. However, ease of processing, tailorable optoelectronic properties, and sensitivity for faint light are still significant challenges. Here, the authors report a novel concept for a tunable spectral detector by combining an innovative transmission cavity structure with organic absorbers to yield narrowband organic photodetection in the wavelength range of 400-1100 nm, fabricated in a full-vacuum process. Benefiting from this strategy, one of the best performed narrowband organic photodetectors is achieved with a finely wavelength-selective photoresponse (full-width-at-half-maximum of ≈40 nm), ultrahigh specific detectivity above 1014 Jones, the maximum response speed of 555 kHz, and a large dynamic range up to 168 dB. Particularly, an array of transmission cavity organic photodetectors is monolithically integrated on a small substrate to showcase a miniaturized spectrometer application, and a true proof-of-concept transmission spectrum measurement is successfully demonstrated. The excellent performance, the simple device fabrication as well as the possibility of high integration of this new concept challenge state-of-the-art low-noise silicon photodetectors and will mature the spectroscopic photodetection into technological realities.

Diffusion-enhanced exciton dissociation in single-material organic solar cells.

Single-material organic solar cells have recently attracted research attention due to their simplicity, morphological robustness and high yield of exciton dissociation. Using α-sexithiophene as a model system, we show that the single-event probability of the exciton dissociation at the boundaries of polycrystalline domains with different molecular orientation is extremely low (∼0.5%), while a high efficiency of charge generation is gained via hundred-fold crossings of the domain boundaries due to the long exciton diffusion length (∼45 nm).

Enhancing sub-bandgap external quantum efficiency by photomultiplication for narrowband organic near-infrared photodetectors.

Detection of electromagnetic signals for applications such as health, product quality monitoring or astronomy requires highly responsive and wavelength selective devices. Photomultiplication-type organic photodetectors have been shown to achieve high quantum efficiencies mainly in the visible range. Much less research has been focused on realizing near-infrared narrowband devices. Here, we demonstrate fully vacuum-processed narrow- and broadband photomultiplication-type organic photodetectors. Devices are based on enhanced hole injection leading to a maximum external quantum efficiency of almost 2000% at -10 V for the broadband device. The photomultiplicative effect is also observed in the charge-transfer state absorption region. By making use of an optical cavity device architecture, we enhance the charge-transfer response and demonstrate a wavelength tunable narrowband photomultiplication-type organic photodetector with external quantum efficiencies superior to those of pin-devices. The presented concept can further improve the performance of photodetectors based on the absorption of charge-transfer states, which were so far limited by the low external quantum efficiency provided by these devices.

The role of spin in the degradation of organic photovoltaics.

Stability is now a critical factor in the commercialization of organic photovoltaic (OPV) devices. Both extrinsic stability to oxygen and water and intrinsic stability to light and heat in inert conditions must be achieved. Triplet states are known to be problematic in both cases, leading to singlet oxygen production or fullerene dimerization. The latter is thought to proceed from unquenched singlet excitons that have undergone intersystem crossing (ISC). Instead, we show that in bulk heterojunction (BHJ) solar cells the photo-degradation of C60 via photo-oligomerization occurs primarily via back-hole transfer (BHT) from a charge-transfer state to a C60 excited triplet state. We demonstrate this to be the principal pathway from a combination of steady-state optoelectronic measurements, time-resolved electron paramagnetic resonance, and temperature-dependent transient absorption spectroscopy on model systems. BHT is a much more serious concern than ISC because it cannot be mitigated by improved exciton quenching, obtained for example by a finer BHJ morphology. As BHT is not specific to fullerenes, our results suggest that the role of electron and hole back transfer in the degradation of BHJs should also be carefully considered when designing stable OPV devices.

Reverse dark current in organic photodetectors and the major role of traps as source of noise.

Organic photodetectors have promising applications in low-cost imaging, health monitoring and near-infrared sensing. Recent research on organic photodetectors based on donor-acceptor systems has resulted in narrow-band, flexible and biocompatible devices, of which the best reach external photovoltaic quantum efficiencies approaching 100%. However, the high noise spectral density of these devices limits their specific detectivity to around 1013 Jones in the visible and several orders of magnitude lower in the near-infrared, severely reducing performance. Here, we show that the shot noise, proportional to the dark current, dominates the noise spectral density, demanding a comprehensive understanding of the dark current. We demonstrate that, in addition to the intrinsic saturation current generated via charge-transfer states, dark current contains a major contribution from trap-assisted generated charges and decreases systematically with decreasing concentration of traps. By modeling the dark current of several donor-acceptor systems, we reveal the interplay between traps and charge-transfer states as source of dark current and show that traps dominate the generation processes, thus being the main limiting factor of organic photodetectors detectivity.

Intrinsic Detectivity Limits of Organic Near-Infrared Photodetectors.

Organic photodetectors (OPDs) with a performance comparable to that of conventional inorganic ones have recently been demonstrated for the visible regime. However, near-infrared photodetection has proven to be challenging and, to date, the true potential of organic semiconductors in this spectral range (800-2500 nm) remains largely unexplored. In this work, it is shown that the main factor limiting the specific detectivity (D*) is non-radiative recombination, which is also known to be the main contributor to open-circuit voltage losses. The relation between open-circuit voltage, dark current, and noise current is demonstrated using four bulk-heterojunction devices based on narrow-gap donor polymers. Their maximum achievable D* is calculated alongside a large set of devices to demonstrate an intrinsic upper limit of D* as a function of the optical gap. It is concluded that OPDs have the potential to be a useful technology up to 2000 nm, given that high external quantum efficiencies can be maintained at these low photon energies.

Orientation dependent molecular electrostatics drives efficient charge generation in homojunction organic solar cells.

Organic solar cells usually utilise a heterojunction between electron-donating (D) and electron-accepting (A) materials to split excitons into charges. However, the use of D-A blends intrinsically limits the photovoltage and introduces morphological instability. Here, we demonstrate that polycrystalline films of chemically identical molecules offer a promising alternative and show that photoexcitation of α-sexithiophene (α-6T) films results in efficient charge generation. This leads to α-6T based homojunction organic solar cells with an external quantum efficiency reaching up to 44% and an open-circuit voltage of 1.61 V. Morphological, photoemission, and modelling studies show that boundaries between α-6T crystalline domains with different orientations generate an electrostatic landscape with an interfacial energy offset of 0.4 eV, which promotes the formation of hybridised exciton/charge-transfer states at the interface, dissociating efficiently into free charges. Our findings open new avenues for organic solar cell design where material energetics are tuned through molecular electrostatic engineering and mesoscale structural control.

Author Correction: Molecular vibrations reduce the maximum achievable photovoltage in organic solar cells.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Molecular vibrations reduce the maximum achievable photovoltage in organic solar cells.

The low-energy edge of optical absorption spectra is critical for the performance of solar cells, but is not well understood in the case of organic solar cells (OSCs). We study the microscopic origin of exciton bands in molecular blends and investigate their role in OSCs. We simulate the temperature dependence of the excitonic density of states and low-energy absorption features, including low-frequency molecular vibrations and multi-exciton hybridisation. For model donor-acceptor blends featuring charge-transfer excitons, our simulations agree very well with temperature-dependent experimental absorption spectra. We unveil that the quantum effect of zero-point vibrations, mediated by electron-phonon interaction, causes a substantial exciton bandwidth and reduces the open-circuit voltage, which is predicted from electronic and vibronic molecular parameters. This effect is surprisingly strong at room temperature and can substantially limit the OSC's efficiency. Strategies to reduce these vibration-induced voltage losses are discussed for a larger set of systems and different heterojunction geometries.

Sub-picosecond charge-transfer at near-zero driving force in polymer:non-fullerene acceptor blends and bilayers.

Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems. Moreover, we establish the influence of the interfacial energetics on the electron and hole transfer rates separately. We demonstrate that charge-transfer timescales remain at a few hundred femtoseconds even at near-zero driving force, which is consistent with the rates predicted by Marcus theory in the normal region, at moderate electronic coupling and at low re-organization energy. Thus, in the design of highly efficient devices, the energy offset at the donor:acceptor interface can be minimized without jeopardizing the charge-transfer rate and without concerns about a current-voltage tradeoff.

The Cost of Converting Excitons into Free Charge Carriers in Organic Solar Cells.

Efficient exciton dissociation and subsequent generation of free charge carriers at the organic donor-acceptor interface requires a number of electron-transfer processes. It is a common view that these steps result in an unavoidable energy loss in organic photovoltaic devices that is not present in other types of solar cells. The currently best performing organic solar cells with power conversion efficiencies over 16% challenge this view, and no interfacial charge-transfer states with energy significantly lower than the strongly absorbing singlet states are detected within the gap of the used donor and acceptor materials. This Perspective will discuss implications, the remaining sources of energy loss, and open questions to be solved to achieve power conversion efficiencies over 20%.