Oxidative-Reductive Near-Infrared Electrochromic Switching Enabled by Porous Vertically Stacked Multilayer Devices.

Here, we demonstrate for the first time the ability of a porous π-conjugated semiconducting polymer film to enable facile electrolyte penetration through vertically stacked redox-active polymer layers, thereby enabling electrochromic switching between p-type and/or n-type polymers. The polymers P1 and P2, with structures diketopyrrolopyrrole (DPP)-πbridge-3,4,-ethylenedioxythiophene (EDOT)-πbridge [πbridge = 2,5-thienyl for P1 and πbridge = 2,5-thiazolyl for P2] are selected as the p-type polymers and N2200 (a known naphthalenediimide-dithiophene semiconductor) as the n-type polymer. Single-layer porous and dense (control) polymer films are fabricated and extensively characterized using optical microscopy, atomic force microscopy, scanning electron microscopy, and grazing incidence wide-angle X-ray scattering. The semiconducting films are then incorporated into single and multilayer electrochromic devices (ECDs). It is found that when a p-type (P2) porous top layer is used in a multilayer ECD, it enables electrolyte penetration to the bottom layer, enabling oxidative electrochromic switching of the P1 bottom layer at low potentials (+0.4 V versus +1.2 V with dense P2). Importantly, when using a porous P1 as the top layer with an n-type N2200 bottom layer, dynamic oxidative-reductive electrochromic switching is also realized. These results offer a proof of concept for development of new types of multilayer electrochromic devices where precise control of the semiconductor film morphology and polymer electronic structure is essential.

Anthradithiophene (ADT)-Based Polymerized Non-Fullerene Acceptors for All-Polymer Solar Cells.

Realizing efficient all-polymer solar cell (APSC) acceptors typically involves increased building block synthetic complexity, hence potentially unscalable syntheses and/or prohibitive costs. Here we report the synthesis, characterization, and implementation in APSCs of three new polymer acceptors P1-P3 using a scalable donor fragment, bis(2-octyldodecyl)anthra[1,2-b : 5,6-b']dithiophene-4,10-dicarboxylate (ADT) co-polymerized with the high-efficiency acceptor units, NDI, Y6, and IDIC. All three copolymers have comparable photophysics to known polymers; however, APSCs fabricated by blending P1, P2 and P3 with donor polymers PM5 and PM6 exhibit modest power conversion efficiencies (PCEs), with the champion P2-based APSC achieving PCE=5.64 %. Detailed morphological and microstructural analysis by AFM and GIWAXS reveal a non-optimal APSC active layer morphology, which suppresses charge transport. Despite the modest efficiencies, these APSCs demonstrate the feasibility of using ADT as a scalable and inexpensive electron rich/donor building block for APSCs.

Atomic-Scale Interface for Pt Nanoparticles on SrTiO3 (001).

The interfacial structure formed by Pt nanoparticles grown epitaxially on a SrTiO3 (001) surface by pulsed laser deposition was studied by X-ray standing-wave (XSW) excited core-level photoelectron emission. The XSW-generated 3D atomic map of the Pt and interfacial oxygens for the oxidized Pt/SrTiO3 interface differs significantly from that of the as-deposited interface. After oxidation, the Pt atoms shifted upward and their atomic occupation at fcc-like sites evolved as the oxidation temperature increased. Interfacial oxygen atoms were differentiated from bulk O atoms by the chemical shift in the binding energy of their 1s electrons. After oxidation, the interfacial oxygen atoms rearranged to form a TiO2 bilayer at the interface. These results provide a more complete description of the strong metal-support interaction process at the interface.

Monolithically integrated high-density vertical organic electrochemical transistor arrays and complementary circuits.

Organic electrochemical transistors (OECTs) can be used to create biosensors, wearable devices and neuromorphic systems. However, restrictions in the micro- and nanopatterning of organic semiconductors, as well as topological irregularities, often limit their use in monolithically integrated circuits. Here we show that the micropatterning of organic semiconductors by electron-beam exposure can be used to create high-density (up to around 7.2 million OECTs per cm2) and mechanically flexible vertical OECT arrays and circuits. The energetic electrons convert the semiconductor exposed area to an electronic insulator while retaining ionic conductivity and topological continuity with the redox-active unexposed areas essential for monolithic integration. The resulting p- and n-type vertical OECT active-matrix arrays exhibit transconductances of 0.08-1.7 S, transient times of less than 100 µs and stable switching properties of more than 100,000 cycles. We also fabricate vertically stacked complementary logic circuits, including NOT, NAND and NOR gates.

Study and modular synthesis of unsymmetrical bis(phosphino)pyrrole ligands.

We report the facile and modular synthesis of unsymmetrical 1,2-bis(phosphino)pyrrole ligands and their coordination chemistry. These ligands offer a promising alternative to their 1,2-bis(phosphino)benzene congeners, retaining a similar steric profile with attenuated electron donation. Proof-of-principle application of a bis(phosphino)pyrrole ligand in a nickel-catalyzed C-N cross-coupling reaction under mild conditions is demonstrated.