Structure influence on charge transport in naphthalenediimide-thiophene copolymers

Reported here is a characterisation of a series of NDI-thiophene copolymers with 1, 2, 3 and 4 thiophene units synthesized using Stille polycondensation of dibromo-naphthalene diimide and the trimethylstannylthiophene monomers. The effect of extension of the thiophene donor group is studied in terms of structure-charge transport correlation. The influence of side chains located on the thiophene units of copolymers with 2 and 4 thiophene units per monomer is also investigated. Charge transport of both signs is studied experimentally in field-effect transistors. Microstructural data obtained by near-edge x-ray absorption fine structure (NEXAFS) and grazing incidence wide-angle x-ray scattering (GIWAXS) is supported by AFM topography scans. UPS and UV-Vis spectroscopy data are employed in measurement of energy levels and changes with annealing temperature are also discussed. Most of the polymers reach excellent electron as well as hole mobility with one copolymer (NDI-T4) exhibiting an especially balanced ambipolar charge transport of 0.03 cm2V-1s-1. An odd-even effect in hole mobility is observed with higher values for polymers with even number of thiophene units. The reported findings indicate that the final charge transport properties are a result of the interplay of many factors, including crystallinity, planarity and linearity of chain, spacing between acceptor units and packing of solubilizing branched side chains.CRM acknowledges support from the Australian Research Council (FT100100275, DP130102616) and thanks Dr. Nigel Kirby and Dr. Steven Mudie of the Australian Synchrotron for technical support. The work in Mons is supported by the European Commission / Région Wallonne (FEDER – Smartfilm RF project), the Interuni-versity Attraction Pole program of the Belgian Federal Science Policy Office (PAI 7/05) and the Programme d’Excellence de la Région Wallonne (OPTI2MAT project). MMS acknowledges support from the Winton Programme for the Physics of Sustainability. MiS acknowledges funding from the Fonds der chemischen In-dustrie.This is the accepted manuscript. The final published version is available from ACS at http://pubs.acs.org/doi/abs/10.1021/cm5033578

Different energetics at donor:acceptor interfaces in bilayer and bulk-heterojunction polymer:non-fullerene organic solar cells

To understand the limitations placed on the open-circuit voltage of bulk heterojunction (BHJ) organic solar cells, the energy levels of neat donor and acceptor samples are often characterized and applied to study BHJ blends. However, energy levels derived from neat samples may not necessarily reflect those at the donor:acceptor interface in blends. The properties of organic semiconductors are sensitive to microstructural changes, with non-fullerene acceptors (NFAs) in particular known to exhibit different thin-film polymorphs. To investigate the influence of differences in molecular packing in neat and blend films, temperature-dependent current–voltage characteristics are measured for bilayer (BL) and BHJ devices. Herein, the fullerene acceptor PC71BM is compared—whose energy levels are expected to be less sensitive to molecular packing—with the NFA ITIC, paired with the same donor polymer PTB7-Th. It is found that the interfacial energy levels differ for BL and BHJ devices for the PTB7-Th:ITIC system but remain the same for the PTB7-Th:PC71BM system. Furthermore, X-ray scattering measurements identify that ITIC exhibits a different packing mode in neat films and in BHJ blends. Such microstructure-dependent differences between neat and blend samples need to be considered when studying energy losses in NFA BHJ solar cells

Microstructural control suppresses thermal activation of electron transport at room temperature in polymer transistors

Recent demonstrations of inverted thermal activation of charge mobility in polymer field- effect transistors have excited the interest in transport regimes not limited by thermal bar- riers. However, rationalization of the limiting factors to access such regimes is still lacking. An improved understanding in this area is critical for development of new materials, establishing processing guidelines, and broadening of the range of applications. Here we show that precise processing of a diketopyrrolopyrrole-tetrafluorobenzene-based electron transporting copo- lymer results in single crystal-like and voltage-independent mobility with vanishing activation energy above 280 K. Key factors are uniaxial chain alignment and thermal annealing at temperatures within the melting endotherm of films. Experimental and computational evi- dences converge toward a picture of electrons being delocalized within crystalline domains of increased size. Residual energy barriers introduced by disordered regions are bypassed in the direction of molecular alignment by a more efficient interconnection of the ordered domains following the annealing process

An alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor with high crystallinity exhibiting single junction solar cell efficiencies greater than 13% with low voltage losses

A new synthetic route, to prepare an alkylated indacenodithieno[3,2-b]thiophene-based nonfullerene acceptor (C8-ITIC), is reported. Compared to the reported ITIC with phenylalkyl side chains, the new acceptor C8-ITIC exhibits a reduction in the optical band gap, higher absorptivity, and an increased propensity to crystallize. Accordingly, blends with the donor polymer PBDB-T exhibit a power conversion efficiency (PCE) up to 12.4%. Further improvements in efficiency are found upon backbone fluorination of the donor polymer to afford the novel material PFBDB-T. The resulting blend with C8-ITIC shows an impressive PCE up to 13.2% as a result of the higher open-circuit voltage. Electroluminescence studies demonstrate that backbone fluorination reduces the energy loss of the blends, with PFBDB-T/C8-ITIC-based cells exhibiting a small energy loss of 0.6 eV combined with a high JSCof 19.6 mA cm-2

Understanding charge transport in lead iodide perovskite thin-film field-effect transistors

Fundamental understanding of the charge transport physics of hybrid lead halide perovskite semiconductors is important for advancing their use in high-performance optoelectronics. We use field-effect transistors (FETs) to probe the charge transport mechanism in thin films of methylammonium lead iodide (MAPbI$_{3}$). We show that through optimization of thin-film microstructure and source-drain contact modifications, it is possible to significantly minimize instability and hysteresis in FET characteristics and demonstrate an electron field-effect mobility (μ$_{FET}$) of 0.5 cm$^{2}$/Vs at room temperature. Temperature-dependent transport studies revealed a negative coefficient of mobility with three different temperature regimes. On the basis of electrical and spectroscopic studies, we attribute the three different regimes to transport limited by ion migration due to point defects associated with grain boundaries, polarization disorder of the MA$^{+}$ cations, and thermal vibrations of the lead halide inorganic cages.S.P.S. acknowledges funding from the Royal Society London for a Newton Fellowship. B.Y. acknowledges support from China Council Scholarship and Cambridge Overseas Trust. A.S. and R.H.F. acknowledge funding and support from the Engineering and Physical Sciences Research Council (EPSRC) through the India-U.K. APEX project. P.D. acknowledges support from the European Union through the award of a Marie Curie Intra-European Fellowship. X.M. is grateful for the support from the Royal Society. B.N. is grateful for the support from Gates Cambridge and the Winton Program for the Physics of Sustainability. We acknowledge funding from the EPSRC through a program grant (EP/M005143/1). We acknowledge funding from the German Federal Ministry of Education and Research under agreement number 01162525/1. This work was performed in part on the SAXS/WAXS beamline of the Australian Synchrotron, Victoria, Australia (55, 56). C.R.M. acknowledges support from the Australian Research Council (DP13012616)

Resolving the backbone tilt of crystalline poly(3-hexylthiophene) with resonant tender X-ray diffraction

The way in which conjugated polymers pack in the solid state strongly affects the performance of polymer-based optoelectronic devices. However, even for the most crystalline conjugated polymers the precise packing of chains within the unit cell is not well established. Here we show that by performing resonant X-ray diffraction experiments at the sulfur K-edge we are able to resolve the tilting of the planar backbones of crystalline poly(3-hexylthiophene) (P3HT) within the unit cell. This approach exploits the anisotropic nature of the X-ray optical properties of conjugated polymers, enabling us to discern between different proposed crystal structures. By comparing our data with simulations based on different orientations, a tilting of the planar conjugated backbone with respect to the side chain stacking direction of 30 ± 5° is determined

Correlation between Photovoltaic Performance and Interchain Ordering Induced Delocalization of Electronics States in Conjugated Polymer Blends

In this paper we correlate the solar cell performance with bimolecular packing of donor:acceptor bulk heterojunction (BHJ) organic solar cells (OSCs), where interchain ordering of the donor molecule and its influence on morphology, optical properties, and charge carrier dynamics of BHJ solar cells are studied in detail. Solar cells that are fabricated using more ordered defect free 100% regioregular poly(3-hexylthiophene) (DF-P3HT) as the donor polymer show ca. 10% increase in the average power conversion efficiency (PCE) when compared to that of the solar cell fabricated using 92% regioregularity P3HT, referred to as rr-P3HT. EQE and UV-vis absorption spectrum show a clear increase in the 607 nm vibronic shoulder of the DF-P3HT blend suggesting better interchain ordering which was also reflected in the less Urbach energy (Eu) value for this system. The increase in ordering inside the blend has enhanced the hole-mobility which is calculated from the single carrier device J-V characteristics. Electroluminance (EL) studies on the DF-P3HT system showed a red-shifted peak when compared to rr-P3HT-based devices suggesting low CT energy states in DF-P3HT. The morphologies of the blend films are studied using AFM and grazing-incidence wide-angle X-ray scattering (GIWAXS) suggesting increase in the roughness and phase segregation which could enhance the internal scattering of the light inside the device and improvement in the crystallinity along alkyl and π-stacking direction. Hence, higher PCE, lower Eu, red-shifted EL emission, high hole-mobility, and better crystallinity suggest improved interchain ordering has facilitated a more delocalized HOMO state in DF-P3HT-based BHJ solar cells.We acknowledge these organizations for funds and CEN & NCPRE IITB for device fabrication and characterizations, respectively. N.C. acknowledges the IITB-Monash Research Academy for the fellowship. A.S. and R.H.F. would like to acknowledge the support from EPSRC and the India-UK APEX project

Simpson's Paradox, Lord's Paradox, and Suppression Effects are the same phenomenon – the reversal paradox

This article discusses three statistical paradoxes that pervade epidemiological research: Simpson's paradox, Lord's paradox, and suppression. These paradoxes have important implications for the interpretation of evidence from observational studies. This article uses hypothetical scenarios to illustrate how the three paradoxes are different manifestations of one phenomenon – the reversal paradox – depending on whether the outcome and explanatory variables are categorical, continuous or a combination of both; this renders the issues and remedies for any one to be similar for all three. Although the three statistical paradoxes occur in different types of variables, they share the same characteristic: the association between two variables can be reversed, diminished, or enhanced when another variable is statistically controlled for. Understanding the concepts and theory behind these paradoxes provides insights into some controversial or contradictory research findings. These paradoxes show that prior knowledge and underlying causal theory play an important role in the statistical modelling of epidemiological data, where incorrect use of statistical models might produce consistent, replicable, yet erroneous results