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The distinction of different organic materials in phase mixtures is hampered in electron microscopy because electron scattering does not strongly differ in carbon-based materials that mainly consist of light elements. A successful strategy for contrast enhancement is selective staining where one phase of a material mixture is labeled by heavier elements, but suitable staining agents are not available for all organic materials. This is also the case for bulk-heterojunction (BHJ) absorber layers of organic solar cells, which consist of interpenetrating networks of donor and acceptor domains. The domain structure strongly influences the power conversion efficiency, and nanomorphology optimization often requires real-space information on the sizes and interconnectivity of domains with nanometer resolution. In this work, we have developed an efficient approach to selectively stain sulfur-containing polymers by homogeneous Cu infiltration, which generates strong material contrast in scanning (transmission) electron microscopy (S(T)EM) images of polymer:fullerene BHJ layers. Cross-section lamellae of BHJ layers are prepared for STEM by focused-ion-beam milling and are attached to a Cu lift-out grid as a copper source. After thermal treatment at 200 °C for 3 h in air, sulfur-containing polymers are homogeneously infiltrated by Cu, while the fullerenes are not affected. Selective Cu staining is applied to map the phase distribution in PTB7:PC71BM BHJ layers fabricated with different processing additives to tailor the nanomorphology. The strong contrast between polymer and fullerene domains is the prerequisite for the three-dimensional reconstruction of the domain structure by focused-ion-beam/scanning-electron-microscopy tomography.

Future low‐cost, high‐throughput production of organic solar cells in roll‐to‐roll printing processes calls for all‐solution‐processable device architectures. Mechanical flexibility and robustness are mandatory to roll the solar foils during printing and to eventually comply with certain end‐user requirements. Here, we report on semitransparent organic solar cells, comprising top and bottom silver nanowire (AgNW) electrodes that were embedded into conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The devices exhibited excellent robustness in bending experiments with radii of 5 and 2.5 mm as well as upon folding. To avoid short circuits from nanowires that could stick out of the bottom electrodes, the PEDOT:PSS:AgNW layers were flattened by hot‐pressing after deposition. All solar cells were fabricated in air by doctor blading and exhibited a clear (haze‐free) transparency due to the absence of bus bars. On photoactive areas of 0.5 cm2, power conversion efficiencies of 3.8 % were obtained. Just what the doctor‐blade ordered: All‐doctor‐bladed semitransparent organic solar cells were fabricated on mechanically flexible PET substrates in air using environmentally benign solvents. Dispersions from conductive polymers and silver nanowires as bottom and top electrode were integrated into a printable, robust, four‐layer solar cell architecture. Solar cells with photoactive areas of 0.5 cm2yielded high power conversion efficiencies with a visible light transmission of 25 %.

This work analyzes in detail the effect of ferroelectric polarization patterns in methylammonium lead iodide (MAPbI3) thin-films on the J-V characteristics of the corresponding solar cells. The simulations are based on a finite-element discretization of the drift-diffusion equations and take into account the polarization pattern experimentally derived from piezoresponse force micrographs. Based on the knowledge of the crystalline structure, symmetry considerations and electrical simulations, we discuss models for the polarization orientation pattern and magnitude of the ferroelectric domains. We conclude that the in-plane polarization vectors have 45° orientation towards the domain walls and form herring-bone structures. The presence of ordered ferroelectric domains, even with a weak characteristic polarization magnitude enhances the power conversion efficiencies and are mandatory to reproduce the experimental J-V characteristics.

Nanoparticle dispersions open up an ecofriendly route toward printable organic solar cells. They can be formed from a variety of organic semiconductors by using miniemulsions that employ surfactants to stabilize the nanoparticles in dispersion and to prevent aggregation. However, whenever surfactant-based nanoparticle dispersions have been used to fabricate solar cells, the reported performances remain moderate. In contrast, solar cells from nanoparticle dispersions formed by precipitation (without surfactants) can exhibit power conversion efficiencies close to those of state-of-the-art solar cells processed from blend solutions using chlorinated solvents. In this work, we use small-angle neutron scattering measurements and transient absorption spectroscopy to investigate why surfactant-free nanoparticles give rise to efficient organic solar cells. We show that surfactant-free nanoparticles comprise a uniform distribution of small semiconductor domains, similar to that of bulk-heterojunction films formed using traditional solvent processing. This observation differs from surfactant-based miniemulsion nanoparticles that typically exhibit core–shell structures. Hence, the surfactant-free nanoparticles already possess the optimum morphology for efficient energy conversion before they are assembled into the photoactive layer of a solar cell. This structural property underpins the superior performance of the solar cells containing surfactant-free nanoparticles and is an important design criterion for future nanoparticle inks.

We report on solution‐processed, semitransparent organic solar cells that are implemented as lenses in sunglasses. The electrical power provided by the lens‐fitted solar cells sustains a microelectronic circuit that is used to read out temperature and illumination intensity sensors and to make this information available on two displays integrated into the temples of the “Solar Glasses”. The microelectronic circuit is designed to operate at illumination intensities down to 500 lux, rendering the Solar Glasses suitable for outdoor and indoor use as well as for operation in diffuse light. Hence, this case study provides an example for consumer‐oriented mobile applications, self‐powered by integrated solar cells, which specifically exploit the unique properties of organic solar cells. Solar Glasses: Toned lenses of sunglasses were replaced with semitransparent organic solar cells. Even in low light, the power sustained a micro‐electronic circuit and two displays, demonstrating the potential of organic solar cells in mobile consumer applications.

The plethora of design opportunities renders organic light emitting diodes (OLEDs) ideal luminaires for general lighting applications. Progressing from lab-scale device concepts to large-area applications calls for smart device designs that are scalable and, at the same time, unsusceptible to resistive losses within the electrodes. By employing direct pulsed femtosecond laser structuring, we fabricate OLED luminaires comprising monolithically interconnected OLED arrays. We determine the laser ablation thresholds and the optimized process parameters for all functional layers. The clean laser cuts with precise ablation depths show no detectable damage to adjacent layers or any ridges, hence avoiding unwanted short-cuts or device isolation. All processes are scalable. The 3-fold structuring of the OLED luminaire is confined within 45 μm and hence below the resolution limit of the human eye, yielding a geometric fill factor beyond 99% and therefore a very homogeneous device perception.

For future integration into building facades or overhead glazing, the direct deposition of organic solar modules on glass substrates in sheet‐to‐sheet processes may be more cost efficient than postproduction lamination. Complying with the special requirements for the deposition of the layer stack on glass substrates, we report on all‐doctor‐bladed organic solar modules yielding power conversion efficiencies of 4.5 and 3.6 % on photoactive areas of 1 and 20 cm2, respectively. The bottom electrode is doctor bladed from a silver ink atop an adhesion enhancing primer. The top electrode is applied from silver nanowires, dispersed in poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), which thereby avoids any visible bus bars and reduces shading of the active layer. Importantly, all layers are deposited under ambient conditions by using only non‐chlorinated, eco‐compatible solvents. Printable solar modules: All‐doctor‐bladed organic solar modules are fabricated in air by using eco‐compatible solvents. Opaque silver cathodes and transparent conductive polymer anodes are employed. Solar modules with photoactive areas of 20 cm2yield power conversion efficiencies of 3.6 %.

Tandem organic light emitting diodes (OLEDs) utilizing fluorescent polymers in both sub-OLEDs and a regular device architecture were fabricated from solution, and their structure and performance characterized. The charge carrier generation layer comprised a zinc oxide layer, modified by a polyethylenimine interface dipole, for electron injection and either MoO3, WO3, or VOxfor hole injection into the adjacent sub-OLEDs. ToF-SIMS investigations and STEM-EDX mapping verified the distinct functional layers throughout the layer stack. At a given device current density, the current efficiencies of both sub-OLEDs add up to a maximum of 25 cd/A, indicating a properly working tandem OLED.

The morphology of the active layer in organic photovoltaics (OPVs) is of crucial importance as it greatly influences charge generation and transport. A templating interlayer between the electrode and the active layer can change active layer morphology and influence the domain orientation. A series of amphiphilic interface modifiers (IMs) combining a hydrophilic polyethylene-glycol (PEG) oligomer and a hydrophobic hexabenzocoronene (HBC) were designed to be soluble in PEDOT:PSS solutions, and surface accumulate on drying. These IMs are able to self-assemble in solution. When IMs are deposited on top of a poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) film, they induce a morphology change of the active layer consisting of discotic fluorenyl-substituted HBC (FHBC) and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). However, when only small amounts (0.2 wt %) of IMs are blended into PEDOT:PSS, a profound change of the active layer morphology is also observed. Morphology changes were monitored by grazing incidence wide-angle X-ray scattering (GIWAXS), transmission electron microscopy (TEM), TEM tomography, and low-energy high-angle angular dark-field scanning transmission electron microscopy (HAADF STEM). The interface modification resulted in a 20% enhancement of power conversion efficiency.

In this study, the nanomorphology of fluorenyl hexa-peri-hexabenzocoronene:[6,6]-phenyl C61-butyric acid methyl ester (FHBC:PC61BM) absorber layers of organic solar cells was investigated. Different electron microscopical techniques, atomic force microscopy, and grazing incidence wide-angle X-ray scattering were applied for a comprehensive nanomorphology analysis. The development of the nanomorphology upon sample annealing and the associated change of the device performance were investigated. It was shown that the annealing process enhances the phase separation and therefore the bulk heterojunction structure. Due to π–π stacking, the FHBC molecules assemble into columnar stacks, which are already present before annealing. While the nonannealed sample consists of a mixture of homogeneously distributed PC61BM molecules and FHBC stacks with a preferential in-plane stack orientation, crystalline FHBC precipitates occur in the annealed samples. These crystals, which consist of hexagonal arranged FHBC stacks, grow with increased annealing time. They are distributed homogeneously over the whole volume of the absorber layer as revealed by electron tomography. The FHBC stacks, whether in the two phase mixture or in the pure crystalline precipitates, exhibit an edge-on orientation, according to results from grazing incidence wide-angle X-ray scattering (GIWAXS), dark-field transmission electron microscopy (DF TEM) imaging and selective area electron diffraction (SAED). The best solar cell efficiencies were obtained after 20 or 40 s sample annealing. These annealing times induce an optimized degree of phase separation between donor and acceptor material.

The efficiency of thin-film solar cells with large optical band gaps, such as organic bulk heterojunction or amorphous silicon solar cells, is limited by their inability to harvest the (infra)red part of the solar spectrum. Photochemical upconversion based on triplet–triplet annihilation (TTA-UC) can potentially boost those solar cells by absorbing sub-bandgap photons and coupling the upconverted light back into the solar cell in a spectral region that the cell can efficiently convert into electrical current. In the present study we augment two types of organic solar cells and one amorphous silicon (a-Si:H) solar cell with a TTA-upconverter, demonstrating a solar cell photocurrent increase of up to 0.2% under a moderate concentration (19 suns). The behavior of the organic solar cells, whose augmentation with an upconverting device is so-far unreported, is discussed in comparison to a-Si:H solar cells. Furthermore, on the basis of the TTA rate equations and optical simulations, we assess the potential of TTA-UC augmented solar cells and highlight a strategy for the realization of a device-relevant current increase by TTA-upconversion.

In the past, benzotriazole acceptor units have been incorporated successfully into donor–acceptor polymers for highly efficient photovoltaic devices. Here, we explore 2-phenyl-2H-benzotriazole oligomers as model systems for donor–acceptor polymers. We designed and synthesized acceptor–donor–acceptor oligomers incorporating 2-phenyl-2H-benzotriazole acceptor and naphthodithiophene donor units. Supported by quantum chemical calculations we investigated the optoelectronic properties, such as electronic levels and intramolecular charge transfer, by means of optical and fluorescence spectroscopy. We built bulk-heterojunction solar cells comprising these oligomers and [6,6]-phenyl C61-butyric acid methyl ester. In doing so, the film-forming conditions were optimized as the absorber layer morphology is strongly affected by the deposition conditions, in particular drying time and drying temperature.

The efficiency of organic bulk heterojunction solar cells strongly depends on the multiscale morphology of the interpenetrating polymer–fullerene network. Understanding the molecular assembly and the identification of influencing parameters is essential for a systematic optimization of such devices. Here, we investigate the molecular ordering during the drying of doctor-bladed polymer–fullerene blends on PEDOT:PSS-coated substrates simultaneously using in situgrazing incidence X-ray diffraction (GIXD) and laser reflectometry. In the process of blend crystallization, we observe the nucleation of well-aligned P3HT crystallites in edge-on orientation at the interface at the instant when P3HT solubility is crossed. A comparison of the real-time GIXD study at ternary blends with the binary phase diagrams of the drying blend film gives evidence of strong polymer–fullerene interactions that impede the crystal growth of PCBM, resulting in the aggregation of PCBM in the final drying stage. A systematic dependence of the film roughness on the drying time after crossing P3HT solubility has been shown. The highest efficiencies have been observed for slow drying at low temperatures which showed the strongest P3HT interchain π–π-ordering along the substrate surface. By adding the “unfriendly” solvent cyclohexanone to a chlorobenzene solution of P3HT:PCBM, the solubility can be crossed prior to the drying process. Such solutions exhibit randomly orientated crystalline structures in the freshly cast film which results in a large crystalline orientation distribution in the dry film that has been shown to be beneficial for solar cell performance.

Summary:Monodisperse oligophenothiazines are rapidly synthesized in good yields by use of Suzuki arylation. These well defined oligomers reveal both highly fluorescence and low oxidation potentials. As a consequence of intense electronic coupling as supported by cyclic voltammetry a selected trimer shows hole‐transport properties in a hole‐conductor‐only set‐up of a diode with relatively low on‐set voltage.

Due to their high transparency, electrodes fabricated from conductive polymers are often implemented in semitransparent organic solar cells. Opaque solar cells usually employ metal back electrodes with high reflectivity for best photon confinement in the light‐harvesting layer. Herein, a bilayer back electrode comprising conductive polymers and nanofoamed poly(methyl methacrylate) (PMMA) is investigated, the latter of which creates diffuse reflection of the incoming light. By tuning the thickness of the nanofoamed PMMA layer, absorption and transmission of the solar cells can be tailored from opaque to vastly transparent. Due to its diffusive character, this versatile electrode enhances the light absorption in the wavelength regimes with lower absorption coefficient. The solar cells are particularly suited for deployment in frosted window applications. A bilayer polymer electrode comprising conductive polymers and supercritical nanofoamed poly(methyl methacrylate) (PMMA) is applied to organic solar cells. Gas inclusions inside the PMMA act as light‐scattering centers. By adjusting the thickness of the nanofoamed layer, the performance and translucency of the solar cell can be tailored. The logo is reproduced with permission from Karlsruhe Institute of Technology.

Bulk-heterojunction nanoparticle dispersions in water or alcohol can be employed as eco-friendly inks for the fabrication of organic solar cells by printing or coating. However, one major drawback is the need for stabilizing surfactants, which facilitate nanoparticle formation but later hamper device performance. When surfactant-free dispersions are formulated, a strong limitation is imposed by the dispersion concentration due to the tendency of nanoparticles to aggregate. In this work, pyridine end-capped poly(3-hexylthiophene) (P3HT-Py) is synthesized and included as an additive for the stabilization of P3HT:indene-C60bis-adduct (ICBA) nanoparticle dispersions. In the presence of acetic acid (AcOH), a surface-active pyridinium acetate end-capped P3HT ion pair, P3HT-PyH+AcO–, is formed which effectively stabilizes the dispersion and hence allows the formation of dispersions with smaller nanoparticle sizes and higher concentrations of up to 30 mg/mL in methanol. The dispersions exhibit an enhanced shelf-lifetime of at least 60 days at room temperature. After the deposition of light-harvesting layers from the nanoparticle dispersions, the ion-pair formation is reversed at elevated temperatures leading to regeneration of P3HT-Py and AcOH. The AcOH evaporates from the active layer, while the performance of the corresponding solar cells is not affected by the residual P3HT-Py in the devices. Enhanced nanoparticle stability is achieved with only 0.017 wt % pyridine in the P3HT/ICBA formulation.

The microstructure of absorber layers is pivotally important for all thin‐film solar technologies. Using electron backscattered diffraction (EBSD), the crystal orientation in methylammonium lead iodide thin films with submicrometer resolution is reported. For the vast majority of (110) oriented grains, the c‐axis of the perovskite unit cell is oriented in‐plane. Although some adjacent grains exhibit the same in‐plane horizontal orientation of the c‐axis, no universal horizontal orientation of the c‐axis within the sample plane exists. The (110) crystal orientation correlates with an in‐plane orientation of the ferroelectric polarization as investigated by vertical and lateral piezoresponse force microscopy (PFM). The individual grains with different crystal orientations that exhibit different ferroelectric patterns and surface potentials are identified. The strong correlation between crystal orientation and ferroelectric polarization allows conclusions to be drawn about the microstructure from PFM measurements and, likewise, the ferroelectric polarization to be derived from crystallographic observations by EBSD. The spatially resolved correlation of electron backscattered diffraction and piezoresponse force microscopy data provides insight into the microstructure of methylammonium lead iodide thin films that are commonly incorporated into perovskite solar cells.

Solar Glasses: The clear view through lens‐fitted solar cells of smart glasses exemplifies the outstanding properties of organic solar cells. Their color, shape, and transparency can be tailored to match the specific requirements of self‐sustaining future mobile applications. Even under low light conditions, here down to 500 Lux, they still provide sufficient power output to operate a microcontroller and two liquid crystal displays integrated into the temples of the glasses. This work from Alexander Colsmann′s group at Karlsruhe Institute of Technology describes the Solar Glasses in detail and provides a fresh view on how organic solar cells may enable new applications. More details can be found in the Full Paper by Dominik Landerer et al. on page 1936 in Issue 11, 2017(10.1002/ente.201700226).