• Atomic-layer-deposited aluminum and zirconium oxides for surface passivation of TiO 2 in High-Efficiency Organic Photovoltaics

      Vasilopoulou, Maria; Georgiadou, Dimitra G.; Soultati, Anastasia; Boukos, Nikos; Gardelis, Spyros; Palilis, Leonidas C.; Fakis, Mihalis; Skoulatakis, Georgios; Kennou, Stella; Botzakaki, Martha A.; et al. (Wiley, 2014-06-23)
      The reduction in electronic recombination losses by the passivation of surfaces is a key factor enabling high-efficiency solar cells. Here we investigate a strategy to passivate surface trap states of TiO 2 films used as cathode interlayers in organic photovoltaics (OPVs) through applying alumina (Al2O3) or zirconia (ZrO2) insulating nanolayers by thermal atomic layer deposition (ALD). Our results suggest that the surface traps in TiO 2 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 was 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 exhibited a significant enhancement of more than 30% in their power conversion efficiencies (PCEs) as compared to their reference devices without the insulating metal oxide nanolayers as a result of significant suppression of charge recombination and enhanced electron extraction rates at the TiO2/ALD metal-oxide/organic interface.
    • Avoiding ambient air and light induced degradation in high-efficiency polymer solar cells by the use of hydrogen-doped zinc oxide as electron extraction material

      Polydorou, Ermioni; Sakelis, Elias; Soultati, Anastasia; Kaltzoglou, Andreas; Papadopoulos, Theodoros A.; Briscoe, Joe; Tsikritzis, Dimitris; Fakis, Mihalis; Palilis, Leonidas C.; Kennou, Stella; et al. (Elsevier, 2017-02-24)
      Polymer solar cells have undergone rapid development in recent years. Their limited stability to environmental influence and during illumination, however, still remains a major stumbling block to the commercial application of this technology. Several attempts have been made to address the instability issue, mostly concentrated on the insertion of charge transport interlayers in the device stack. Although zinc oxide (ZnO) is one of the most common electron transport materials in those cells, the presence of defects at the surface and grain boundaries significantly affects the efficiency and stability of the working devices. To address these issues, we herein employ hydrogen-doping of ZnO electron extraction material. It is found that devices based on photoactive layers composed of blends of poly(3-hexylthiophene) (P3HT) with electron acceptors possessing different energy levels, such as [6,6]-phenyl-C70butyric acid methyl ester (PC70BM) or indene-C60 bisadduct (IC60BA) essentially enhanced their photovoltaic performance when using the hydrogen-doped ZnO with maximum power conversion efficiency (PCE) reaching values of 4.62% and 6.65%, respectively, which are much higher than those of the cells with the pristine ZnO (3.08% and 4.51%). Most significantly, the degradation of non-encapsulated solar cells when exposed to ambient or under prolonged illumination is studied and it is found that devices based on un-doped ZnO showed poor environmental stability and significant photo-degradation while those using hydrogen-doped ZnO interlayers exhibited high long-term ambient stability and maintained nearly 80–90% of their initial PCE values after 40 h of 1.5 AM illumination. All mechanisms responsible for this enhanced stability are elucidated and corresponding models are proposed. This work successfully addresses and tackles the instability problem of polymer solar cells and the key findings pave the way for the upscaling of these and, perhaps, of related devices such as perovskite solar cells.
    • Computational benchmarking for ultrafast electron dynamics: wavefunction methods vs density functional theory

      Oliveira, Micael J. T.; Mignolet, Benoit; Kus, Tomasz; Papadopoulos, Theodoros A.; Remacle, Francoise; Verstraete, Matthieu J.; University of Chester (American Chemical Society, 2015-05-12)
      Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrodinger equation based on the correlated field-free stationary electronic states computed with the equation-of-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TD-DFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.
    • Control of the dipole layer of polar organic molecules adsorbed on metal surfaces via different charge-transfer channels

      Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Su, Kai-Jun; Wang, Chin-Yung; Pi, Tun-Wen; Metz, Sebastian; Papadopoulos, Theodoros A.; Chiang, Tai-Chang; Ishii, Hisao; et al. (American Physical Society, 2017-02-17)
      Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MES) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and post annealing conditions; the ELA at the interface differs by ~0.4 eV between the Cl-up and -down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density-functional-theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework towards method development for ELA tuning.
    • The effect of irradiation impinging on disparate anchoring configurations of polar-organic molecules adsorbed on bulk and thin-film metal surfaces

      Papadopoulos, Theodoros A.; Metz, Sebastian; Tang, Shu-Jung; University of Chester; Daresbury Laboratory; National Tsing-Hua University (Elsevier, 2019-07-11)
      The behavior of polar metal organic molecules, chloroaluminum phthalocyanine (ClAlPc), upon ultraviolet (UV) irradiation was investigated to evaluate the stability of the adsorption process on the Ag(111) thin film and bulk crystal. Angle-resolved photoelectron spectroscopy (ARPES) was mainly employed to measure the molecular energy states (MES) and vacuum level (VL) shift for 1-ML ClAlPc in the Cl-down configuration. A consistent trend was observed showing that ClAlPc in the Cl-down configuration is energetically more stable on the Ag thin-film surface than on the corresponding surface of the Ag bulk crystal. The intermediate adsorption state in tilted configuration during the irradiation impinging is identified by large positive VL shifts and broad spectra line shapes to infer a flipping mechanism from Cl-down to Cl-up configuration. Strain on the Ag thin films from the underlying mismatched Ge(111) substrate is considered to cause enlarged hollow sites on the Ag(111) thin-films, that anchor the Cl-down configuration more tightly on the thin-film surfaces, as confirmed by density functional theory (DFT) calculations.
    • Energetic fluctuations in amorphous semiconducting polymers: Impact on charge-carrier mobility

      Manjoj Gali, Sai; D'Avino, Gabriele; Aurel, Philippe; Han, Guangchao; Yi, Yuanping; Papadopoulos, Theodoros A.; Coropceanu, Veaceslav; Brédas, Jean-Luc; Hadziiannou, Georges; Muccioli, Luca; et al. (American Institute of Physics, 2017-10-03)
      We present a computational approach to model hole transport in an amorphous semiconducting fluorene-triphenylamine copolymer (TFB), which is based on the combination of molecular dynamics to predict the morphology of the oligomeric system and Kinetic Monte Carlo (KMC), parameterized with quantum chemistry calculations, to simulate hole transport. Carrying out a systematic comparison with available experimental results, we discuss the role that different transport parameters play in the KMC simulation and in particular the dynamic nature of positional and energetic disorder on the temperature and electric field dependence of charge mobility. It emerges that a semi-quantitative agreement with experiments is found only when the dynamic nature of the disorder is taken into account. This study establishes a clear link between microscopic quantities and macroscopic hole mobility for TFB and provides substantial evidence of the importance of incorporating fluctuations, at the molecular level, to obtain results that are in good agreement with temperature and electric field-dependent experimental mobilities. Our work makes a step forward towards the application of nanoscale theoretical schemes as a tool for predictive material screening.
    • Impact of Functionalized Polystyrenes as the Electron Injection Layer on Gold and Aluminum Surfaces: A Combined Theoretical and Experimental Study

      Papadopoulos, Theodoros A.; Li, Hong; Kim, Eung-Gun; Liu, Jie; Cella, James A.; Heller, Christian M.; Shu, Andrew; Kahn, Antoine; Duggal, Anil; Brédas, Jean-Luc; et al. (Wiley, 2014-06-06)
      At metal/organic interfaces, insertion of an organic monolayer can significantly modify the surface properties of the substrate, especially in terms of charge injection across the interface. Here, we study the formation of an insulating monolayer of morpholine or amine-functionalized polystyrene on Al(111) and Au(111) surfaces and its impact on surface work-function and charge injection. First principles calculations based on density functional theory have been carried out and point to a significant decrease of the work-function for the modified metal surfaces, in very good agreement with ultraviolet photoemission spectroscopy measurements performed on the Au(111) surface. In addition, a bilayer cathode consisting of a thin film of high work-function metal, such as Al and Au, and a layer of amine-functionalized polystyrene is also fabricated and tested in organic light-emitting diodes. Such bilayer structures exhibit substantially enhanced efficiency when compared to controls without the functionalized polymers. Our combined theoretical and experimental investigation gives insight into how a thin layer of a commodity polymer can be used to transform rather high work-function metals into high-performance cathodes providing efficient electron injection.
    • Improved Stability of Polymer Solar Cells in Ambient Air via Atomic Layer Deposition of Ultra-Thin Dielectric Layers

      Polydorou, Ermioni; Botzakaki, Martha A.; Sakellis, Ilias; Soultati, Anastasia; Kaltzoglou, Andreas; Papadopoulos, Theodoros A.; Briscoe, Joe; Drivas, Charalabos; Seintis, Kostas; Fakis, Mihalis; et al. (Wiley, 2017-07-12)
      Polymer solar cells have attracted tremendous interest in the highly competitive solar energy sector, due to the practical advantages they exhibit, such as being lightweight, flexible, and low cost, in stark contrast to traditional photovoltaic technologies. However, their successful commercialization is still hindered by issues related to device instability. Here, atomic layer deposition (ALD) is employed to deposit conformal ultrathin dielectrics, such as alumina (Al2O3) and zirconia (ZrO2), on top of ZnO electron extraction layers to address problems that arise from the defect-rich nature of these layers. The deposition of dielectrics on ZnO significantly improves its interfacial electronic properties, manifested primarily with the decrease in the work function of ZnO and the concomitant reduction of the electron extraction barrier as well as the reduced recombination losses. Significant efficiency enhancement is obtained with the incorporation of six ALD cycles of Al2O3 into inverted devices, using photoactive layers, that consist of poly(3-hexylthiophene):indene-C60-bisadduct or poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b] thiophenediyl}):[6,6]-phenyl-C70-butyric acid methyl ester. More importantly, upon performing lifetime studies (over a period of 350 h), a strong improvement in polymer solar cell stability is observed when using the ALD-modified ZnO films.
    • In-depth synthetic, physicochemical and in vitro biological investigation of a new ternary V(IV) antioxidant material based on curcumin.

      Papadopoulos, Theodoros A.; Smith, Graham C.; Halevas, Eleftherios; Salifoglou, Athanasios; Swanson, Claudia H.; Hatzidimitriou, Antonios; Katsipis, George; Pantazaki, Anastasia; Sanakis, I.; Mitrikas, George; et al. (Elsevier, 2018-11-06)
      Curcumin is a natural product with a broad spectrum of beneficial properties relating to pharmaceutical applications, extending from traditional remedies to modern cosmetics. The biological activity of such pigments, however, is limited by their solubility and bioavailability, thereby necessitating new ways of achieving optimal tissue cellular response and efficacy as drugs. Metal ion complexation provides a significant route toward improvement of curcumin stability and biological activity, with vanadium being a representative such metal ion, amply encountered in biological systems and exhibiting exogenous bioactivity through potential pharmaceuticals. Driven by the need to optimally increase curcumin bioavailability and bioactivity through complexation, synthetic efforts were launched to seek out stable species, ultimately leading to the synthesis and isolation of a new ternary V(IV)-curcumin-(2,2’-bipyridine) complex. Physicochemical characterization (elemental analysis, FT-IR, Thermogravimetry (TGA), UV-Visible, NMR, ESI-MS, Fluorescence, X-rays) portrayed the solid-state and solution properties of the ternary complex. Pulsed-EPR spectroscopy, in frozen solutions, suggested the presence of two species, cis- and trans-conformers. Density Functional Theory (DFT) calculations revealed the salient features and energetics of the two conformers, thereby complementing EPR spectroscopy. The well-described profile of the vanadium species led to its in vitro biological investigation involving toxicity, cell metabolism inhibition in S. cerevisiae cultures, Reactive Oxygen Species (ROS)-suppressing capacity, lipid peroxidation, and plasmid DNA degradation. A multitude of bio-assays and methodologies, in comparison to free curcumin, showed that it exhibits its antioxidant potential in a concentration-dependent fashion, thereby formulating a bioreactivity profile supporting development of new efficient vanado-pharmaceuticals, targeting (extra)intra-cellular processes under (patho)physiological conditions.
    • Low Work Function Lacunary Polyoxometalates as Electron Transport Interlayers for Inverted Polymer Solar Cells of Improved Efficiency and Stability

      Tountas, Marinos; Topal, Yasemin; Polydorou, Ermioni; Soultati, Anastasia; Verykios, Apostolos; Kaltzoglou, Andreas; Papadopoulos, Theodoros A.; Auras, Florian; Seintis, Konstantinos; Fakis, Mihalis; et al. (American Chemical Society, 2017-06-06)
      Effective interface engineering has been shown to play a vital role in facilitating efficient charge-carrier transport, thus boosting the performance of organic photovoltaic devices. Herein, we employ water-soluble lacunary polyoxometalates (POMs) as multifunctional interlayers between the titanium dioxide (TiO2) electron extraction/transport layer and the organic photoactive film to simultaneously enhance the efficiency, lifetime, and photostability of polymer solar cells (PSCs). A significant reduction in the work function (WF) of TiO2 upon POM utilization was observed, with the magnitude being controlled by the negative charge of the anion and the selection of the addenda atom (W or Mo). By inserting a POM interlayer with ∼10 nm thickness into the device structure, a significant improvement in the power conversion efficiency was obtained; the optimized POM-modified poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2- 33 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]:[6,6]-phenyl-C70 butyric acid methyl ester (PTB7:PC70BM)-based PSCs exhibited an efficiency of 8.07%, which represents a 21% efficiency enhancement compared to the reference TiO2 cell. Similar results were obtained in POM-modified devices based on poly(3-hexylthiophene) (P3HT) with electron acceptors of different energy levels, such as PC70BM or indene-C60 bisadduct (IC60BA), which enhanced their efficiency up to 4.34 and 6.21%, respectively, when using POM interlayers; this represents a 25–33% improvement as compared to the reference cells. Moreover, increased lifetime under ambient air and improved photostability under constant illumination were observed in POM-modified devices. Detailed analysis shows that the improvements in efficiency and stability synergistically stem from the reduced work function of TiO2 upon POM coverage, the improved nanomorphology of the photoactive blend, the reduced interfacial recombination losses, the superior electron transfer, and the more effective exciton dissociation at the photoactive layer/POM/TiO2 interfaces.
    • A Silanol-Functionalized Polyoxometalate with Excellent Electron Transfer Mediating Behavior to ZnO and TiO 2 Cathode Interlayers for Highly Efficient and Extremely Stable Polymer Solar Cells

      Tountas, Marinos; Topal, Yasemin; Verykios, Apostolos; Soultati, Anastasia; Kaltzoglou, Andreas; Papadopoulos, Theodoros A.; Auras, Florian; Seintis, Kostas; Fakis, Mihalis; Palilis, Leonidas C.; et al. (Royal Society of Chemistry, 2017-12-21)
      Combining high efficiency and long lifetime under ambient conditions still poses a major challenge towards commercialization of polymer solar cells. Here we report a facile strategy that can simultaneously enhance the efficiency and temporal stability of inverted photovoltaic architectures. Inclusion of a silanol-functionalized organic–inorganic hybrid polyoxometalate derived from a PW9O34 lacunary phosphotungstate anion, namely (nBu4N)3[PW9O34(tBuSiOH)3], significantly increases the effectiveness of the electron collecting interface, which consists of a metal oxide such as titanium dioxide or zinc oxide, and leads to a high efficiency of 6.51% for single-junction structures based on poly(3-hexylthiophene):indene-C60 bisadduct (P3HT:IC60BA) blends. The above favourable outcome stems from a large decrease in the work function, an effective surface passivation and a decrease in the surface energy of metal oxides which synergistically result in the outstanding electron transfer mediating capability of the functionalized polyoxometalate. In addition, the insertion of a silanol-functionalized polyoxometalate layer significantly enhances the ambient stability of unencapsulated devices which retain nearly 90% of their original efficiencies (T90) after 1000 hours.
    • Surface passivation effect by fluorine plasma treatment on ZnO for efficiency and lifetime improvement of inverted polymer solar cells

      Polydorou, Ermioni; Zeniou, Angelos; Tsikritzis, Dimitris; Soultati, Anastasia; Sakellis, Ilias; Gardelis, Spyros; Papadopoulos, Theodoros A.; Briscoe, Joe; Palilis, Leonidas C.; Kennou, Stella; et al. (Royal Society of Chemistry, 2016-06-24)
      Zinc oxide (ZnO) is an important material for polymer solar cells (PSCs) where the characteristics of the interface can dominate both the efficiency and lifetime of the device. In this work we study the effect of fluorine (SF6) plasma surface treatment of ZnO films on the performance of PSCs with an inverted structure. The interaction between fluorine species present in the SF6 plasma and the ZnO surface is also investigated in detail. We provide fundamental insights into the passivation effect of fluorine by analyzing our experimental results and theoretical calculations and we propose a mechanism according to which a fluorine atom substitutes an oxygen atom or occupies an oxygen vacancy site eliminating an electron trap while it may also attract hydrogen atoms thus favoring hydrogen doping. These multiple fluorine roles can reduce both the recombination losses and the electron extraction barrier at the ZnO/fullerene interface improving the selectivity of the cathode contact. Therefore, the fabricated devices using the fluorine plasma treated ZnO show high efficiency and stable characteristics, irrespective of the donor : acceptor combinations in the photoactive blend. Inverted polymer solar cells, consisting of the P3HT:PC71BM blend, exhibited increased lifetime and high power conversion efficiency (PCE) of 4.6%, while the ones with the PCDTBT:PC71BM blend exhibited a PCE of 6.9%. Our champion devices with the PTB7:PC71BM blends reached a high PCE of 8.0% and simultaneously showed exceptional environmental stability when using the fluorine passivated ZnO cathode interlayers.