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W e would like to start off by thanking the authors of the comment, Wetzelaer and Blom, for their very helpful and constructive analysis. They present an interesting alternative view on an important and timely research topic. Before discussing the mechanism suggested in their comment, from the viewpoint of our experimental results, we would like to summarize our findings. In our work, 1 we experimentally showed that • The contact between donor molecules in the active layer of organic solar cells (OSCs) and a molybdenum oxide (MoO 3) hole extraction layer (HEL) causes an increase in nonradiative recombination losses, proportional to the extent of contacts. • We attributed these losses to surface recombination, and we proved that the losses can be suppressed by inserting a thin interfacial fullerene layer at the anode side. • Analyzing various donor−acceptor mixing ratios, with and without a fullerene-modified HEL, we decoupled and quantified the contribution from surface recombi-nation on the total nonradiative losses occurring in these devices. In the best case, we showed an improvement of 150 meV in V OC , as compared to the reference device. This demonstrates that surface recombination is a considerable contributor to nonradiative voltage losses in these solar cells, which are otherwise commonly occurring through charge-transfer states or energetic trap states because of defects in the bulk. We consider this the main result of our work. • Measurements by a modified charge extraction by linearly increasing voltage (CELIV) technique provided evidence that the improvement in V OC could be attributed to an enhanced built-in potential (V bi), reducing the presence of minority charge carriers at the respective electrodes. Although the authors of the comment in general agree with our experimental findings, they argue that the V bi does not play a direct role in suppressing the surface recombination of minority carriers. The introduction of a C 60 interlayer, they argue, renders the MoO 3 contact ohmic. 2 The reduced anodic injection barrier simultaneously increases the V bi , minimizes nonradiative voltage losses upon the extraction of majority carriers (holes), and suppresses minority-carrier (electron) surface recombination, the latter being the result of hole accumulation and associated band bending near the ohmic hole contact. Therefore, the ohmic contact formation suppresses both majority-and minority-carrier surface recombination losses, whereas the built-in voltage per se, they reason, does not play a major role. It is our opinion that the authors of the comment provide a very reasonable alternative explanation for the reduced surface recombination. Injection barriers at the contacts are well-known to be detrimental for the performance of OSC as being a major cause of a reduced V bi and increased surface recombination. Injection barriers have been shown to reduce not only the V OC but also the fill factor (FF), sometimes even leading to s-shaped JV curves. 3−5 It has been suggested that, in the case of very large injection barriers, the V OC is given by V bi. 6,7 Although V bi is determined by the difference in the work functions of the contacts, because of Fermi level pinning and the associated band bending, the built-in potential across the active layer, the effective V bi , typically cannot exceed the effective gap of the bulk-heterojunction blend. In other words, the anode Fermi level pins to the highest occupied molecular orbital (HOMO) of the donor, whereas the cathode pins to the lowest unoccupied molecular orbital (LUMO) of the acceptor. In addition, because of disorder, Fermi level pinning typically occurs to discrete gap or tail states, causing additional band bending, which further limits the effective V bi. 8,9 If there is an injection barrier at one contact, an increase or decrease in this barrier is directly reflected in the V bi. 5 Sachsische Aufbaubank [100325708]; Academy of FinlandAcademy of Finland

Omnipresent quality monitoring in food products, blood-oxygen measurement in lightweight conformal wrist bands, or data-driven automated industrial production: Innovation in many fields is being empowered by sensor technology. Specifically, organic photodetectors (OPDs) promise great advances due to their beneficial properties and low-cost production. Recent research has led to rapid improvement in all performance parameters of OPDs, which are now on-par or better than their inorganic counterparts, such as silicon or indium gallium arsenide photodetectors, in several aspects. In particular, it is possible to directly design OPDs for specific wavelengths. This makes expensive and bulky optical filters obsolete and allows for miniature detector devices. In this review, recent progress of such narrowband OPDs is systematically summarized covering all aspects from narrow-photo-absorbing materials to device architecture engineering. The recent challenges for narrowband OPDs, like achieving high responsivity, low dark current, high response speed, and good dynamic range are carefully addressed. Finally, application demonstrations covering broadband and narrowband OPDs are discussed. Importantly, several exciting research perspectives, which will stimulate further research on organic-semiconductor-based photodetectors, are pointed out at the very end of this review.

Organic photovoltaics (PV) is an energy-harvesting technology that offers many advantages, such as flexibility, low weight and cost, as well as environmentally benign materials and manufacturing techniques. Despite growth of power conversion efficiencies to around 19 % in the last years, organic PVs still lag behind inorganic PV technologies, mainly due to high losses in open-circuit voltage. Understanding and improving open circuit voltage in organic solar cells is challenging, as it is controlled by the properties of a donor-acceptor interface where the optical excitations are separated into charge carriers. Here, we provide an electrostatic model of a rough donor-acceptor interface and test it experimentally on small molecule PV materials systems. The model provides concise relationships between the open-circuit voltage, photovoltaic gap, charge-transfer state energy, and interfacial morphology. In particular, we show that the electrostatic bias generated across the interface reduces the photovoltaic gap. This negative influence on open-circuit voltage can, however, be circumvented by adjusting the morphology of the donor-acceptor interface. Organic solar cells, despite their high power conversion efficiencies, suffer from open circuit voltage losses making them less appealing in terms of applications. Here, the authors, supported with experimental data on small molecule photovoltaic cells, relate open circuit voltage to photovoltaic gap, charge-transfer state energy, and donor-acceptor interfacial morphology. Open Access funding enabled and organized by Projekt DEAL. This publication is based on work supported by the KAUST Office of Sponsored Research (OSR) under award nos. OSR-2018-CARF/CCF-3079 and OSR-CRG2018- 3746. D.A. also acknowledges the KAUST PSE Division for hosting his sabbatical in the framework of the Division’s Visiting Faculty program. D.A. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for financial support through the collaborative research centers TRR 146, SPP 2196, and grant number 460766640. We thank Kun-Han Lin, Leanne Paterson, Wenlan Liu, Mukunda Mandal, and Naomi Kinaret for fruitful discussions and proof reading of the manuscript. Furthermore, the authors acknowledge Dr. Beatrice Beyer from Fraunhofer Institut FEP for supplying the donor molecule ZnF4Pc. J.B. and K.L. acknowledge the German Federal Ministry of Education and Research (BMBF) for funding through the projects “Pergamon” (16ME0012) and “Flexmonirs” (01DR20008A).

Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction. This work uses a neat C60 interlayer on the anode to experimentally reveal that surface recombination is a significant contributor to nonradiative recombination losses in organic solar cells. These losses are shown to proportionally increase with the extent of contact between donor molecules in the photoactive layer and a molybdenum oxide (MoO3) hole extraction layer, proven by calculating voltage losses in low- and high-donor-content bulk heterojunction device architectures. Using a novel in-device determination of the built-in voltage, the suppression of surface recombination, due to the insertion of a thin anodic-C60 interlayer on MoO3, is attributed to an enhanced built-in potential. The increased built-in voltage reduces the presence of minority charge carriers at the electrodes-a new perspective on the principle of selective charge extraction layers. The benefit to device efficiency is limited by a critical interlayer thickness, which depends on the donor material in bilayer devices. Given the high popularity of MoO3 as an efficient hole extraction and injection layer and the increasingly popular discussion on interfacial phenomena in organic optoelectronic devices, these findings are relevant to and address different branches of organic electronics, providing insights for future device design.

Sb2Se3 is a typical V2VI3 binary chalcogenide compound characterized by a single crystalline phase and a fixed composition. Sb2Se3 displays a narrow energy gap ranging from 1.1 to 1.3 eV, which are quite optimal values for single-junction solar cells. Earth-abundant and non-toxic components make this material a good candidate for low-cost thin-film solar cells. In substrate configuration, a world record efficiency of 9.2% was recently obtained. Sb2Se3 thin films exhibit an accentuated predisposition to form (Sb4Se6)n ribbons along the [001] direction. This anisotropy heavily influences the charge transport of the photogenerated carriers. In this work, structural characterization of the Sb2Se3 films showed that the crystalline quality and preferential orientation are strongly dependent on the window layer used. To better understand the growth mechanism, Sb2Se3 thin films were deposited by close-spaced sublimation on five different window layers, such as CdS, CdS:F, CdSe, As2S3, and ZnCdS. Sb2Se3-based solar cells, realized in superstrate configuration on these different substrates, evidently demonstrate the influence of the Sb2Se3 preferential orientation on the photovoltaic parameters.

Charge generation and recombination processes at interfaces between electron donating (donor, D) and accepting molecules (acceptor, A) are mediated by intermolecular charge-transfer (CT) states. Si...

Application of spectroscopic photo-detecting technologies in future innovations such as wearable or integrated electronics will require miniaturized spectrometers. This can be achieved by using an array of small-area, wavelength-selective photodetectors. Here, filterless narrowband photodetectors based on a novel device concept are demonstrated. The narrowband photoresponse is realized by utilizing nanometer-thick 2,2-((3,4-dimethyl-[2,2:5,2:5,2:5,2-quinquethiophene]-5,5-diyl)bis (methanylylidene))-dimalononitrile (DCV5T-Me):C60 photo-active layers (3-6 nm) in a Fabry-Perot cavity. By varying the cavity thickness, achieved by adjusting the transport layer thicknesses, we realize continuously tunable detection wavelengths, spanning the entire visible region (400-700 nm). Most importantly, because the active layer is only nanometer-thick, position of the active layer can be adjusted within the cavity. Thus, with an optimized position of the active layer, the photodetectors exhibit an overtone free, monochro...

The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C

Extraction barriers are usually undesired in organic semiconductor devices since they lead to reduced device performance. In this work, we intentionally introduce an extraction barrier for holes, leading to nonlinear photoresponse. The effect is utilized in near-infrared (NIR) organic photodetectors (OPDs) to perform distance measurements, as delineated in the focus-induced photoresponse technique (FIP). The extraction barrier is introduced by inserting an anodic interlayer with deeper highest occupied molecular orbital (HOMO), compared to the donor material, into a well-performing OPD. With increasing irradiance, achieved by decreasing the illumination spot area on the OPD, a higher number of holes pile up at the anode, counteracting the built-in field and increasing charge-carrier recombination in the bulk. This intended nonlinear response of the photocurrent to the irradiance allows determining the distance between the OPD and the light source. We demonstrate fully vacuum-deposited organic NIR optical distance photodetectors with a detection area up to 256 mm2 and detection wavelengths at 850 and 1060 nm. Such NIR OPDs have a high potential for precise, robust, low-cost, and simple optical distance measurement setups.

Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction. This work uses a neat C

Interfaces between organic electron-donating (D) and electron-accepting (A) materials can show efficient free charge carrier generation upon illumination, enabling organic photovoltaic devices and photodetectors with photon to electron conversion yields approaching 100%. Recently, organic light-emitting diodes (OLEDs) based on charge transfer (CT) (or exciplex) emission occurring at such D-A interfaces have been shown to exhibit high electroluminescence external quantum yields (EQEEL). However, no organic D-A combination with both a high EQEEL, as well as a high free carrier generation yield has been discovered so far. Such a system would result in significantly higher operating voltages in organic solar cells, reduced dark current in organic photodetectors, and reduced driving voltages for OLEDs.

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 achievableD* is calculated alongside a large set of devices to demonstrate an intrinsic upper limit ofD* 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. Vandewal, K (corresponding author), UHasselt Hasselt Univ, Inst Mat Res IMO, Agoralaan 1,Bldg D, B-3590 Diepenbeek, Belgium ; IMEC, Associated Lab IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. Armin, A (corresponding author), Swansea Univ, Dept Phys, Singleton Pk, Swansea SA2 8PP, W Glam, Wales. ardalan.armin@swansea.ac.uk; koen.vandewal@uhasselt.be

Three furan-fused BODIPYs were synthesized with perfluorinated methyl, ethyl and n-propyl groups on the meso-carbon. They were obtained with high yields by reacting the furan-fused 2-carboxylpyrrole in corresponding perfluorinated acid and anhydride. With the increase in perfluorinated alkyl chain length, the molecular packing in the single crystal is influenced, showing increasing stacking distance and decreasing slope angle. All the BODIPYs were characterized as intense absorbers in near infrared region in solid state, peaking at similar to 800 nm with absorption coefficient of over 280 000 cm(-1). Facilitated by high thermal stability, the furan-fused BODIPYs were employed in vacuum-deposited organic solar cells as electron donors. All devices exhibit PCE over 6.0% with the EQE maximum reaching 70% at similar to 790 nm. The chemical modification of the BODIPY donors have certain influence on the active layer morphology, and the highest PCE of 6.4% was obtained with a notably high jsc of 13.6 mA cm(-2). Sensitive EQE and electroluminance studies indicated that the energy losses generated by the formation of a charge transfer state and the radiative recombination at the donor-acceptor interface were comparable in the range of 0.14-0.19 V, while non-radiative recombination energy loss of 0.38 V was the main energy loss route resulting in the moderate V-oc of 0.76 V.

Dynamic control of solar transmission by photovoltaic-powered electrochromic smart windows is an up-and-coming approach towards the reduction of energy consumption in buildings. Selectively-absorbing transparent organic solar cells are capable of exhibiting excellent visible-light transparency as well as respectable power conversion efficiencies. This work presents three different transparent small-molecule solar cells (TSCs) with an area of 2.52 cm2, two of which are UV-absorbing and one of which absorbs in the NIR, each in combination with an organic electrochromic device (EC). The NIR-absorbing TSC uses a BDP-OMe:C60 combination, and has a power conversion efficiency of 4% with an average visible light transmission (AVT) of 40%. The two UV-harvesting systems, α-6T/B4PYMPM and NPB:B4PYMPM, each have an AVT of 50–65%, as well as high open-circuit voltages of 1.5–2.0 V. We demonstrate that these photogenerated voltages are sufficient to power a fluoran dye-based organic EC, which has excellent optical properties: its color ranges from highly transparent to deep black, and its on/off contrast ratio is higher than 80% in the range between 390 nm and 640 nm. Self-powered smart windows made by the combination of TSCs and ECs provide a way to significantly reduce energy consumption from air conditioning and lighting, towards zero-energy buildings.

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 approximate to 40 nm), ultrahigh specific detectivity above 10(14) 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. China Scholarship CouncilChina Scholarship Council [201706070125, 201706890003, 201706140127]; DFGGerman Research Foundation (DFG)European Commission [VA 1035/5-1]; Sachsische Aufbaubank [100325708]

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 ...

Organic spectrometers are attractive for biomedicine and industrial process monitoring but are currently limited in terms of spectral selectivity and the accessible wavelength range. Here, we achieve narrowband enhancement of the below-gap near-infrared response of charge-transfer (CT) excitations in organic photodiodes by introducing them into a high-quality microcavity. The device architecture includes a nonconductive distributed Bragg reflector and thin metal electrodes, leading to the formation of sharp Tamm plasmon-polariton resonances. We demonstrate how to tailor the arising multimode spectra for spectroscopic photodetectors and present efficient single-resonance devices with remarkable line widths below 22 nm, which are partially transparent for visible wavelengths. Taking advantage of the spectrally broad CT band, we vary the resonator thickness to provide a proof of concept that benefits from the spectral selectivity of our high-quality microcavities. Finally, utilizing transfer-matrix calculati...

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes. This work was supported by the German Federal Ministry for Education and Research (BMBF) through the InnoProfille project "Organische p-i-n Bauelemente 2.2". F.O. would like to thank the German Research Foundation (DFG) for financial support (Grant OR 349/1). This work was partly supported by the DFG within the Cluster of Excellence "Center for Advancing Electronics Dresden." F.P. and D.N. acknowledge funding by the DFG via the SFB 951 "HIOS". T.V. acknowledges the Agency for Innovation by Science and Technology in Flanders (IWT) for funding his Ph.D. The work at Georgia Tech was supported by the Department of the Navy, Office of Naval Research Award No. N00014-14-1-0580 (CAOP MURI) and through a state-sponsored scholarship for graduate students to Y.F. from the China Scholarship Council. We acknowledge the Center for Information Services and High Performance Computing (ZIH) at TU Dresden for computational resources. We thank Prof. Bauerle from the University of Ulm for the supply of DH4T and DH6T and Markus Hummert for P4-Ph4-DIP and BP-Bodipy.

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., Strong light-matter coupling can tune exciton properties but its effect in photovoltaics remains unexplored. Here Nikolis et al. show that the photon energy loss from optical gap to open-circuit voltage can be reduced to unprecedented values by embedding organic solar cells in optical microcavities.

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. V.C.N. and Y.D. contributed equally to this work. The authors would like to thank Prof. Dr. Dieter Neher for providing measurement time on the electroluminescence setup of his lab at University of Potsdam. They would also like to acknowledge the Optoelectronics group in the University of Cambridge for sharing the global analysis codes. This work was supported by the German Federal Ministry of Education and Research (BMBF) through the InnoProfile project "Organische p-i-n Bauelemente2.2" (FKZ 03IPT602X). A.A.B. is a Royal Society university research fellow. Open access funding enabled and organized by Projekt DEAL. Nikolis, VC (corresponding author), Tech Univ Dresden, Dresden Integrated Ctr Appl Phys & Photon Mat IAP, Nothnitzer Str 61, D-01187 Dresden, Germany ; Tech Univ Dresden, Inst Appl Phys, Nothnitzer Str 61, D-01187 Dresden, Germany. Bakulin, AA (corresponding author), Imperial Coll London, Mol Sci Res Hub, London W12 0BE, England. Vandewal, K (corresponding author), Hasselt Univ, Inst Mat Res IMO IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. vasileios_christos.nikolis1@tu-dresden.de; a.bakulin@imperial.ac.uk; koen.vandewal@uhasselt.be

We thank O. Kaveh and D. Schutze for performing conductivity measurements, D. Wohrle for supplying F 8 ZnPc, and M.L. Tietze for insightful discussions. M.S. acknowledges financial support by the German Research Foundation (DFG) through the project MatWorldNet LE-747/44-1, the German Academic Exchange Service within the frame of the IPID4all Program and the Graduate Academy of TU Dresden. A.H. acknowledges financial support from the project UNVEiL of the German Federal Ministry of Education and Research (BMBF). S.K. thanks JSPS for financial support (KAKENHI 26248062). N.U. acknowledges support of the Global-COE Program of MEXT (G03) and 21st Century-COE Program of MEXT(G-4) for developing an ultrahigh-sensitivity UPS system. B.N. received funding from the European Union Seventh Framework Programme under grant agreement no. 607232 (THINFACE). F.O. would like to thank the DFG for financial support (project OR-349/1). Grants for computing time from the Zentrum fur Informationsdienste und Hochleistungsrechnen Dresden (ZIH) are gratefully acknowledged.

Organic solar cells are a promising technology for a large area conversion of sunlight into electricity. In particular for solar cells based on oligomers (small molecules), efficient donor materials absorbing wavelengths larger than 780 nm are still rare. Here, we investigate three aza-BODIPY dyes absorbing in the infrared. The addition of side groups leads to a red shift of the optical gap from 802 to 818 nm. In optimized devices using these donors in a bulk heterojunction with C-60, we observe a higher charge carrier mobility and a higher power conversion efficiency for the molecules without a methyl or methoxy side group lowering the molecular reorganization energy. Surprisingly, the donor-acceptor blend with the lowest energy loss during the electron transfer to the C-60 yields the highest short circuit current. With increasing size of the attached side chain, the devices exhibit a larger trap density, measured by impedance spectroscopy. Based on the investigation of different blend ratios, we conclude that these traps are mainly present in the donor phase. (C) 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The authors would like to acknowledge the Interreg Euregio-Maas-Rijn project 'ORGANEXT' and the IWT-SBO-project Polyspec for funding. They are also grateful for financial support by the Research Programme of the Research Foundation - Flanders (FWO) (project G.0415.14N and M.ERA-NET project RADESOL).

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., Interfaces of organic donor-acceptor blends provide intermolecular charge-transfer states with red-shifted but weak absorption. By introducing an optical micro-cavity; Siegmund et al., enhance their photoresponse to achieve narrowband NIR photodetection with broad spectral tunability.

Organic solar cells demonstrate external quantum efficiencies and fill factors approaching those of conventional photovoltaic technologies. However, as compared with the optical gap of the absorber materials, their open-circuit voltage is much lower, largely due to the presence of significant non-radiative recombination. Here, we study a large data set of published and new material combinations and find that non-radiative voltage losses decrease with increasing charge-transfer-state energies. This observation is explained by considering non-radiative charge-transfer-state decay as electron transfer in the Marcus inverted regime, being facilitated by a common skeletal molecular vibrational mode. Our results suggest an intrinsic link between non-radiative voltage losses and electron-vibration coupling, indicating that these losses are unavoidable. Accordingly, the theoretical upper limit for the power conversion efficiency of single-junction organic solar cells would be reduced to about 25.5% and the optimal optical gap increases to (1.45-1.65) eV, that is, (0.2-0.3) eV higher than for technologies with minimized non-radiative voltage losses.

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D-A complexes occur at photon energies below the optical gaps of both the donors and the C

We investigate the photodegradation in inert atmosphere of (poly 3-hexylthiophene:[6,6]-phenyl-C61-butyric acid methyl ester) (P3HT:PCBM) heterojunction solar cells under continuous illumination using advanced electrical characterization and a device modeling tool. Our results indicate that different failure mechanisms contribute to the performance loss. The first 250 h of illumination induced p-type doping and recombination related to traps in the blend which mainly decreases the short-circuit current and the efficiency of the cells. Device modeling and simulation allowed us to prove that increased p-type doping of the blend provoke the loss in the short-circuit current and the quantum efficiency by simultaneous reduction of charge carrier mobility and the electric field together with a shrink of the space charge region. Transmission electron microscopy (TEM) measurements reveal a change in the blend morphology upon long illumination times manifested by phase segregation in the blend. The reduction in the open-circuit voltage is reported to be related to a slight reduction of the charge transfer energy (CT) upon 700 h of illumination aging. The final failure mechanism was a rapid drop in the fill factor which occurs upon 1000 h of illumination and manifested by the appearance of an S-shape J–V characteristic. This failure mechanism is linked to the reduction of charge extraction caused by a reduced surface recombination velocity at the contacts.

For an increased lifetime of polymer:fullerene bulk heterojunction (BHJ) solar cells, an understanding of the chemical and morphological degradation phenomena taking place under operational conditions is crucial. Phase separation between polymer and fullerene induced by thermal stress has been pointed out as a major issue to overcome. While often the effect of thermal stress on the morphology of polymer:fullerene BHJ is investigated in the darkness, here we observe that light exposure slows down fullerene crystallization and phase separation induced at elevated temperatures. The observed photo-stabilizing effect on active layer morphology is quite independent on the polymer and is attributed to light-induced dimerization of the fullerene. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1209–1214

P3HT:PCBM blends applied as active layers for bulk heterojunction organic solar cells generally show unstable morphologies upon prolonged thermal annealing, severely limiting the lifetime of the devices. As such, the thermodynamic instability of the blend is a limiting factor in the overall performance of organic photovoltaics, and a strong disadvantage in the fierce competition with other photovoltaic technologies. This paper shows whether different blend preparation conditions and intrinsic structural changes in the side chains of poly(3-alkylthiophene) (P3AT) derivatives can influence the thermal stability of the resulting solar cells. A combination of Bright Field Transmission Electron Microscopy (BFTEM) and the analysis of Selected Area Electron Diffraction (SAED) patterns revealed that the investigated preparation conditions do not really affect the thermal stability, whereas the introduction of a small ratio (10%) of specific functional moieties in the side chains of random P3AT copolymers does improve the thermal stability significantly. It was demonstrated that demixing of the blend components upon prolonged thermal annealing is strongly delayed in the functionalized P3AT:PCBM blends. The enhanced thermal stability was confirmed by in-situ monitoring of the short circuit current of organic solar cells based on the respective active layers. The introduction of functionalized side chains hence represents an attractive approach to increase the operational stability of organic photovoltaics based on the bulk heterojunction concept.

We report on the synthesis of new thermally cross-linkable all-conjugated diblock copolymers composed of a poly(3-hexylthiophene) (P3HT) block and an acrylate-functionalized polythiophene block. These copolymers are then used in bulk heterojunction (BHJ) solar cells with [6,6]-phenyl C61-butyric acid methyl ester (PCBM), and their photovoltaic performances are compared with standard P3HT/PCBM devices. Thermal cross-linking of the functional copolymers/PCBM blends is performed to improve the thermal stability of the active layer. BHJ photovoltaic cells with cross-linkable copolymers and PCBM show initial power conversion efficiencies slightly lower than that of P3HT devices. However, solar cells with cross-linkable copolymers retain more than 85% of their initial power efficiency value after 165 h of thermal annealing (accelerated aging test), whereas the same devices with P3HT retain less than 65% of their initial power efficiency. This improvement of the thermal stability of BHJ photovoltaic cells is the...

The non-geminate recombination of charge carriers in polymer-fullerene solar cells has been modeled in the last few years with a trap-assisted recombination model, which states that the apparent recombination order depends on the concentration of trapped charges tailing into the band gap. Higher concentrations of trapped charges lead to higher apparent recombination orders. In this work, the mass fraction f of highly crystalline nanofibrillar P3HT to the total P3HT content in P3HT:PCBM solar cells is consistently varied, controlling the temperature of a nanofibers-P3HT casting dispersion. A systematic study of the apparent recombination order, measured with a transient photovoltage technique, as a function of f is presented. A correlation is shown between the apparent recombination order, the P3HT crystallinity, and the trap concentration in the band gap measured with an admittance spectroscopy technique

This paper focuses on the characterization of the ZnO/poly(3- hexylthiophene) (P3HT) interfaces in nanostructured hybrid solar cells, aiming to elucidate the relationship between thermal treatment, local morphology, and device performance. An equivalent impedimetric model for the device is proposed, allowing us to extract information about the ZnO/P3HT interface morphology and its impact on the photovoltaic properties by comparing devices with and without nanopatterning. It is found that the influence of thermal treatment on performance lies solely in the interface, resulting from a different interfacial morphology of P3HT depending on which crystal direction of ZnO is present. © 2011 American Chemical Society. ispartof: Journal of Physical Chemistry C vol:115 issue:33 pages:16695-16700 status: published

The use of nanostructured non-conventional semiconductors such as conjugated polymers and metal oxides (e.g. TiO2), opens promising perspectives towards a new generation of solar cells based on the concept of donor:acceptor bulk heterojunctions. In this concept donor material and acceptor material form interpenetrating networks allowing light absorption, charge transfer and charge transport throughout the entire bulk of the thin film. Since nanomorphology is of crucial importance for this type of solar cells, in this contribution the use of nanofibers in bulk heterojunction solar cells is explored in order to obtain highways for charge transport. We investigate in particular the use of P3AT (poly(3-alkylthiophene)) nanofibers and show that the polymer fraction aggregated into fibers can be easily controlled by temperature. We find an optimal efficiency at intermediate fiber fraction and show that it can be linked to the morphology of the active layer.

Although platinum (Pt) is a rare and very expensive material, Pt counter electrodes are still very commonly used for reaching high efficiencies in dye-sensitized solar cells (DSCs). The use of alternative cheaper catalyst materials did not yet yield equivalent efficiencies. In this work, we tried to understand how to reduce the amount of deposited Pt-material and simultaneously deliver higher DSC performances. We systematically compared the properties of Pt-counter electrodes prepared by simple solution deposition methods such as spray-coating, dip-coating, brushing with reference to the Pt-electrodes prepared by sputtering onto fluorine doped-tin oxides (FTOs). The morphological and structural characterizations of the deposited Pt-layers were performed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The composition of Pt-material was quantified using SEM electron dispersive X-ray (EDX) mapping measurements which were further compared with optical transmission measurements. Also contact angle and sheet resistance measurements were performed. By taking Pt-layers composition, morphology and structural factors into account, 9.16% efficient N3 dye based DSCs were assembled. The DSCs were subjected to various opto-electrical characterization techniques like current–voltage (I–V), external quantum efficiency (EQE), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and transient photo voltage (TPV) measurements. The obtained experimental data suggest that the Pt counter electrodes prepared by solution deposition methods can also reach high DSC device performances with a consumption of very little amount of Pt material as compared with sputtered Pt-layers. This process also proves that higher DSC performances are not limited to the usage of sputtered Pt-layer as counter electrode.

Graphene has potential for applications in solar cells. We show that the short circuit current density of P3HT (Poly(3-hexylthiophene-2,5-diyl):PCBM((6,6)-Phenyl C61 butyric acid methyl ester) solar cells is enhanced by 10% upon the addition of graphene, with a 15% increase in the photon to electric conversion efficiency. We discuss the performance enhancement by studying the crystallization of P3HT, as well as the electrical transport properties. We show that graphene improves the balance between electron and hole mobilities with respect to a standard P3HT:PCBM solar cell.

Lately, research efforts in photovoltaics towards hybrid solar cells based on nanostructured metal oxides and conjugated polymers have been intensifying. However, very limited effort has been spent so far to investigate their recombination kinetics in comparison with their fully organic counterpart. In this work, impedance spectroscopy under different illumination intensities is used to probe the recombination kinetics of hybrid solar cells based on ZnO nanorod arrays and poly(3-hexylthiophene). A recombination-based model developed for fully organic solar cells is effectively applied in our hybrid solar cells, demonstrating their similarity in device physics and establishing the nanorod array/polymer compound as true bulk heterojunction.

Metal-substituted phthalocyanine thin films such as copper-phthalocyanine (CuPc) are often used as photo-active and hole transporting layers (HTLs) in fully organic photovoltaic devices. In this work, CuPc is vacuum sublimated on an electron acceptor layer of mesoporous titania (TiO(2)) for the formation of hybrid TiO(2):CuPc solar cell devices. The performance of these hybrid solar cell devices was demonstrated without and with dye sensitization at the TiO(2):CuPc interface. The charge separation and photocurrent contribution at the interfaces in these multilayer hybrid devices was studied by using a variety of optoelectrical and photophysical characterization techniques. It is important to understand the fundamental interface properties of these multilayer hybrid solar cell devices for optimized performance.

Electrical transport properties of poly (3-hexylthiophene) (P3HT) (6,6)-phenyl C61-butyric acid methyl ester (PCBM) solar cells, with and without encapsulation, have been investigated and analyzed using admittance spectroscopy and capacitance voltage measurements at different temperatures. The admittance spectroscopy clearly reveals two defect states with activation energies of 53 and 100 meV, and a concentration ten times higher in the unencapsulated sample. These defects seem to have a strong effect on the charge transport and the solar cell performance when they are present with a high concentration, since they lead to a decrease of the mobility and also the short-circuit current and the efficiency. The origin of these defects has been assigned to reaction of the blend with O2 which is also known to induce p-type doping in pure P3HT. In an attempt to understand the effect of these defects on the organic solar cell performance, modeling and simulation were carried out using the effective medium layer model and gave good agreement with the measurements results.

The molecular weight of poly(3-hexylthiophene) is an important factor influencing the photovoltaic properties of bulk heterojunction organic solar cells based on this material. However, since different synthetic processes or repetitive soxhlet extractions - generally applied to obtain the different molecular weight batches under study - result in samples with simultaneously varying regioregularity (RR) and polydispersity index (PDI), it has not been possible yet to find an unambiguous correlation between the molecular weight and the photovoltaic performance. In the present work preparative gel permeation chromatography is introduced as a versatile technique to fractionate the donor polymer and thereby obtain a systematic variation of the number average molecular weight (M-n = 11-91 kg mol (1)) with an almost constant PDI and RR. Polymer crystallinity and conjugation length are evaluated by UV-Vis spectroscopy, rapid heat-cool calorimetry and selected area electron diffraction, and are found to be deeply affected by Mn. This in turn influences the behavior of the charge transfer state energy, measured via Fourier transform photocurrent spectroscopy, and therefore the open-circuit voltage. The short-circuit current is also affected by Mn, but mainly due to a change in absorption coefficient. The apparent recombination order is shown to be linked to the morphology of the polymer: fullerene blend and is determined using transient photovoltage and photocurrent techniques. Finally, a correlation between recombination and fill factor is also suggested.