High‐Performance Ta2O5/Al‐Doped Ag Electrode for Resonant Light Harvesting in Efficient Organic Solar Cells

A efficient indium tin oxide (ITO)‐free transparent electrode based on an improved Ag film is designed by introducing small amount of Al during co‐deposition, producing ultrathin and smooth Ag film with low loss. A transparent electrode as thin as 4 nm is achieved by depositing the film on top of Ta₂O₅ layer, and organic solar cells based on such ultrathin electrode are built, producing power conversion efficiency over 7%. The device efficiency can be optimized by simply tuning Ta₂O₅ layer thickness external to the organic photovoltaic (OPV) structure to create an optical cavity resonance inside the photoactive layer. Therefore Ta₂O₅/Al‐doped Ag films function as a high‐performance electrode with high transparency, low resistance, improved photon management capability and mechanical flexibility.     

Broadband Plasmonic Photocurrent Enhancement in Planar Organic Photovoltaics Embedded in a Metallic Nanocavity

A substantial broadband increase in the external quantum efficiency (EQE) of thin‐film organic photovoltaic (OPV) devices using near‐field coupling to surface plasmons is reported, significantly enhancing absorption at surface plasmon resonance (SPR). The devices tested consist of an archetypal boron subpthalocyanine chloride/fullerene (SubPc/C₆₀) donor/acceptor heterojunction embedded within a planar semitransparent metallic nanocavity. The absorption and EQE are modeled in detail and probed by attenuated total internal reflection spectroscopy with excellent agreement. At SPR, the EQE can be enhanced fourfold relative to normal incidence, due to simulated ninefold enhancement in active layer absorption efficiency. The response at SPR is thickness‐independent, down to a few monolayers, suggesting the ability to excite monolayer‐scale junctions with an EQE of ≈6% and a 16‐fold absorption enhancement over normal incidence. These results potentially impact the future design of plasmonically enhanced thin‐film photovoltaics and photodetectors and enable the direct analysis of the dynamics of photocurrent production at OPV heterojunctions.     

Ultra‐High Voltage Multijunction Organic Solar Cells for Low‐Power Electronic Applications

Low power electronics are an ideal application for organic photovoltaics (OPV) where a low‐cost OPV device can be integrated directly with a battery to provide a constant power source. We demonstrate ultra‐high voltage small molecule multijunction devices with open circuit voltage (V_OC) values of up to 7V. Optical modelling is employed to aid the optimisation of the complex multi‐layer stacks and ensure current balancing is achieved between sub‐cells, and optimised multijunction devices show power conversion efficiencies of up to 3.4% which is a modest increase over the single junction devices. Sub‐cell donor/acceptor pairs of boron subphthalocyanine chloride (SubPc)/fullerene (C₆₀) and SubPc/Cl₆‐SubPc were selected both for their high V_OC in order to minimise the required number of junctions, but also for their absorption overlap to reduce the spectral dependence of the device performance. As a result, the devices are shown to directly charge a micro‐energy cell type battery under both low illumination intensity white light and monochromatic illumination.     

Interface Design to Improve the Performance and Stability of Solution‐Processed Small‐Molecule Conventional Solar Cells

A systematic study on the effect of various cathode buffer layers on the performance and stability of solution‐processed small‐molecule organic solar cells (SMOSCs) based on tris{4‐[5‐(1,1‐dicyanobut‐1‐en‐2‐yl)‐2,2‐bithiophen‐5‐yl]phenyl}amine (N(Ph‐2T‐DCN‐Et)₃):6,6‐phenyl‐C71‐butyric acid methyl ester (N(Ph‐2T‐DCN‐Et)₃:PC₇₀BM) is presented. The power conversion efficiency (PCE) in these systems can be significantly improved from approximately 4% to 5.16% by inserting a metal oxide (ZnO) layer between the active layer and the Al cathode instead of an air‐sensitive Ba or Ca layer. However, the low work‐function Al cathode is susceptible to chemical oxidation in the atmosphere. Here, an amine group functionalized fullerene complex (DMAPA‐C₆₀) is inserted as a cathode buffer layer to successfully modify the interface towards ZnO/Ag and active layer/Ag functionality. For devices with ZnO/DMAPA‐C₆₀/Ag and DMAPA‐C₆₀/Ag cathodes the PCEs are improved from 2.75% to 4.31% and to 5.40%, respectively, compared to a ZnO/Ag device. Recombination mechanisms and stability aspects of devices with various cathodes are also investigated. The significant improvement in device performance and stability and the simplicity of fabrication by solution processing suggest this DMAPA‐C₆₀‐based interface as a promising and practical pathway for developing efficient, stable, and roll‐to‐roll processable SMOSCs.     

Cyclopenta[c]thiophene‐4,6‐dione‐Based Copolymers as Organic Photovoltaic Donor Materials

A class of “push‐pull” conjugated copolymers based on cyclopenta[c]thiophene‐4,6‐dione (CTD) and benzodithiophene (BDT) is synthesized for application as an electron donor in organic photovoltaics (OPV). Given the diverse electronic and structural tunability of the CTD unit, specific CTD‐containing copolymers are chosen with the aid of theoretical calculations from a broad array of potential candidate materials. Evaluation of the chosen materials as OPV absorbers includes characterization of the optical, electronic, and structural properties of the polymer films using UV‐vis absorbance, photoluminescence, cyclic voltammetry, and X‐ray diffraction techniques. In addition, the contactless time‐resolved microwave conductivity (TRMC) technique is used to measure the photoconductance of polymer/fullerene blends. Excellent correlation between measured photoconductance and OPV device efficiency is demonstrated with these materials and TRMC is discussed as a tool for screening potential active layer materials for OPV devices.     

Ambient Method for the Production of an Ionically Gated Carbon Nanotube Common Cathode in Tandem Organic Solar Cells

A method of fabricating organic photovoltaic (OPV) tandems that requires no vacuum processing is presented. These devices are comprised of two solution-processed polymeric cells connected in parallel by a transparent carbon nanotubes (CNT) interlayer. This structure includes improvements in fabrication techniques for tandem OPV devices. First the need for ambient-processed cathodes is considered. The CNT anode in the tandem device is tuned via ionic gating to become a common cathode. Ionic gating employs electric double layer charging to lower the work function of the CNT electrode. Secondly, the difficulty of sequentially stacking tandem layers by solution-processing is addressed. The devices are fabricated via solution and dry-lamination in ambient conditions with parallel processing steps. The method of fabricating the individual polymeric cells, the steps needed to laminate them together with a common CNT cathode, and then provide some representative results are described. These results demonstrate ionic gating of the CNT electrode to create a common cathode and addition of current and efficiency as a result of the lamination procedure.     

Porphyrin‐Based Bulk Heterojunction Organic Photovoltaics: The Rise of the Colors of Life

Organic photovoltaics (OPV) represent a thin‐film PV technology that offers attractive prospects for low‐cost and aesthetically appealing (colored, flexible, uniform, semitransparent) solar cells that are printable on large surfaces. In bulk heterojunction (BHJ) OPV devices, organic electron donor and acceptor molecules are intimately mixed within the photoactive layer. Since 2005, the power conversion efficiency of said devices has increased substantially due to insights in the underlying physical processes, device optimization, and chemical engineering of a vast number of novel light‐harvesting organic materials, either small molecules or conjugated polymers. As Nature itself has developed porphyrin chromophores for solar light to energy conversion, it seems reasonable to pursue artificial systems based on the same types of molecules. Porphyrins and their analogues have already been successfully implemented in certain device types, notably in dye‐sensitized solar cells, but they have remained largely unexplored in BHJ organic solar cells. Very recent successes do show, however, the strong (latent) prospects of porphyrinoid semiconductors as light‐harvesting and charge transporting materials in such devices. Here, an overview on the state‐of‐the‐art of porphyrin‐based solution‐processed BHJ OPV is provided and insights are given into the pathways to follow and hurdles to overcome toward further improvements of porphyrinic materials and devices.     

A Three-Dimensional Plasmonic Nanostructure with Extraordinary Optical Transmission

We report a 3D plasmonic nanostructure having an extraordinary optical transmission due to localized surface plasmon (LSP) coupling between nanoholes and nanodisks. The nanostructure contains a free-standing gold nanohole array (NHA) film above a cavity and an array of nanodisks at the bottom of the cavity that is aligned with the NHA. For the device, the LSP-mediated resonance position was dependent on the hole and nanodisk diameter as well as the separation distance. Also, the effect of LSP coupling between each hole and corresponding nanodisk became negligible for cavities deeper than 200 nm as observed as a disappearance of the LSP resonance. The greatest LSP resonance transmission and the highest electric field intensity were observed for the structure with the shallowest cavity. In addition, the structure had high surface plasmon resonance sensitivity and may have potential for surface-enhanced Raman spectroscopy and optical trapping applications.     

Perylene Sensitization of Fullerenes for Improved Performance in Organic Photovoltaics

We present the addition of an energy relay dye to fullerenes resulting in increased light harvesting and significantly improved power conversion efficiency for organic photovoltaic (OPV) devices. Although exhibiting excellent properties as electron acceptors, visible light absorption of fullerenes is limited. Strongly light absorbing donor materials are needed for efficient light harvesting in the thin active layer of OPV devices. Therefore, photocurrent generation and thus power conversion efficiency of this type of solar cell is confined by the overlap of the relatively narrow absorption band of commonly used donor molecules with the solar spectrum. Herein the concept of fullerene dye sensitization is presented, which allows increased light harvesting on the electron acceptor side of the heterojunction. The concept is exemplarily shown for an UV absorbing small molecule and a near infrared absorbing polymer, namely hexa‐peri‐hexabenzocoronene (HBC) and Poly[2,1,3‐benzothiadiazole‐4,7‐diyl[4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b']dithiophene‐2,6‐diyl]] (PCPDTBT), respectively. In both systems remarkably higher power conversion efficiency is achieved via perylene sensitization of the fullerene acceptor. Steady state photoluminescence, transient absorption and transient photocurrent decay studies reveal pathways of the additionally generated excited states at the sensitizer molecule. The findings suggest fluorescence resonance energy transfer from the photo‐excited dye to the fullerene enabling decoupling of light absorption and charge transport. The presented sensitization method is proposed as a viable new concept for performance enhancement in organic photovoltaic devices.     

Plasmon‐Active Nano‐Aperture Window Electrodes for Organic Photovoltaics

A lithography free approach to fabricating optically thin (～10 nm) noble metal electrodes with a dense array of sub‐wavelength apertures is reported. These nano‐structured electrodes support surface plasmon resonances which couple strongly with visible light concentrating it near to the electrode surface. They are also remarkably robust and can be fabricated on glass and plastic substrates with a sheet resistance of <15 Ω sq^?1. As the window electrode in solution processed and vacuum deposited organic photovoltaics (OPV) the photocurrent is increased by as much as 28% as compared to identical devices without apertures, demonstrating that the apertures do not need to have a tight size and/or shape distribution to be effective. As a drop‐in replacement for the indium‐tin oxide electrode in flexible OPV these plasmon‐active electrodes offer superior performance; 5.1% vs. 4.6%, demonstrating that this class of electrode is a truly viable alternative to conducting oxide window electrodes for OPV.     

High Performance Thick‐Film Nonfullerene Organic Solar Cells with Efficiency over 10% and Active Layer Thickness of 600 nm

Developing efficient organic solar cells (OSCs) with relatively thick active layer compatible with the roll to roll large area printing process is an inevitable requirement for the commercialization of this field. However, typical laboratory OSCs generally exhibit active layers with optimized thickness around 100 nm and very low thickness tolerance, which cannot be suitable for roll to roll process. In this work, high performance of thick‐film organic solar cells employing a nonfullerene acceptor F–2Cl and a polymer donor PM6 is demonstrated. High power conversion efficiencies (PCEs) of 13.80% in the inverted structure device and 12.83% in the conventional structure device are achieved under optimized conditions. PCE of 9.03% is obtained for the inverted device with active layer thickness of 500 nm. It is worth noting that the conventional structure device still maintains the PCE of over 10% when the film thickness of the active layer is 600 nm, which is the highest value for the NF‐OSCs with such a large active layer thickness. It is found that the performance difference between the thick active layer films based conventional and inverted devices is attributed to their different vertical phase separation in the active layers.     

Impact of Hole Transport Layer Surface Properties on the Morphology of a Polymer‐Fullerene Bulk Heterojunction

Investigations on the impact of interfacial modification on organic optoelectronic device performance often attribute the improved device performance to the optoelectronic properties of the modifier. A critical assumption of such conclusions is that the organic active layer deposited on top of the modified surface (interface) remains unaltered. Here the validity of this assumption is investigated by examining the impact of substrate surface properties on the morphology of poly(3‐hexylthiophene):1‐(3‐methoxycarbonyl)‐propyl‐1‐phenyl‐[6,6]C₆₁ (P3HT:PCBM) bulk‐heterojunction (BHJ). A set of four nickel oxide and poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) hole transport layers (HTL) with contrasting surface properties and performance in organic photovoltaic (OPV) devices is studied. Differences in vertical composition variation and structural morphologies are observed across the samples, but only in the near‐interface region of <～20 nm. Near‐interface differences in morphology are most closely correlated with surface polarity and surface roughness of the HTL. Surface polarity is more influenced by surface composition than surface roughness and crystal structure. These findings corroborate the previously mentioned conclusions that the differences in device performance observed in solar cells employing these HTLs are dominated by the electronic properties of the HTL/organic photoactive active layer interface and not by unintentional alteration in the BHJ active layer morphology.     

Nanofiber‐Based Bulk‐Heterojunction Organic Solar Cells Using Coaxial Electrospinning

Nanofibers consisting of the bulk heterojunction organic photovoltaic (BHJ–OPV) electron donor–electron acceptor pair poly(3‐hexylthiophene):phenyl‐C₆₁‐butyric acid methyl ester (P3HT:PCBM) are produced through a coaxial electrospinning process. While P3HT:PCBM blends are not directly electrospinnable, P3HT:PCBM‐containing fibers are produced in a coaxial fashion by utilizing polycaprolactone (PCL) as an electrospinnable sheath material. Pure P3HT:PCBM fibers are easily obtained after electrospinning by selectively removing the PCL sheath with cyclopentanone (average diameter 120 ± 30 nm). These fibers are then incorporated into the active layer of a BHJ–OPV device, which results in improved short‐circuit current densities, fill factors, and power‐conversion efficiencies (PCE) as compared to thin‐film devices of identical chemical composition. The best‐performing fiber‐based devices exhibit a PCE of 4.0%, while the best thin‐film devices have a PCE of 3.2%. This increase in device performance is attributed to the increased in‐plane alignment of P3HT polymer chains on the nanoscale, caused by the electrospun fibers, which leads to increased optical absorption and subsequent exciton generation. This methodology for improving device performance of BHJ–OPVs could also be implemented for other electron donor–electron acceptor systems, as nanofiber formation is largely independent of the PV material.     

Carrier‐Selectivity‐Dependent Charge Recombination Dynamics in Organic Photovoltaic Cells with a Ferroelectric Blend Interlayer

Interfacial energetics determines the performance of organic photovoltaic (OPV) cells based on a thin film of organic semiconductor blends. Here, an approach to modulating the “carrier selectivity” at the charge collecting interfaces and the consequent variations in the nongeminate charge carrier recombination dynamics in OPV devices are demonstrated. A ferroelectric blend interfacial layer composed of a solution‐processable ferroelectric poly­mer and a wide bandgap semiconductor is introduced as a tunable electron selective layer in inverted OPV devices with non‐Ohmic contact electrodes. The direct rendering of dipole alignment within the ferroelectric blend layer is found to increase the carrier selectivity of the charge collecting interfaces up to two orders of magnitude. Transient photovoltaic analyses reveal that the increase of carrier selectivity significantly reduces the diffusion and recombination among minority carriers in the vicinity of the electrodes, giving rise to the 85% increased charge carrier lifetime. Furthermore, the carrier‐selective charge extraction leads to the constitution of the internal potential within the devices, even with energetically identical cathodes and anodes. With these carrier‐selectivity‐controlled interlayers, the devices based on various photoactive materials commonly display significant increments in the device performances, especially with the high fill factor of up to 0.76 under optimized conditions.     

Gold Nanowire and Nanorod Plasmonic Mechanisms for Increasing Ultra-Thin Organic Photovoltaic Active Layer Absorption

We theoretically investigate the effect of incorporating gold cylindrical- and ellipsoidal-shaped nanowires and gold nanorods situated centrally within the active layer of organic bulk-heterojunction photovoltaic devices, on the optical absorption performance using finite element electromagnetic simulations. Gold cylindrical nanowire-embedded devices show increased active layer absorption enhancement with increasing radius; however, this effect decreases with the introduction of a polystyrene dielectric capping layer around the nanowires. Active layer absorption, with respect to changes in the orientation, aspect ratio, periodicity, and spacing between ellipsoidal nanowires were optimized. A maximum absorption enhancement weighted by AM 1.5 solar spectrum of 17 % is predicted for gold ellipsoidal nanowires of aspect ratio of 1.167 with in-plane horizontal orientation and arranged with periodicity of 35 nm within a 30-nm thin active layer. We attribute this enhancement primarily to interparticle electromagnetic coupling between adjacent nanowires, where, a maximum spatial and spectral overlap of the electromagnetic field with the absorption band of the active layer material is achieved. This effect increases with decreasing aspect ratio as well as decreasing periodicity with a trade-off observed between nanowire packing density and the active layer absorption enhancement. For gold nanorod-embedded organic photovoltaic devices, the inter-particle electromagnetic coupling effects are weaker and longitudinal surface–plasmon resonances supported by the nanorods are more pronounced. However, since the longitudinal surface–plasmon resonances occur at wavelengths greater than the absorption edge of the photovoltaic active layer, a mere 3.4 % increase in absorption enhancement is achieved for the photovoltaic device incorporating gold nanorods with aspect ratio of 1.167 and periodicity of 35 nm.     

A Simple Approach for Unraveling Optoelectronic Processes in Organic Solar Cells under Short-Circuit Conditions

The short-circuit current (J_sc) of organic solar cells is defined by the interplay of exciton photogeneration in the active layer, geminate and non-geminate recombination losses and free charge carrier extraction. The method proposed in this work allows the quantification of geminate recombination and the determination of the mobility-lifetime product (µτ) as a single integrated parameter for charge transport and non-geminate recombination. Furthermore, the extraction efficiency is quantified based on the obtained µτ product. Only readily available experimental methods (current-voltage characteristics, external quantum efficiency measurements) are employed, which are coupled with an optical transfer matrix method simulation. The required optical properties of common organic photovoltaic (OPV) materials are provided in this work. The new approach is applied to three OPV systems in inverted or conventional device structures, and the results are juxtaposed against the µτ values obtained by an independent method based on the voltage–capacitance spectroscopy technique. Furthermore, it is demonstrated that the new method can accurately predict the optimal active layer thickness.     

Enhanced Nucleation of Atomic Layer Deposited Contacts Improves Operational Stability of Perovskite Solar Cells in Air

Metal‐halide perovskites show promise as highly efficient solar cells, light‐emitting diodes, and other optoelectronic devices. Ensuring long‐term stability is now a major priority. In this study, an ultrathin (2 nm) layer of polyethylenimine ethoxylated (PEIE) is used to functionalize the surface of C₆₀ for the subsequent deposition of atomic layer deposition (ALD) SnO₂, a commonly used electron contact bilayer for p–i–n devices. The enhanced nucleation results in a more continuous initial ALD SnO₂ layer that exhibits superior barrier properties, protecting Cs_0.25FA_0.75Pb(Br_0.20I_0.80)₃ films upon direct exposure to high temperatures (200 °C) and water. This surface modification with PEIE translates to more stable solar cells under aggressive testing conditions in air at 60 °C under illumination. This type of “built‐in” barrier layer mitigates degradation pathways not addressed by external encapsulation, such as internal halide or metal diffusion, while maintaining high device efficiency up to 18.5%. This nucleation strategy is also extended to ALD VO_x films, demonstrating its potential to be broadly applied to other metal oxide contacts and device architectures.     

Low Substrate Temperature Encapsulation for Flexible Electrodes and Organic Photovoltaics

Encapsulation is of key importance to improve the stability and lifetime of organic conductors and devices, mainly in applications such as flexible electrodes or organic photovoltaics (OPV). Here, a single‐layer conformal encapsulation method is demonstrated via initiated chemical vapor deposition (iCVD) for organic conductor, poly (3,4‐ethylenedioxythiophene) (PEDOT). The accelerated degradation tests at 100 °C show that the conductivity of encapsulated PEDOT can be retained up to 17 times longer than that of the unencapsulated counterpart. PEDOT degradation and encapsulation mechanisms are also discussed. Furthermore, the versatility of the iCVD encapsulation on a top‐illuminated OPV architecture that can be used to produce low‐cost photovoltaics devices on various unconventional substrates (e.g., paper) is demonstrated. Unlike previous approaches of using solely water/oxygen barriers, the encapsulation effect of polymer films on OPV devices is improved by a thin layer capping of evaporated UV‐screening material, Cerium(IV) oxide (CeO₂) over the iCVD polymer layer. This bilayer encapsulation strategy efficiently slows the degradation of OPVs and represents a new method to encapsulate OPV and other organic devices.     

Atomic‐Layer‐Deposited Aluminum and Zirconium Oxides for Surface Passivation of TiO2 in High‐Efficiency Organic Photovoltaics

The reduction in electronic recombination losses by the passivation of surfaces is a key factor enabling high‐efficiency solar cells. Here a strategy to passivate surface trap states of TiO₂ films used as cathode interlayers in organic photovoltaics (OPVs) through applying alumina (Al₂O₃) or zirconia (ZrO₂) insulating nanolayers by thermal atomic layer deposition (ALD) is investigated. The results suggest that the surface traps in TiO₂ are oxygen vacancies, which cause undesirable recombination and high electron extraction barrier, reducing the open‐circuit voltage and the short‐circuit current of the complete OPV device. It is found that the ALD metal oxides enable excellent passivation of the TiO₂ surface followed by a downward shift of the conduction band minimum. OPV devices based on different photoactive layers and using the passivated TiO₂ electron extraction layers exhibit a significant enhancement of more than 30% in their power conversion efficiencies compared to their reference devices without the insulating metal oxide nanolayers. This is a result of significant suppression of charge recombination and enhanced electron extraction rates at the TiO₂/ALD metal oxide/organic interface.     

Optical Absorption Modeling of Plasmonic Organic Solar Cells Embedding Silica-Coated Silver Nanospheres

We numerically study plasmonic solar cells in which a square periodic array of core–shell Ag@SiO₂ nanospheres (NSs) are placed on top of the indium tin oxide (ITO) layer using a 3D finite-difference time-domain (FDTD) method. We investigate the influence of various parameters such as the periodicity of the array, the Ag core diameter, the active layer thickness, the shell thickness, and the refractive index of the shell materials on the optical performance of the organic solar cells (OSC). Our results show that the optimal periodicity of the array of NSs is dependent on the size of Ag core NSs in order to maximize optical absorption in the active layer. A very thin active layer (<70 nm) and an ultrathin (<5 nm) SiO₂ shell are needed in order to obtain the highest optical absorption enhancement. Strong electric field localization is observed around the plasmonic core–shell nanoparticles as a result of localized surface plasmon resonance (LSPR) excited by Ag NSs with and without silica shell. Embedding 50 nm Ag NSs with 1-nm-thick SiO₂ shell thickness on top of ITO leads to an enhanced intrinsic optical absorption in a 40-nm-thick poly(3-hexylthiophene):phenyl-C₆₁-butyric acid methyl ester (P3HT:PCBM) active layer by 24.7% relative to that without the NSs. The use of 1-nm-thick ZnO shell instead of SiO₂ leads to an enhanced intrinsic absorption in a 40-nm-thick P3HT:PCBM active layer by 27%.