Temperature-Dependent Charge-Transfer-State Absorption and Emission Reveal the Dominant Role of Dynamic Disorder in Organic Solar Cells

The energetic landscape of charge-transfer (CT) states at the interface of electron donating and electron accepting domains in organic optoelectronic devices is crucial for their performance. Central questions - such as the role of static energetic disorder and vibrational effects - are under ongoing dispute. This study provides an in-depth analysis of temperature-dependent broadening of the spectroscopic absorption and emission features of CT states in devices with small molecule-fullerene blends. We confirm the validity of the electro-optical reciprocity relation between the photovoltaic external quantum efficiency and electroluminescence, enabling us to validate the device temperature during the experiment. The validated temperature allows us to fit our experimental data with several models, and compare extracted CT state energies with the corresponding open-circuit voltage limit at 0 K. Our findings reveal that the absorption and emission characteristics are usually not symmetric, and dominated by temperature-activated broadening (vibrational) effects instead of static disorder

Reducing Non-Radiative Voltage Losses by Methylation of Push–Pull Molecular Donors in Organic Solar Cells

Organic solar cells are approaching power conversion efficiencies of other thin-film technologies. However, in order to become truly market competitive, the still substantial voltage losses need to be reduced. Here, the synthesis and characterization of four novel arylamine-based push-pull molecular donors was described, two of them exhibiting a methyl group at the para-position of the external phenyl ring of the arylamine block. Assessing the charge-transfer state properties and the effects of methylation on the open-circuit voltage of the device showed that devices based on methylated versions of the molecular donors exhibited reduced voltage losses due to decreased non-radiative recombination. Modelling suggested that methylation resulted in a tighter interaction between donor and acceptor molecules, turning into a larger oscillator strength to the charge-transfer states, thereby ensuing reduced non-radiative decay rates

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

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

Field Effect versus Driving Force: Charge Generation in Small-Molecule Organic Solar Cells

Efficient charge generation in organic semiconductors usually requires an interface with an energetic gradient between an electron donor and an electron acceptor in order to dissociate the photogenerated excitons. However, single-component organic solar cells based on chloroboron subnaphthalocyanine (SubNc) have been reported to provide considerable photocurrents despite the absence of an energy gradient at the interface with an acceptor. In this work, it is shown that this is not due to direct free carrier generation upon illumination of SubNc, but due to a field-assisted exciton dissociation mechanism specific to the device configuration. Subsequently, the implications of this effect in bilayer organic solar cells with SubNc as the donor are demonstrated, showing that the external and internal quantum efficiencies in such cells are independent of the donor-acceptor interface energetics. This previously unexplored mechanism results in efficient photocurrent generation even though the driving force is minimized and the open-circuit voltage is maximized

Doping-induced carrier profiles in organic semiconductors determined from capacitive extraction-current transients

A method to determine the doping induced charge carrier profiles in lightly and moderately doped organic semiconductor thin films is presented. The theory of the method of Charge Extraction by a Linearly Increasing Voltage technique in the doping-induced capacitive regime (doping-CELIV) is extended to the case with non-uniform doping profiles and the analytical description is verified with drift-diffusion simulations. The method is demonstrated experimentally on evaporated organic small- molecule thin films with a controlled doping profile, and solution-processed thin films where the non- uniform doping profile is unintentional, probably induced during the deposition process, and a priori unknown. Furthermore, the method offers a possibility of directly probing charge-density distributions at interfaces between highly doped and lightly doped or undoped layers

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

Organic narrowband near-infrared photodetectors based on intermolecular charge-transfer absorption

Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection

Stacked Dual-Wavelength Near-Infrared Organic Photodetectors

Organic near-infrared (NIR) detectors have potential applications in biomedicine, agriculture, and manufacturing industries to identify and quantify materials contactless, in real time and at a low cost. Recently, tunable narrow-band NIR sensors based on charge-transfer state absorption of bulk-heterojunctions embedded into Fabry-Pérot micro-cavities have been demonstrated. In this work, this type of sensor is further miniaturized by stacking two sub-cavities on top of each other. The resulting three-terminal device detects and distinguishes photons at two specific wavelengths. By varying the thickness of each sub-cavity, the detection ranges of the two sub-sensors are tuned independently between 790 and 1180, and 1020 and 1435 nm, respectively, with full-width-at-half-maxima ranging between 35 and 61 nm. Transfer matrix modeling is employed to select and optimize device architectures with a suppressed cross-talk in the coupled resonator system formed by the sub-cavities, and thus to allow for two distinct resonances. These stacked photodetectors pave the way for highly integrated, bi-signal spectroscopy tunable over a broad NIR range. To demonstrate the application potential, the stacked dual sensor is used to determine the ethanol concentration in a water solution