Jeremy R. Niskala

Enhanced Solid-State Order and Field-Effect Hole Mobility through Control of Nanoscale Polymer Aggregation

Efficient charge carrier transport in organic field-effect transistors (OFETs) often requires thin films that display long-range order and close π-π packing that is oriented in-plane with the substrate. Although some polymers have achieved high field-effect mobility with such solid-state properties, there are currently few general strategies for controlling the orientation of π-stacking within polymer films. In order to probe structural effects on polymer-packing alignment, furan-containing diketopyrrolopyrrole (DPP) polymers with similar optoelectronic properties were synthesized with either linear hexadecyl or branched 2-butyloctyl side chains. Differences in polymer solubility were observed and attributed to variation in side-chain shape and polymer backbone curvature. Averaged field-effect hole mobilities of the polymers range from 0.19 to 1.82 cm(2)/V·s, where PDPP3F-C16 is the least soluble polymer and provides the highest maximum mobility of 2.25 cm(2)/V·s. Analysis of the films by AFM and GIXD reveal that less soluble polymers with linear side chains exhibit larger crystalline domains, pack considerably more closely, and align with a greater preference for in-plane π-π packing. Characterization of the polymer solutions prior to spin-coating shows a correlation between early onset nanoscale aggregation and the formation of films with highly oriented in-plane π-stacking. This effect is further observed when nonsolvent is added to PDPP3F-BO solutions to induce aggregation, which results in films with increased nanostructural order, in-plane π-π orientation, and field-effect hole mobilities. Since nearly all π-conjugated materials may be coaxed to aggregate, this strategy for enhancing solid-state properties and OFET performance has applicability to a wide variety of organic electronic materials.

A Mechanistic Understanding of Processing Additive‐Induced Efficiency Enhancement in Bulk Heterojunction Organic Solar Cells

The addition of processing additives is a widely used approach to increase power conversion efficiencies for many organic solar cells. We present how additives change the polymer conformation in the casting solution leading to a more intermixed phase-segregated network structure of the active layer which in turn results in a 5-fold enhancement in efficiency.

Solution‐Processed, Molecular Photovoltaics that Exploit Hole Transfer from Non‐Fullerene, n‐Type Materials

J. D. Douglas, M. S. Chen, J. R. Niskala, O. P. Lee, A. T. Yiu, E. P. Young, J. M. J. Fréchet, Departments of Chemistry and Chemical and Biomolecular Engineering University of California, Berkeley Berkeley, CA, 94720–1460, USA E-mail: mschen@berkeley.edu J. D. Douglas, M. S. Chen, J. R. Niskala, O. P. Lee, A. T. Yiu, J. M. J. Fréchet, Materials Science Division Lawrence Berkeley National Laboratory Berkeley, CA 94720, USA Dr. M. S. Chen Departments of Chemistry and Chemical and Biomolecular Engineering University of California Berkeley, Berkeley, CA 94720–1460, USA Prof. J. M. J. Fréchet King Abdullah University of Science and Technology (KAUST) Thuwal 23955–6900, Saudi Arabia E-mail: jean.frechet@kaust.edu.sa

Comprehensive Investigation of Self-Assembled Monolayer Formation on Ferromagnetic Thin Film Surfaces

We report a simple, universal method for forming high surface coverage SAMs on ferromagnetic thin (< or =100 nm) films of Ni, Co, and Fe. Unlike previous reports, our technique is broadly applicable to different types of SAMs and surface types. Our data constitutes the first comprehensive examination of SAM formation on three different ferromagnetic surface types using two different surface-binding chemistries (thiol and isocyanide) under three different preparation conditions: (1) SAM formation on electroreduced films using a newly developed electroreduction approach, (2) SAM formation on freshly evaporated surfaces in the glovebox, and (3) SAM formation on films exposed to atmospheric conditions beforehand. The extent of SAM formation for all three conditions was probed by cyclic voltammetry for surfaces functionalized with either (11-thiolundecyl)ferrocene (Fc-(CH2) 11-SH) or (11-isocyanoundecyl)ferrocene (Fc-(CH2) 11-NC). SAM formation was also probed for straight-chain molecules, hexadecanethiol and hexadecaneisocyanide, with contact angle measurements, X-ray photoelectron spectroscopy, and reflection-absorption infrared spectroscopy (RAIRS). The results show that high surface coverage SAMs with low surface-oxide content can be achieved for thin, evaporated Ni and Co films using our electroreduction process with thiols. The extent of SAM formation on electroreduced films is comparable to what has been observed for SAMs/Au and to what we observe for SAMs/Ni, Co, and Fe samples prepared in the glovebox.

Tunneling Characteristics of Au–Alkanedithiol–Au Junctions formed via Nanotransfer Printing (nTP)

Construction of permanent metal-molecule-metal (MMM) junctions, though technically challenging, is desirable for both fundamental investigations and applications of molecule-based electronics. In this study, we employed the nanotransfer printing (nTP) technique using perfluoropolyether (PFPE) stamps to print Au thin films onto self-assembled monolayers (SAMs) of alkanedithiol formed on Au thin films. We show that the resulting MMM junctions form permanent and symmetrical tunnel junctions, without the need for an additional protection layer between the top metal electrode and the molecular layer. This type of junction makes it possible for direct investigations into the electrical properties of the molecules and the metal-molecule interfaces. Dependence of transport properties on the length of the alkane molecules and the area of the printed Au electrodes has been examined systematically. From the analysis of the current-voltage (I-V) curves using the Simmons model, the height of tunneling barrier associated with the molecule (alkane) has been determined to be 3.5 ± 0.2 eV, while the analysis yielded an upper bound of 2.4 eV for the counterpart at the interface (thiol). The former is consistent with the theoretical value of ~3.5-5.0 eV. The measured I-V curves show scaling with respect to the printed Au electrode area with lateral dimensions ranging from 80 nm to 7 μm. These results demonstrate that PFPE-assisted nTP is a promising technique for producing potentially scalable and permanent MMM junctions. They also demonstrate that MMM structures (produced by the unique PFPE-assisted nTP) constitute a reliable test bed for exploring molecule-based electronics.

Metal−Molecule−Metal Junctions via PFPE Assisted Nanotransfer Printing (nTP) onto Self-Assembled Monolayers

We report a simple method to form metal-molecule-metal junctions (MMMs) via nanotransfer printing with low surface energy perfluoropolyether (PFPE) based stamps. Transfer printing is demonstrated onto thermally deposited metal thin film electrodes where the root-mean-squared roughness of these films is controlled by the deposition process and varies by 40% or more. Transfer of Au and Co thin films is reported onto Au/SAM and Co/SAM electrodes in well-ordered, 200 nm MMM arrays; furthermore, nickel nanotransfer printing is shown for the first time in the construction of 200 nm arrays of Ni/SAM/Ni junctions. The nanotransfer printing we report is reproducible in high fidelity which is required in the application of practical molecular electronic devices. Current-voltage characteristics are presented.

Laterally patterned magnetic nanoparticles

Laterally patterning magnetic nanoparticles (MNPs) through self-assembly and simple solution processing constitutes an important step toward inexpensive nanoparticle-based devices. In this work, MNPs were laterally patterned on metal thin films using laterally patterned self-assembled monolayers (SAMs) as a template. SAMs of inactive molecules were first patterned on an Au thin film using the soft-lithographic technique, microcontact printing. The active, bifunctional molecules, 1,10-decanedithiol or 4-(11-mercaptoundecyl)benzene-1,2-diol, were then patterned through backfilling. The MNPs selectively bind to the terminal thiols or modified catechols when the substrates are submerged into a solution of MNPs. By adjusting the deposition conditions, both monolayers and partial multilayers were controllably formed. Co, Ni, Fe3O4, and FePt MNPs, as well as Au non-magnetic nanoparticles were successfully patterned by this process. This generalized approach is anticipated to be adaptable to many other kinds of nanoparticlesvia judicious selection of the substrates, surfactant ligands (on the nanoparticle), and/or surface-bound monolayers.