Spectroscopic near-infrared photodetectors enabled by strong light-matter coupling in (6,5) single-walled carbon nanotubes.

Strong light-matter coupling leads to the formation of mixed exciton-polariton states, allowing for a rigorous manipulation of the absorption and emission of excitonic materials. Here, we demonstrate the realization of this promising concept in organic photodetectors. By hybridizing the E11 exciton of semiconducting (6,5) single-walled carbon nanotubes (SWNTs) with near-infrared cavity photons, we create spectrally tunable polariton states within a photodiode. In turn, we are able to red-shift the detection peak that coincides with the lower polariton band. Our photodiodes comprise a metal cavity to mediate strong coupling between light and SWNTs and utilize P3HT and PC70BM as the electron donor and acceptor, respectively. The diodes are formed either via mixing of SWNTs, P3HT, and PC70BM to create a bulk heterojunction or by sequential processing of layers to form flat heterojunctions. The resulting near-infrared sensors show tunable, efficient exciton harvesting in an application-relevant wavelength range between 1000 nm and 1300 nm, with optical simulations showing a possible extension beyond 1500 nm.

Organic indoor PV: vanishing surface recombination allows for robust device architecture.

As a promising candidate to drive low-power, off-grid applications, organic indoor photovoltaics are beginning to attract research and commercial attention. In organic photovoltaic devices, charge transport layers are often used to promote the extraction of majority carriers, while blocking minority carriers. They can however be a source of device degradation and introduce additional complexity to the fabrication of the device stack. Here, a simplified, yet performant indoor OPV architecture is demonstrated with extended absorber thickness and without electron transport layer (ETL). We show that the diminished impact of the ETL on indoor OPV results from a drastically reduced surface recombination in thick absorber devices. However, the ETL remains important under strong, outdoor illumination, since in that case the reduced surface recombination is overwhelmed by bulk recombination. The proposed simplified device architecture with thick absorber (>500 nm) has great potential in large-scale production of indoor OPV.

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.

Strong light-matter coupling for reduced photon energy losses in organic photovoltaics.

Strong light-matter coupling can re-arrange the exciton energies in organic semiconductors. Here, we exploit strong coupling by embedding a fullerene-free organic solar cell (OSC) photo-active layer into an optical microcavity, leading to the formation of polariton peaks and a red-shift of the optical gap. At the same time, the open-circuit voltage of the device remains unaffected. This leads to reduced photon energy losses for the low-energy polaritons and a steepening of the absorption edge. While strong coupling reduces the optical gap, the energy of the charge-transfer state is not affected for large driving force donor-acceptor systems. Interestingly, this implies that strong coupling can be exploited in OSCs to reduce the driving force for electron transfer, without chemical or microstructural modifications of the photo-active layer. Our work demonstrates that the processes determining voltage losses in OSCs can now be tuned, and reduced to unprecedented values, simply by manipulating the device architecture.

Fast Organic Near-Infrared Photodetectors Based on Charge-Transfer Absorption.

We present organic near-infrared photodetectors based on the absorption of charge-transfer (CT) states at the zinc-phthalocyanine-C60 interface. By using a resonant optical cavity device architecture, we achieve a narrowband detection, centered around 1060 nm and well below (>200 nm) the optical gap of the neat materials. We measure transient photocurrent responses at wavelengths of 532 and 1064 nm, exciting dominantly the neat materials or the CT state, respectively, and obtain rise and fall times of a few nanoseconds at short circuit, independent of the excitation wavelength. The current transients are modeled with time-dependent drift-diffusion simulations of electrons and holes which reconstruct the photocurrent signal, including capacitance and series resistance effects. The hole mobility of the donor material is identified as the limiting factor for the high-frequency response. With this knowledge, we demonstrate a new device concept, which balances hole and electron extraction times and achieves a cutoff frequency of 68 MHz upon 1064 nm CT excitation.

Polymer:Fullerene Bimolecular Crystals for Near-Infrared Spectroscopic Photodetectors.

Spectroscopic photodetection is a powerful tool in disciplines such as medical diagnosis, industrial process monitoring, or agriculture. However, its application in novel fields, including wearable and biointegrated electronics, is hampered by the use of bulky dispersive optics. Here, solution-processed organic donor-acceptor blends are employed in a resonant optical cavity device architecture for wavelength-tunable photodetection. While conventional photodetectors respond to above-gap excitation, the cavity device exploits weak subgap absorption of intermolecular charge-transfer states of the intercalating poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bimolecular crystal. This enables a highly wavelength selective, near-infrared photoresponse with a spectral resolution down to 14 nm, as well as dark currents and detectivities comparable with commercial inorganic photodetectors. Based on this concept, a miniaturized spectrophotometer, comprising an array of narrowband cavity photodetectors, is fabricated by using a blade-coated PBTTT:PCBM thin film with a thickness gradient. As an application example, a measurement of the transmittance spectrum of water by this device is demonstrated.

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.

Exciton Diffusion Length and Charge Extraction Yield in Organic Bilayer Solar Cells.

A method for resolving the diffusion length of excitons and the extraction yield of charge carriers is presented based on the performance of organic bilayer solar cells and careful modeling. The technique uses a simultaneous variation of the absorber thickness and the excitation wavelength. Rigorously differing solar cell structures as well as independent photoluminescence quenching measurements give consistent results.