Geminate and Nongeminate Pathways for Triplet Exciton Formation in Organic Solar Cells

Abstract: Organic solar cells (OSCs) have recently shown a rapid improvement in their performance, bringing power conversion efficiencies to above 18%. However, the open‐circuit voltage of OSCs remains low relative to their optical gap and this currently limits efficiency. Recombination to spin‐triplet excitons is a key contributing factor, and is widely, but not universally, observed in donor–acceptor blends using both fullerene and nonfullerenes as electron acceptors. Here, an experimental framework that combines time‐resolved optical and magnetic resonance spectroscopies to detect triplet excitons and identify their formation mechanisms, is reported. The methodology is applied to two well‐studied polymer:fullerene systems, PM6:PC60BM and PTB7‐Th:PC60BM. In contrast to the more efficient nonfullerene acceptor systems that show only triplet states formed via nongeminate recombination, the fullerene systems also show significant triplet formation via geminate processes. This requires that geminate electron–hole pairs be trapped long enough to allow intersystem crossing. It is proposed that this is a general feature of fullerene acceptor systems, where isolated fullerenes are known to intercalate within the alkyl sidechains of the donor polymers. Thus, the study demonstrates that engineering good donor and acceptor domain purity is key for suppressing losses via triplet excitons in OSCs

Direct observation and evolution of electronic coupling between organic semiconductors

The electronic wave functions of an atom or molecule are affected by its interactions with its environment. These interactions dictate electronic and optical processes at interfaces, and is especially relevant in the case of thin film optoelectronic devices such as organic solar cells. In these devices, charge transport and interfaces between multiple layers occur along the thickness or vertical direction, and thus such electronic interactions between different molecules—same or different—are crucial in determining the device properties. Here, we introduce an in situ spectroscopic ellipsometry data analysis method called differential analysis in real time (DART) with the ability to directly probe electronic coupling due to intermolecular interactions along the thickness direction using vacuum-deposited organic semiconductor thin films as a model system. The analysis, which does not require any model fitting, reveals direct observations of electronic coupling between frontier orbitals under optical excitations leading to delocalization of the corresponding electronic wave functions with thickness or, equivalently, number of molecules away from the interface in C60 and MeO-TPD deposited on an insulating substrate ( Si O 2 ) . Applying the same methodology for C60 deposited on phthalocyanine thin films, the analyses shows strong, anomalous features—in comparison to C60 deposited on Si O 2 —of the electronic wave functions corresponding to specific excitation energies in C60 and phthalocyanines. Translation of such interactions in terms of dielectric constants reveals plasmonic type resonance absorptions resulting from oscillations of the excited state wave functions between the two materials across the interface. Finally, reproducibility, angstrom-level sensitivity, and simplicity of the method are highlighted showcasing its applicability for studying electronic coupling between any vapor-deposited material systems where real-time measurements during thin film growth are possible

Optimizing the morphology of metal multilayer films for indium tin oxide (ITO)-free inverted organic solar cells

We present metal multilayers consisting of aluminum and silver in different combinations serving as semitransparent top contacts for organic solar cells. Scanning electron microscopy, atomic force microscopy, and optical spectroscopy are used to illustrate how ultrathin Al interlayers influence the morphology of Ag layers evaporated on top of organic materials and how closed layers with good conductivity can be achieved. Multilayer metal contacts are used to fabricate top-illuminated small-molecule organic solar cells (SM-OSCs) which reach efficiencies comparable to conventional SM-OSCs that employ tin-doped indium oxide as electrode. It is shown that combinations of Al and Au lead to similar results, suggesting a similar mechanism for the influence on morphological development of both Ag and Au. © 2009 American Institute of Physics

Improved photocurrent by using n-doped 2,3,8,9,14,15-hexachloro-5,6,11,12, 17,18-hexaazatrinaphthylene as optical spacer layer in p-i-n type organic solar cells

We introduce 2,3,8,9,14,15-hexachloro-5,6,11,12,17,18-hexaazatrinaphthylene (HATNA-Cl6) as n-dopable electron transport material (ETM) for small molecule organic solar cells. Because of its large optical energy gap of 2.7 eV and its well suited energy level positions, the material can be implemented as a semitransparent spacer layer between the reflecting metal contact and the photoactive C60 acceptor layer in p-i-n type solar cells. By varying the ETM thickness, it is possible to shift the position of the photoactive area with respect to the interference maximum of the optical field distribution. Applying n-HATNA-Cl6 instead of the parasitically absorbing reference ETM n-C60 results in a considerably improved photocurrent density and accordingly in a higher efficiency. At dETM = 100 nm the power conversion efficiency is more than doubled as it increases from (100 nm n-C60) = 0.5% to (100 nm n-HATNA-Cl6) = 1.1%. © 2011 American Institute of Physics.</p

Towards efficient tin-doped indium oxide (ITO)-free inverted organic solar cells using metal cathodes

We present zinc phthalocyanine (ZnPc): C60 bulk-heterojunction top-illuminated organic solar cells using ultrathin metal layers as transparent top contacts. We show that solar cell performance sensitively depends on the interface and morphology of the cathode, which can be influenced by varying the composition and layer structure of the metal contact. We investigate various metal combinations, such as 3 nm Al/8 nm Ag and 7 nm Al/14 nm Ag, to illustrate the necessity to find a suitable combination of morphology and electrical and optical properties. Solar cells using standard materials and a 1 nm Al/14 nm Ag cathode exhibit promising efficiencies of over 2.2%. © 2009 American Institute of Physics.</em

Highly doped layers as efficient electron-hole recombination contacts for tandem organic solar cells

A key feature of stacked organic solar cells is an efficient recombination contact at the interface between the solar cells in the stack. Here, an electron current has to be converted into a hole current without loss of energy. Furthermore, the recombination contact has to be highly transparent. We present a new approach for small molecule organic solar cells using highly doped organic layers. Our approach adapts the use of tunnel diodes known from inorganic tandem solar cells. We compare a metal cluster based recombination contact reported in literature to the new approach using different organic tandem solar cell structures. For this purpose, current-voltage characteristics of adequate solar cells are measured. The experiments show that highly doped layers as recombination contacts in tandem organic solar cells are superior to the metal cluster based approach. The proposed concept allows an addition of the open circuit voltages of the subcells of a tandem solar cell, without absorption or reflection at the recombination contact. The results further show that our concept does not depend on the specific choice of materials as it is seen for metal cluster based recombination contacts. It therefore represents a general approach which is compatible to mass manufacturing. © 2010 American Institute of Physics

Perspectives of organic and perovskite‐based spintronics

Spin-related phenomena in optoelectronic materials can revolutionize several technological applications in the areas of data processing and storage, quantum computing, lighting, energy harvesting, sensing, and healthcare. A fundamental boost to this promising field can be envisaged thanks to the use of two emerging materials, which have recently been receiving increasing scientific attention: organic semiconductors (OSCs) and halide perovskites (HPs). Here, the first progress in the resulting fields, organic- and perovskite-based spintronics, is reviewed, which will enable the manipulation of spin, charges, and photons in spin/optoelectronic devices. A link between these two classes of materials is created by highlighting the pros and cons of each technology, and their potential applications in new multifunctional spintronic devices are discussed. Current challenges in the field are also outlined, and convenient approaches to overcome them are proposed

Improved light harvesting in tin-doped indum oxide (ITO)-free inverted bulk-heterojunction organic solar cells using capping layers

We show that ultrathin metal layers (Ag or Al/Ag) are feasible as transparent top contacts for zinc phthalocyanine: C60 bulk-heterojunction inverted organic solar cells thermally evaporated on glass substrates. Furthermore, it is demonstrated that the introduction of an organic capping layer drastically increases light incoupling and photon harvesting, in accordance with optical simulations. Proof of principle tin-doped indium oxide (ITO)-free solar cells employing a transparent metal contact and a capping layer reach efficiencies of 1.06%, compared to 0.69% without addition of the capping layer. © 2008 American Institute of Physics.</p

Femtosecond dynamics of photoexcited C60 films

The well-known organic semiconductor C60 is attracting renewed attention due to its centimetre-long electron diffusion length and high performance of solar cells containing 95% fullerene. Yet, its photophysical properties remain poorly understood. Here, we elucidate the dynamics of Frenkel and intermolecular (inter- C60) charge transfer (CT) excitons in neat and diluted C60 films from high quality femtosecond transient absorption (TA) measurements, performed at low fluences and free from oxygen or pump-induced photo-dimerization. We find from preferential excitation of either species that the CT excitons give rise to a strong electro-absorption signal but are extremely short-lived. The Frenkel exciton relaxation and triplet yield depend strongly on the C60 aggregation. Finally, TA measurements on full devices with applied electric field allow us to optically monitor the dissociation of CT excitons into free charges for the first time and to demonstrate the influence of cluster size on the spectral signature of the C60 anion

Organic solar cells with inverted layer sequence incorporating optical spacers - Simulation and experiment

In this paper we present detailed optical simulations of organic bulk-heteroj unction solar cells built with inverted layer sequence as compared to the commonly used setup which is based on indium tin oxide (ITO) covered glass or plastic substrates and where the metal electrode is evaporated on top of the active absorber blend. The inverted setup may have production related advantages over the conventional setup, as the metal electrode is first evaporated onto the substrate and afterwards only wet chemical processes are needed. Additionally ITO can be replaced with a suited module concept. The effects of light trapping with an optical spacer, namely a transparent conductive layer between the absorber and the metallic electrode are investigated for the inverted setup. The results show that the insertion of an optical spacer does not increase the maximal obtainable short circuit current density and is only beneficial if a decrease of film thickness of the active absorber results in a higher internal quantum efficiency, open circuit voltage or fill factor. In the experimental section we show that the inversion of the layer sequence can be realised without any loss in device efficiency as compared to devices with the conventional layer sequence