Highly Efficient Indoor Organic Photovoltaics with Spectrally Matched Fluorinated Phenylene‐Alkoxybenzothiadiazole‐Based Wide Bandgap Polymers

The unique electro‐optical features of organic photovoltaics (OPVs) have led to their use in applications that focus on indoor energy harvesters. Various adoptable photoactive materials with distinct spectral absorption windows offer enormous potential for their use under various indoor light sources. An in‐depth study on the performance optimization of indoor OPVs is conducted using various photoactive materials with different spectral absorption ranges. Among the materials, the fluorinated phenylene‐alkoxybenzothiadiazole‐based wide bandgap polymer—poly[(5,6‐bis(2‐hexyldecyloxy)benzo[c][1,2,5]thiadiazole‐4,7‐diyl)‐alt‐(5,50‐(2,5‐difluoro‐1,4‐phenylene)bis(thiophen‐2‐yl))] (PDTBTBz‐2F_anti)‐contained photoactive layer—exhibits a superior spectrum matching with indoor lights, particularly a light‐emitting diode (LED), which results in an excellent power absorption ratio. These optical properties contribute to the state‐of‐the‐art performance of the PDTBTBz‐2F_anti:[6,6]‐phenyl‐C₇₁ butyric acid methyl ester (PC₇₁BM)‐based OPV with an unprecedented high power‐conversion efficiency (PCE) of 23.1% under a 1000 lx LED. Finally, its indoor photovoltaic performance is observed to be better than that of an interdigitated‐back‐contact‐based silicon photovoltaic (PCE of 16.3%).     

All‐Day Operating Quaternary Blend Organic Photovoltaics

The unique properties of organic photovoltaics (OPVs) offer great promise in emerging applications such as wearable electronics or the Internet of Things. For their successful utilization, OPV operation should be designed for versatile irradiation circumstances in addition to solar light since they should be capable of providing electric power when there is no sunlight or when they operate indoors. Here, a quaternary OPV (Q‐OPV) as a semitransparent, colorful energy platform that operates efficiently under both solar and artificial light irradiation is demonstrated. The experimentally optimized Q‐OPV shows a broadened spectral response and improved charge transport process with suppressed recombination, thereby providing high output powers that are sufficient to autonomously operate low‐power electronic devices. In addition, the Q‐OPV benefits from improved morphological stability with a reduced driving force for grain growth by the increased entropy in the quaternary blend system. The important features of the Q‐OPV platform such as semitransparency, high tolerance to film thickness, and color codability, while pursuing the improved performance and thermal durability, further open new opportunities as an all‐day (24/7/365) power generator in broad practical applications.     

Self‐Assembly of Selective Interfaces in Organic Photovoltaics

The composition of polymer‐fullerene blends is a critical parameter for achieving high efficiencies in bulk‐heterojunction (BHJ) organic photovoltaics. Achieving the “right” materials distribution is crucial for device optimization as it greatly influences charge‐carrier mobility. The effect of the vertical concentration profile of materials in spin‐coated BHJs on device properties has stirred particularly vigorous debate. Despite available literature on this subject, the results are often contradictory and inconsistent, likely due to differences in sample preparation and experimental considerations. To reconcile published results, the influence of heating, surface energy, and solvent additives on vertical segregation and doping in polymer‐fullerene BHJ organic photovoltaics are studied using neutron reflectometry and near edge X‐ray absorption fine structure spectroscopy. It is shown that surface energies and solvent additives greatly impact heat‐induced vertical segregation. Interface charging due to Fermi level mismatch increases (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM)‐enrichment at the BHJ/cathode interface. Current–voltage measurements show that self‐assembly of interfaces affects the open‐circuit voltage, resulting in clear changes to the power conversion efficiency.     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Durable Ultraflexible Organic Photovoltaics with Novel Metal‐Oxide‐Free Cathode

Flexible and stretchable organic photovoltaics (OPVs) are promising as a power source for wearable devices with multifunctions ranging from sensing to locomotion. Achieving mechanical robustness and high power conversion efficiency for ultraflexible OPVs is essential for their successful application. However, it is challenging to simultaneously achieve these features by the difficulty to maintain stable performance under a microscale bending radius. Ultraflexible OPVs are proposed by employing a novel metal‐oxide‐free cathode that consists of a printed ultrathin metallic transparent electrode and an organic electron transport layer to achieve high electron‐collecting capabilities and mechanical robustness. In fact, the proposed ultraflexible OPV achieves a power conversion efficiency of 9.7% and durability with 74% efficiency retention after 500 cycles of deformation at 37% compression through buckling. The proposed approach can be applied to active layers with different morphologies, thus suggesting its universality and potential for high‐performance ultraflexible OPV devices.     

Broadband Finite‐Difference Time‐Domain Modeling of Plasmonic Organic Photovoltaics

We develop accurate finite‐difference time‐domain (FDTD) modeling of polymer bulk heterojunction solar cells containing Ag nanoparticles between the hole‐transporting layer and the transparent conducting oxide‐coated glass substrate in the wavelength range of 300 nm to 800 nm. The Drude dispersion modeling technique is used to model the frequency dispersion behavior of Ag nanoparticles, the hole‐transporting layer, and indium tin oxide. The perfectly matched layer boundary condition is used for the top and bottom regions of the computational domain, and the periodic boundary condition is used for the lateral regions of the same domain. The developed FDTD modeling is employed to investigate the effect of geometrical parameters of Ag nanospheres on electromagnetic fields in devices. Although negative plasmonic effects are observed in the considered device, absorption enhancement can be achieved when favorable geometrical parameters are obtained.     

Organic Bulk‐Heterojunction Photovoltaics Based on Alkyl Substituted Discotics

The photovoltaic behavior of three hexa‐peri‐hexabenzocoronene (HBC) derivatives has been investigated with respect to the influence of the alkyl side chains. Upon increasing the side chain length, the HBC chromophore becomes diluted, thus decreasing the amount of light absorbed. Differential scanning calorimetry and powder X‐ray analysis reveal that the HBC with the 2‐ethyl‐hexyl side chain is in a crystalline state at room temperature, while the other two HBCs containing 2‐hexyl‐decyl and 2‐decyl‐tetradecyl substituents in so‐called plastic crystalline state. The HBC with the shortest side chain is proven to be the best donor for perylenediimide, showing a highest external quantum efficiency of 12 %. Furthermore, scanning electron microscopy imaging suggested an important role of the morphology of the active film in determining the performance of the device.     

Reticulated Organic Photovoltaics

This paper shows how the self‐assembled interlocking of two nanostructured materials can lead to increased photovoltaic performance. A detailed picture of the reticulated 6‐DBTTC/C₆₀ organic photovoltaic (OPV) heterojunction, which produces devices approaching the theoretical maximum for these materials, is presented from near edge X‐ray absorption spectroscopy (NEXAFS), X‐ray photoelectron spectroscopy (XPS), Grazing Incidence X‐ray diffraction (GIXD) and transmission electron microscopy (TEM). The complementary suite of techniques shows how self‐assembly can be exploited to engineer the interface and morphology between the cables of donor (6‐DBTTC) material and a polycrystalline acceptor (C₆₀) to create an interpenetrating network of pure phases expected to be optimal for OPV device design. Moreover, we find that there is also a structural and electronic interaction between the two materials at the molecular interface. The data show how molecular self‐assembly can facilitate 3‐D nanostructured photovoltaic cells that are made with the simplicity and control of bilayer device fabrication. The significant improvement in photovoltaic performance of the reticulated heterojunction over the flat analog highlights the potential of these strategies to improve the efficiency of organic solar cells.     

A Versatile Self‐Organization Printing Method for Simplified Tandem Organic Photovoltaics

Despite recent dramatic enhancements in power conversion efficiencies (PCEs) resulting in values over 10%, the manufacturing of tandem organic solar cells (OSCs) via current printing technologies is subject to tremendous challenges. Existing complicated tandem structures consisting of six or more component layers have been a major obstacle that significantly increases the complexity of printing processes and substantially sacrifices the PCE for printed devices. Here, an innovative printing method is reported that simplifies the fabrication process of the tandem OSCs. By developing a new printing technique using a nanocomposites containing interfacial and photoactive materials, a simultaneously printed bilayer of consisting of interfacial and photoactive layers, achieved through vertical self‐organization, is successfully demonstrated, resulting in tandem OSCs with only four printed layers. Moreover, by rigorously controlling the molecular weight of the interfacial materials, the self‐assembly characteristics are improved and an efficient tandem OSC is yielded with a PCE of 9.1% achieved in printed layers.     

Boron Subphthalocyanine Chloride as an Electron Acceptor for High‐Voltage Fullerene‐Free Organic Photovoltaics

High‐efficiency fullerene‐free single‐heterojunction (SHJ) organic photovoltaic (OPV) cells consisting of tetracene (Tc) as a typical donor material and boron subphthalocyanine chloride (SubPc) as an acceptor material are reported. Cells containing SubPc as a direct replacement for C₆₀ exhibit an ～60% improvement in open circuit voltage (V_oc) achieving a maximum V_oc of 1.24 V, which is amongst the highest values acheived to date for SHJ devices. This resulted in an overall improvement of ～60% in power conversion efficiency from 1.8%, for Tc/C₆₀ cells, to 2.9% for Tc/SubPc. The OPV device results are complemented by soft X–ray photoelectron spectroscopy (PES) measurements of the interfacial energetics of both systems. The results demonstrate that SubPc shows considerable promise as an electron acceptor material for future cell designs.     

Trap‐Assisted Recombination via Integer Charge Transfer States in Organic Bulk Heterojunction Photovoltaics

Organic photovoltaics are under intense development and significant focus has been placed on tuning the donor ionization potential and acceptor electron affinity to optimize open circuit voltage. Here, it is shown that for a series of regioregular‐poly(3‐hexylthiophene):fullerene bulk heterojunction (BHJ) organic photovoltaic devices with pinned electrodes, integer charge transfer states present in the dark and created as a consequence of Fermi level equilibrium at BHJ have a profound effect on open circuit voltage. The integer charge transfer state formation causes vacuum level misalignment that yields a roughly constant effective donor ionization potential to acceptor electron affinity energy difference at the donor–acceptor interface, even though there is a large variation in electron affinity for the fullerene series. The large variation in open circuit voltage for the corresponding device series instead is found to be a consequence of trap‐assisted recombination via integer charge transfer states. Based on the results, novel design rules for optimizing open circuit voltage and performance of organic bulk heterojunction solar cells are proposed.     

Organic N‐Type Molecule: Managing the Electronic States of Bulk Perovskite for High‐Performance Photovoltaics

The power conversion efficiency (PCE) of planar p–i–n perovskite solar cells (pero‐SCs) is commonly lower than that of the n–i–p pero‐SCs, due to the severe nonradiative recombination stemming from the more p‐type perovskite with prevailing electron traps. Here, two n‐type organic molecules, DMBI‐2‐Th and DMBI‐2‐Th‐I, with hydrogen‐transfer properties for the doping of bulk perovskite aimed at regulating its electronic states are synthesized. The generated radicals in these n‐type dopants with high‐lying singly occupied molecular orbitals enable easy transfer of the thermally activated electrons to the MAPbI₃ perovskite for the realization of n‐doped perovskites. The n‐doping degree could be further enhanced by using the iodine ionized dopant DMBI‐2‐Th‐I. The doping effect could reduce the electron trap density, increase the electron concentration of the bulk perovskite, and simultaneously improve the surface electronic contact. When the DMBI‐2‐Th‐I‐doped perovskite is used in planar p–i–n pero‐SCs, the nonradiative recombination is significantly suppressed. As a result, the photovoltaic performance improved significantly, as evidenced by an excellent PCE of 20.90% and a robust ambient stability even under high relative humidity. To the best of the knowledge, this work represents the first example where organic n‐type dopants are used to tune the electronic states of a bulk perovskite film for efficient planar p–i–n pero‐SCs.     

Photoconductivity of C60 as an Origin of Bias‐Dependent Photocurrent in Organic Photovoltaics

The bulk‐ionized photoconductivity of C₆₀ is reported as an origin of the bias‐dependent linear change of the photocurrent in copper phthalocyanine (CuPc)/C₆₀ planar heterojunction solar cells, based on the observation of the variation of the bias‐dependent photocurrent on excitation wavelengths and the thickness‐dependent photocurrent of the C₆₀ layer. A theoretical model, which is a combination of the Braun‐Onsager model for the dissociation of excitons at the donor/acceptor interface and the Onsager model for the bulk ionization of excitons in the C₆₀ layer, describes the bias‐dependent photocurrent in the devices very well. The bulk‐ionized photoconductivity of C₆₀ must generally contribute to the photocurrent in organic photovoltaics, since fullerene and fullerene derivatives are widely used in these devices.     

Microcavity Structure Provides High‐Performance (>8.1%) Semitransparent and Colorful Organic Photovoltaics

High‐performance colored aesthetic semitransparent organic photovoltaics (OPVs) featuring a silver/indium tin oxide/silver (Ag/ITO/Ag) microcavity structure are prepared. By precisely controlling the thickness of the ITO layer, OPV devices exhibiting high transparency and a wide and high‐purity color gamut are obtained: blue ( B ), green ( G ), yellow‐green ( YG ), yellow ( Y ), orange ( O ), and red ( R ). The power conversion efficiencies (PCEs) of the G , YG , and Y color devices are greater than 8% (AM 1.5G irradiation, 100 mW cm^?2) with maximum transmittances (T_MAX) of greater than 14.5%. An optimized PCE of 8.2% was obtained for the YG OPV [CIE 1931 coordinates: (0.364, 0.542)], with a value of T_MAX of 17.3% (at 561 nm). As far as it is known, this performance is the highest ever reported for a transparent colorful OPV. Such high transparency and desired transmitted colors, which can perspective see the clear images, suggest great potential for use in building‐integrated photovoltaic applications.     

Poly(3‐hexylthiophene) Nanorods with Aligned Chain Orientation for Organic Photovoltaics

A structured polymer solar cell architecture featuring a large interface between donor and acceptor with connecting paths to the respective electrodes is explored. To this end, poly‐(3‐hexylthiophene) (P3HT) nanorods oriented perpendicularly to indium tin oxide (ITO) glass are fabricated using an anodic aluminum oxide template. It is found that the P3HT chains in bulk films or nanorods are oriented differently; perpendicular or parallel to the ITO substrate, respectively. Such chain alignment of the P3HT nanorods enhanced the electrical conductivity up to tenfold compared with planar P3HT films. Furthermore, the donor/acceptor contact area could be maximised using P3HT nanorods as donor and C60 as acceptor. In a photovoltaic device employing this structure, remarkable photoluminescence quenching (88%) and a seven‐fold efficiency increase (relative to a device with a planar bilayer) are achieved.     

Solution‐Processable Ultrathin Black Phosphorus as an Effective Electron Transport Layer in Organic Photovoltaics

2D van der Waals crystals, possessing excellent electronic and physical properties, have been intriguing building blocks for organic optoelectronic devices. Most of the 2D materials are served as hole transport layers in organic devices. Here,it is reported that solution exfoliated few layers black phosphorus (BP) can be served as an effective electron transport layer (ETL) in organic photovoltaics (OPVs) for the first time. The power conversion efficiencies (PCEs) of the BP‐incorporated OPVs can be improved to 8.18% in average with the relative enhancement of 11%. The incorporation of BP flakes with the optimum thickness of ≈10 nm can form cascaded band structure in OPVs, which can facilitate electron transport and enhance the PCEs of the devices. This study opens an avenue in using solution exfoliated BP as a highly efficient ETL for organic optoelectronics.     

Lending Triarylphosphine Oxide to Phenanthroline: a Facile Approach to High‐Performance Organic Small‐Molecule Cathode Interfacial Material for Organic Photovoltaics utilizing Air‐Stable Cathodes

Cathode interfacial material (CIM) is critical to improving the power conversion efficiency (PCE) and long‐term stability of an organic photovoltaic cell that utilizes a high work function cathode. In this contribution, a novel CIM is reported through an effective and yet simple combination of triarylphosphine oxide with a 1,10‐phenanthrolinyl unit. The resulting CIM possesses easy synthesis and purification, a high T _g of 116 °C and attractive electron‐transport properties. The characterization of photovoltaic devices involving Ag or Al cathodes shows that this thermally deposited interlayer can considerably improve the PCE, due largely to a simultaneous increase in V _oc and FF relative to the reference devices without a CIM. Notably, a PCE of 7.51% is obtained for the CIM/Ag device utilizing the active layer PTB7:PC₇₁BM, which far exceeds that of the reference Ag device and compares well to that of the Ca/Al device. The PCE is further increased to 8.56% for the CIM/Al device (with J _sc = 16.81 mA cm^?2, V _oc = 0.75 V, FF = 0.68). Ultraviolet photoemission spectroscopy studies reveal that this promising CIM can significantly lower the work function of the Ag metal as well as ITO and HOPG, and facilitate electron extraction in OPV devices.     

Ultrathin Transparent Au Electrodes for Organic Photovoltaics Fabricated Using a Mixed Mono‐Molecular Nucleation Layer

A rapid, solvent free method for the fabrication of highly transparent ultrathin (～8 nm) Au films on glass has been developed. This is achieved by derivatizing the glass surface with a mixed monolayer of 3‐mercaptopropyl(trim­ethoxysilane) and 3‐aminopropyl(trimethoxysilane) via co‐deposition from the vapor phase, prior to Au deposition by thermal evaporation. The mixed mono­layer modifies the growth kinetics, producing highly conductive films (～11 Ω per square) with a remarkably low root‐mean‐square roughness (～0.4 nm) that are exceptionally robust towards UV/O₃ treatment and ultrasonic agitation in a range of common solvents. As such, they are potentially widely applicable for a variety of large area applications, particularly where stable, chemically well‐defined, ultrasmooth substrate electrodes are required, such as in organic optoelectronics and the emerging fields of nanoelectronics and nanophotonics. By integrating microsphere lithography into the fabrication process, we also demonstrate a means of tuning the transparency by incorporating a random array of circular apertures into the film. The application of these nanostructured Au electrodes is demonstrated in efficient organic photovoltaic devices where it offers a compelling alternative to indium tin oxide coated glass.