Operando Characterization of Organic Mixed Ionic/Electronic Conducting Materials.

Operando characterization plays an important role in revealing the structure-property relationships of organic mixed ionic/electronic conductors (OMIECs), enabling the direct observation of dynamic changes during device operation and thus guiding the development of new materials. This review focuses on the application of different operando characterization techniques in the study of OMIECs, highlighting the time-dependent and bias-dependent structure, composition, and morphology information extracted from these techniques. We first illustrate the needs, requirements, and challenges of operando characterization then provide an overview of relevant experimental techniques, including spectroscopy, scattering, microbalance, microprobe, and electron microscopy. We also compare different in silico methods and discuss the interplay of these computational methods with experimental techniques. Finally, we provide an outlook on the future development of operando for OMIEC-based devices and look toward multimodal operando techniques for more comprehensive and accurate description of OMIECs.

Closely packed, low reorganization energy π-extended postfullerene acceptors for efficient polymer solar cells.

New organic semiconductors are essential for developing inexpensive, high-efficiency, solution-processable polymer solar cells (PSCs). PSC photoactive layers are typically fabricated by film-casting a donor polymer and a fullerene acceptor blend, with ensuing solvent evaporation and phase separation creating discrete conduits for photogenerated holes and electrons. Until recently, n-type fullerene acceptors dominated the PSC literature; however, indacenodithienothiophene (IDTT)-based acceptors have recently enabled remarkable PSC performance metrics, for reasons that are not entirely obvious. We report two isomeric IDTT-based acceptors 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz-(5, 6)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']di-thiophene (ITN-C9) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-benz(6,7)indanone))-5,5,11,11-tetrakis(4-nonylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITzN-C9) that shed light on the exceptional IDTT properties vis-à-vis fullerenes. The neat acceptors and blends with fluoropolymer donor poly{[4,8-bis[5-(2- ethylhexyl)-4-fluoro-2-thienyl]benzo[1,2-b:4,5-b']dithiophene2,6-diyl]-alt-[2,5-thiophenediyl[5,7-bis(2-ethylhexyl)-4,8-dioxo4H,8H-benzo[1,2-c:4,5-c']dithiophene-1,3-diyl]]} (PBDB-TF) are investigated by optical spectroscopy, cyclic voltammetry, thermogravimetric analysis, differential scanning calorimetry, single-crystal X-ray diffraction, photovoltaic response, space-charge-limited current transport, atomic force microscopy, grazing incidence wide-angle X-ray scattering, and density functional theory-level quantum chemical analysis. The data reveal that ITN-C9 and ITzN-C9 organize such that the lowest unoccupied molecular orbital-rich end groups have intermolecular π-π distances as close as 3.31(1) Å, with electronic coupling integrals as large as 38 meV, and internal reorganization energies as small as 0.133 eV, comparable to or superior to those in fullerenes. ITN-C9 and ITzN-C9 have broad solar-relevant optical absorption, and, when blended with PBDB-TF, afford devices with power conversion efficiencies near 10%. Performance differences between ITN-C9 and ITzN-C9 are understandable in terms of molecular and electronic structure distinctions via the influences on molecular packing and orientation with respect to the electrode.

Fluorination Effects on Indacenodithienothiophene Acceptor Packing and Electronic Structure, End-Group Redistribution, and Solar Cell Photovoltaic Response.

Indacenodithienothiophene (IDTT)-based postfullerene electron acceptors, such as ITIC (2,2'-[[6,6,12,12-tetrakis(4-hexylphenyl)-6,12-dihydrodithieno[2,3- d:2',3'- d']-s-indaceno[1,2- b:5,6- b']dithiophene-2,8-diyl]-bis[methylidyne(3-oxo-1 H-indene-2,1(3 H)-diylidene)]]bis[propanedinitrile]), have become synonymous with high power conversion efficiencies (PCEs) in bulk heterojunction (BHJ) polymer solar cells (PSCs). Here we systematically investigate the influence of end-group fluorination density and positioning on the physicochemical properties, single-crystal packing, end-group redistribution propensity, and BHJ photovoltaic performance of a series of ITIC variants, ITIC- nF ( n = 0, 2, 3, 4, and 6). Increasing n from 0 → 6 contracts the optical bandgap, but only marginally lowers the LUMO for n > 4. This yields enhanced photovoltaic short-circuit current density and good open-circuit voltage, so that ITIC-6F achieves the highest PCE of the series, approaching 12% in blends with the PBDB-TF donor polymer. Single-crystal diffraction reveals that the ITIC- nF molecules cofacially interleave with ITIC-6F having the shortest π-π distance of 3.28 Å. This feature together with ZINDO-level computed intermolecular electronic coupling integrals as high as 57 meV, and B3LYP/DZP-level reorganization energies as low as 147 meV, rival or surpass the corresponding values for fullerenes, ITIC-0F, and ITIC-4F, and track a positive correlation between the ITIC- nF space-charge limited electron mobility and n. Finally, a heretofore unrecognized solution-phase redistribution process between the 2-(3-oxo-indan-1-ylidene)-malononitrile-derived end-groups (EGs) of IDTT-based NFAs, i.e., EG1-IDTT-EG1 + EG2-IDTT-EG2 ⇌ 2 EG1-IDTT-EG2, with implications for the entire ITIC PSC field, is identified and mechanistically characterized, and the effects on PSC performance are assessed.

Photovoltaic Blend Microstructure for High Efficiency Post-Fullerene Solar Cells. To Tilt or Not To Tilt?

Achieving efficient polymer solar cells (PSCs) requires a structurally optimal donor-acceptor heterojunction morphology. Here we report the combined experimental and theoretical characterization of a benzodithiophene-benzothiadiazole donor polymer series (PBTZF4-R; R = alkyl substituent) blended with the non-fullerene acceptor ITIC-Th and analyze the effects of substituent dimensions on blend morphology, charge transport, carrier dynamics, and PSC metrics. Varying substituent dimensions has a pronounced effect on the blend morphology with a direct link between domain purity, to some extent domain dimensions, and charge generation and collection. The polymer with the smallest alkyl substituent yields the highest PSC power conversion efficiency (PCE, 11%), reflecting relatively small, high-purity domains and possibly benefiting from "matched" donor polymer-small molecule acceptor orientations. The distinctive morphologies arising from the substituents are investigated using molecular dynamics (MD) simulations which reveal that substituent dimensions dictate a well-defined set of polymer conformations, in turn driving chain aggregation and, ultimately, the various film morphologies and mixing with acceptor small molecules. A straightforward energetic parameter explains the experimental polymer domain morphological trends, hence PCE, and suggests strategies for substituent selection to optimize PSC materials morphologies.

A strongly emitting liquid-crystalline derivative of Y(3)N@C(80): bright and long-lived near-IR luminescence from a charge transfer state.

Great balls of fire: C60 and Y3 N@C80 were connected to the same oligo(phenyleneethynylene) unit to investigate their structural and photophysical properties. NMR investigations revealed a fulleroid structure for the Y3 N@C80 derivative, and both dyads gave rise to columnar phases with core-shell cylinders. The black and gray spheres represent the fullerene core units of the Y3 N@C80 derivative, which is an ideal candidate to be involved in energy and electron transfer processes.

Simulation of polymeric mixed ionic and electronic conductors with a combined classical and quantum mechanical model.

In organic polymeric materials with mixed ionic and electronic conduction (OMIEC), the excess charge in doped polymers is very mobile and the dynamics of the polymer chain cannot be accurately described with a model including only fixed point charges. Ions and polymer are comparatively slower and a methodology to capture the correlated motions of excess charge and ions is currently unavailable. Considering a prototypical interface encountered in this type of materials, we constructed a scheme based on the combination of MD and QM/MM to evaluate the classical dynamics of polymer, water and ions, while allowing the excess charge of the polymer chains to rearrange following the external electrostatic potential. We find that the location of the excess charge varies substantially between chains. The excess charge changes across multiple timescales as a result of fast structural fluctuations and slow rearrangement of the polymeric chains. Our results indicate that such effects are likely important to describe the phenomenology of OMIEC, but additional features should be added to the model to enable the study of processes such as electrochemical doping.

Relation between Local Structure, Electric Dipole, and Charge Carrier Dynamics in DHICA Melanin: A Model for Biocompatible Semiconductors.

Eumelanins are a family of natural and synthetic pigments obtained by oxidative polymerization of their natural precursors: 5,6-dihydroxyindole and its 2-carboxy derivative (DHICA). The simultaneous presence of ionic and electronic charge carriers makes these pigments promising materials for applications in bioelectronics. In this computational study we build a structural model of DHICA melanin considering the interplay between its many degrees of freedom, and then we examine the electronic structure of representative oligomers. We find that a nonvanishing dipole along the polymer chain sets this system apart from conventional polymer semiconductors, determining its electronic structure, reactivity toward oxidation and localization of the charge carriers. Our work sheds light on previously unnoticed features of DHICA melanin that not only fit well with its radical scavenging and photoprotective properties but also open new perspectives toward understanding and tuning charge transport in this class of materials.

Application of Rubrene Air-Gap Transistors as Sensitive MEMS Physical Sensors.

Micro-electromechanical systems (MEMS) made of organic materials have attracted efforts for the development a new generation of physical, chemical, and biological sensors, for which the electromechanical sensitivity is the current major concern. Here, we present an organic MEMS made of a rubrene single-crystal air-gap transistor. Applying mechanical pressure on the semiconductor results in high variations in drain current: an unparalleled gauge factor above 4000 has been measured experimentally. Such a high sensitivity is induced by the modulation of charge injection at the interface between the gold electrode and the rubrene semiconductor as an unusual transducing effect. Applying these devices to the detection of acoustic pressure shows that force down to 230 nN can be measured with a resolution of 40 nN. This study demonstrates that MEMS based on rubrene air-gap transistors constitute a step forward in the development of high-performance flexible sensors.