Molecular Electronic Coupling Controls Charge Recombination Kinetics in Organic Solar Cells of Low Bandgap Diketopyrrolopyrrole, Carbazole, and Thiophene Polymers

Low-bandgap diketopyrrolopyrrole- and carbazole-based polymer bulk-heterojunction, solar cells exhibit much faster charge carrier recombination kinetics than that encountered for less-recombining poly(3-hexylthiophene). Solar cells comprising these polymers exhibit energy losses caused by carrier recombination of approximately 100 mV, expressed as reduction in open-circuit voltage, and consequently photovoltaic conversion efficiency lowers in more than 20%. The analysis presented here unravels the origin of that energy loss by connecting the limiting mechanism governing recombination dynamics to the electronic coupling occurring at the donor polymer and acceptor fullerene interfaces. Previous approaches correlate carrier transport properties and recombination kinetics by means of Langevin-like mechanisms. However, neither carrier mobility nor polymer ionization energy helps understanding the variation of the recombination coefficient among the studied polymers In the framework of the charge transfer Marcus theory, it is proposed that recombination time scale is linked with charge transfer molecular mechanisms at,the polymer/fullerene interfaces. As expected for efficient organic solar cells, small electronic coupling existing between donor polymers and acceptor fullerene (V-if < 1 meV) and large reorganization energy (lambda approximate to 0.7 eV) are encountered. Differences in the electronic coupling among polymer/fullerene blends suffice to explain the slowest recombination exhibited by poly(3-hexylthiophene)-based solar, cells. Our approach reveals how to directly connect photovoltaic parameters. as open circuit voltage to molecular properties of blended materials.This work was partially supported by FP7 European Collaborative Project SUNFLOWER (FP7-ICT-2011-7, Contract No. 287594), Ministerio de Educacion y Ciencia (Spain), under Project HOPE CSD2007-00007 (Consolider-Ingenio 2010), and Generalitat Valenciana (Prometeo/2009/058 and ISIC/2012/008 Institute of Nanotechnologies for Clean Energies)

Transition metal speciation as a degradation mechanism with the formation of a solid-electrolyte interphase (SEI) in Ni-rich transition metal oxide cathodes

An ever-growing demand for high-energy density and high-power Li-ion batteries has driven active research for electrode materials with superior capacity. Recent years have seen the development of Ni-rich transition metal oxide cathode materials due to their high reversible capacity and lower cost. To achieve full capacity from the charge compensation process, a high voltage (>4.4 V) charging is required. However, the battery operation at higher voltages eventually results in dramatic capacity fading and voltage decay with a rapid decomposition of the electrolyte upon further charge-discharge. While previous studies have reported the degradation mechanism within the electrode surface, there have been few empirical investigations into the solid-electrolyte interphase (SEI) formation on Ni-rich cathodes. In the current work, we visualize the different nature of the electrode-electrolyte interphase at various cut-off voltages (2.0-4.2 V, 2.0-4.5 V, and 2.0-4.8 V). We correlate the key properties of the SEI layer with the capacity fading mechanism in the high capacity battery system. The speciation of transition metal elements (Ni, Mn, and Co) into various oxidation and spin states has been identified as the dominant process of the capacity degradation

Enhanced diffusion through porous nanoparticle optical multilayers

Herein we demonstrate improved mass transport through nanoparticle one-dimensional photonic crystals of enhanced porosity. Analysis is made by impedance spectroscopy using iodine and ionic liquid based electrolytes and shows that newly created large pores and increased porosity improve the diffusion of species through the photonic crystal. This achievement is based on the use of a polymeric porogen (polyethylene glycol), which is mixed with the precursor suspensions used for the deposition of nanoparticle TiO2 and SiO2 layers and then eliminated to generate a more open interconnected void network, as confirmed by specular reflectance porosimetry . A compromise between pore size and optical quality of these periodic structures is found.España Ministerio de Ciencia e Innovación MAT2008-02166 MAT2011-23593Junta de Andalucía FQM3579 FQM5247CONSOLIDER HOPE CSD2007-0000

Can Laminated Carbon Challenge Gold? Toward Universal, Scalable, and Low-Cost Carbon Electrodes for Perovskite Solar Cells

While perovskite solar cell (PSC) efficiencies are soaring at a laboratory scale, these are most commonly achieved with evaporated gold electrodes, which would present a significant expense in large-scale production. This can be remedied through the use of significantly cheaper carbon electrodes that, in contrast to metals, also do not migrate through the device. To this end, the present work investigates simple-to-prepare aluminum-supported carbon electrodes derived from commercially available, inexpensive materials that can be applied onto various hole-transporting materials and enable photovoltaic performances on par with those provided by gold electrodes. Successful integration of the new carbon-based electrode into flexible devices produced by a roll-to-roll printing technology by both pressing and lamination is demonstrated. However, temperature cycling durability tests reveal that the use of carbon electrodes based on commercial pastes is hindered by incompatibility of adhesive additives with the key components of the PSCs under heating. Resolving this issue, tailor-made graphite electrodes devoid of damaging additives are introduced, which improve the PSC stability under temperature cycling test protocol to the level provided by benchmark gold electrodes. The study highlights current challenges in developing laminated carbon electrodes in PSCs and proposes strategies toward the resolution thereof.This work was funded by the Australian Centre for Advanced Photovoltaics and Australian Renewable Energy Agency. A.N.S. also acknowledges the financial support from the Australian Research Council (Centre of Excellence CE140100012; Future Fellowship FT200100317). Monash Centre for Electron Microscopy (MCEM) and Melbourne Centre for Nano fabrication (MCN) are acknowledged for providing access to their facilities. The authors are grateful to Dr T. Zhang, A. Surmiak, Dr. N. Peris, Dr. D. Senevirathna, and Dr. N. Pai from Monash University for the experimental support throughout this study

Interfacial Modification of Perovskite Solar Cells Using an Ultrathin MAI Layer Leads to Enhanced Energy Level Alignment, Efficiencies, and Reproducibility

For the first time, we intentionally deposit an ultrathin layer of excess methylammonium iodide (MAI) on top of a methylammonium lead iodide (MAPI) perovskite film. Using photoelectron spectroscopy, we investigate the role of excess MAI at the interface between perovskite and spiro-MeOTAD hole-transport layer in standard structure perovskite solar cells (PSCs). We found that interfacial, favorable, energy-level tuning of the MAPI film can be achieved by controlling the amount of excess MAI on top of the MAPI film. Our XPS results reveal that MAI dissociates at low thicknesses (<16 nm) when deposited on MAPbI3. It is not the MAI layer but the dissociated species that leads to the interfacial energy-level tuning. Optimized interface energetics were verified by solar cell device testing, leading to both an increase of 19% in average steady-state power conversion efficiency (PCE) and significantly improved reproducibility, which is represented by a much lower PCE standard deviation (from 15 +/- 2% to 17.2 +/- 0.4%

Design and characterization of alkoxy-wrapped push–pull porphyrins for dye-sensitized solar cells

Three alkoxy-wrapped push–pull porphyrins were designed and synthesized for dye-sensitized solar cell (DSSC) applications. Spectral, electrochemical, photovoltaic and electrochemical impedance spectroscopy properties of these porphyrin sensitizers were well investigated to provide evidence for the molecular desig

Solution processable direct bandgap copper-silver-bismuth iodide photovoltaics : compositional control of dimensionality and optoelectronic properties

Altres ajuts: SRR acknowledges the support from "laCaixa" Foundation (ID 100010434; LCF/BQ/PI20/11760024). Open access publishing facilitated by Monash University, as part of the Wiley - Monash University agreement via the Council of Australian University Librarians.The search for lead-free alternatives to lead-halide perovskite photovoltaic materials resulted in the discovery of copper(I)-silver(I)-bismuth(III) halides exhibiting promising properties for optoelectronic applications. The present work demonstrates a solution-based synthesis of uniform CuAgBiI thin films and scrutinizes the effects of x on the phase composition, dimensionality, optoelectronic properties, and photovoltaic performance. Formation of pure 3D CuAgBiI at x = 1, 2D CuAgBiI at x = 2, and a mix of the two at 1 < x < 2 is demonstrated. Despite lower structural dimensionality, CuAgBiI has broader optical absorption with a direct bandgap of 1.89 ± 0.05 eV, a valence band level at -5.25 eV, improved carrier lifetime, and higher recombination resistance as compared to CuAgBiI. These differences are mirrored in the power conversion efficiencies of the CuAgBiI and CuAgBiI solar cells under 1 sun of 1.01 ± 0.06% and 2.39 ± 0.05%, respectively. The latter value is the highest reported for this class of materials owing to the favorable film morphology provided by the hot-casting method. Future performance improvements might emerge from the optimization of the CuAgBiI layer thickness to match the carrier diffusion length of ≈40-50 nm. Nonencapsulated CuAgBiI solar cells display storage stability over 240 days

Balancing charge extraction for efficient back-contact perovskite solar cells by using an embedded mesoscopic architecture

As the performance of organic–inorganic halide perovskite solar cells approaches their practical limits, the use of back-contact architectures, which eliminate parasitic light absorption, provides an effective route toward higher device efficiencies. However, a poor understanding of the underlying device physics has limited further performance improvements. Here a mesoporous charge-transporting layer is introduced into quasi-interdigitated back-contact perovskite devices and the charge extraction behavior with an increased interfacial contact area is studied. The results show that the incorporation of a thin mesoporous titanium dioxide layer significantly shortens the charge-transfer lifetime and results in more efficient and balanced charge extraction dynamics. A high short-circuit current density of 21.3 mA cm–2 is achieved using a polycrystalline perovskite layer on a mesoscopic quasi-interdigitated back-contact electrode, a record for this type of device architecture.The authors are grateful for the financial support by the Australian Centre for Advanced Photovoltaics (ACAP), the Australian Renewable Energy Agency (ARENA), and the Australian Research Council (ARC) ARC Centre of Excellence in Exciton Science (ACEx: CE170100026). This work was performed in part at the Melbourne Centre for Nanofabrication (MCN) in the Victorian Node of the Australian National Fabrication Facility (ANFF). Q.O. acknowledges the support from the ARC Centre of Excellence in Future Low-Energy Electronics Technologies (FLEET).Peer reviewe

Ionic liquid stabilized perovskite solar modules with power conversion efficiency exceeding 20%

Metal-halide perovskite solar cells (PSCs) exhibit outstanding power conversion efficiencies (PCEs) when fabricated as mm-sized devices, but creation of high-performing large-area modules that are stable on a sufficiently long timescale still presents a significant challenge. Herein, the quality of large-area perovskite film is improved by using ionic liquid additives via forming a new Pb-N bonding between the ionic liquid and Pb2+. This new bond can be modulated by a critical screening of the anion structure of the ionic liquid. The selected ionic liquid effectively reduces the defects of the perovskite films and markedly elongate their carrier lifetimes. As a result, a champion PCE of 24.4% for small-area (0.148 cm2) devices and 20.4% for larger-area (10.0 cm2) modules under AM 1.5G irradiation is achieved. More importantly, the modified devices retain 90% of their peak PCE after aging for 1900 h at 65 ± 5 °C (ISOS-T-1) and 80% after continuous light soaking for 750 h. The non-encapsulated modules maintained 80% of their peak PCE after 1100 h of aging in the air with a relative humidity of 35 ± 5% and temperature of 25 ± 5 °C under dark (ISOS-D-1), showing great potential for future commercialization.This work was financially supported by the National Natural Science Foundation of China (91963209, 52002302, 22075221), the Natural Science Foundation of Hubei Provincial (2020CFB172, 2020CFA087), Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory (XHD2020-001), and the Fundamental Research Funds for the Central Universities (WUT: 2020III032, 2021VA101, 2021IVB038). M.H. acknowledges the support from State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology) and SRR acknowledges the support from ‘laCaixa’ Foundation (ID 100010434) with fellowship code LCF/BQ/PI20/11760024.Peer reviewe

Significant THz absorption in CH3NH2 molecular defect-incorporated organic-inorganic hybrid perovskite thin film

The valid strong THz absorption at 1.58 THz was probed in the organic-inorganic hybrid perovskite thin film, CH3NH3PbI3, fabricated by sequential vacuum evaporation method. In usual solution-based methods such as 2-step solution and antisolvent, we observed the relatively weak two main absorption peaks at 0.95 and 1.87 THz. The measured absorption spectrum is analyzed by density-functional theory calculations. The modes at 0.95 and 1.87 THz are assigned to the Pb-I vibrations of the inorganic components in the tetragonal phase. By contrast, the origin of the 1.58 THz absorption is due to the structural deformation of Pb-I bonding at the grain boundary incorporated with a CH3NH2 molecular defect