Xiaolian Hu

C–H activation: making diketopyrrolopyrrole derivatives easily accessible

Diketopyrrolopyrrole (DPP) derivatives are an important class of high-performance pigment used in inks, paints, plastics, and organic electronics. Until now, DPP derivatives containing sophisticated aryl units at the DPP core have usually been obtained via Suzuki, Stille, or Negishi cross-coupling reactions, which require organometallic precursors. In this work, a series of DPP-based π-conjugated molecules bearing diverse aryl substituents on the thiophene- or benzene-DPPs were facilely synthesized in moderate to excellent yields through the Pd-catalyzed direct arylation of C–H bonds. The synthetic procedures feature advantages over traditional C–C cross-coupling reactions such as: (1) avoidance of the use of organometallic reagents in the starting materials leading to simpler byproducts and higher atom economy, (2) fewer synthetic steps, (3) higher yields, (4) better compatibility with chemically sensitive functional groups, and (5) simpler catalytic systems free of phosphine ligands. These advantages make the present protocol an ideal and versatile strategy for the synthesis of DPP derivatives, especially for structurally complicated DPPs that may possess chemically sensitive functionalities. The optical and electrochemical properties of the synthesized DPPs (17 compounds) were systematically investigated using UV-vis spectroscopy, steady-state fluorescence spectroscopy, and cyclic voltammetry (CV).

An ester-functionalized diketopyrrolopyrrole molecule with appropriate energy levels for application in solution-processed organic solar cells

For highly efficient organic solar cells (OSCs), the electron donor should possess not only a narrow band gap (Eg) but also a low highest occupied molecular orbital (HOMO) energy level. To achieve it, in this paper, we designed and synthesized a diketopyrrolopyrrole (DPP) derivative end capped with an ethyl thiophene-2-carboxylate moiety, 3,6-bis{5-[(ethyl thiophene-2-carboxylate)-2-yl]thiophene-2-yl}-2,5-bis(2-ethylhexyl)pyrrolo[3,4-c]pyrrole-1,4-dione (DPP(CT)2). Through UV-vis absorption and cyclic voltammetry (CV) measurements, we demonstrated that the resulting molecule exhibits both a low optical Eg of 1.65 eV and a lower-lying HOMO energy level of −5.33 eV owing to the electronegativity of the ester group and the conjugation effect of the thiophene ring. Therefore, when DPP(CT)2 is used as the electron donor to blend with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) for solution processable OSCs, a power conversion efficiency (PCE) of 4.02% combined with an open-circuit voltage (VOC) as high as 0.94 V and a broad photovoltaic response range extending to around 750 nm is obtained.

Star-Shaped D–A Small Molecules Based on Diketopyrrolopyrrole and Triphenylamine for Efficient Solution-Processed Organic Solar Cells

Three star-shaped D-A small molecules, (P-DPP)(3)TPA, (4-FP-DPP)(3)TPA, and (4-BuP-DPP)(3)TPA were designed and synthesized with triphenylamine (TPA) as the core, diketopyrrolopyrrole (DPP) as the arm, and unsubstituted or substituted benzene rings (phenyl, P; 4-fluoro-phenyl, 4-FP; 4-n-butyl-phenyl, 4-BuP) as the end-group. All the three small molecules show relatively narrow optical band gaps (1.68-1.72 eV) and low-lying highest occupied molecular orbital (HOMO) energy levels (-5.09∼-5.13 eV), implying that they are potentially good electron donors for organic solar cells (OSCs). Then, photovoltaic properties of the small molecules blended with [6,6]-phenyl-C(61)-butyric acid methyl ester (PC(61)BM) as electron acceptor were investigated. Among three small molecules, the OSC based on (P-DPP)(3)TPA:PCBM blend exhibits a best power conversion efficiency (PCE) of 2.98% with an open-circuit voltage (V(oc)) of 0.72 V, a short-circuit current density (J(sc)) of 7.94 mA/cm(2), and a fill factor (FF) of 52.2%, which may be ascribed to the highest hole mobility of (P-DPP)(3)TPA.

Incorporation of ester groups into low band-gap diketopyrrolopyrrole containing polymers for solar cell applications

To increase the open circuit voltage (VOC) of polymer solar cells based on diketopyrrolopyrrole (DPP) containing polymers, the weakly electron-withdrawing thiophene-3,4-dicarboxylate unit was introduced into the polymer backbone. Two ester group functionalized DPP containing polymers, PCTDPP with a random structure and PDCTDPP with a regular structure, were designed and synthesized by the Stille coupling reaction. The resulting copolymers exhibit broad and strong absorption bands from 350 to 1000 nm with low optical band gaps below 1.40 eV. Through cyclic voltammetry measurements, it is found that regular PDCTDPPs HOMO energy level is 0.18 V lower than that of the corresponding random PCTDPP (−5.14 eV for PCTDPP and −5.32 eV for PDCTDPP). Preliminary photovoltaic properties of the copolymers blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as an electron acceptor were investigated. The PSC based on a PCTDPP:PCBM blend shows a power conversion efficiency (PCE) up to 3.52%, with a VOC of 0.66 V, a short circuit current (ISC) of 8.53 mA cm−2, and a fill factor (FF) of 0.63. For the PDCTDPP:PCBM blend, the highest VOC reaches a value of 0.84 V, and a final PCE (0.92%) is limited by the poor hole mobility of the active layer.

Synthesis and photovoltaic properties from inverted geometry cells and roll-to-roll coated large area cells from dithienopyrrole-based donor–acceptor polymers

A series of donor–acceptor low band gap polymers composed of alternating dithienopyrrole or its derivative as donors and phthalimide or thieno[3,4-c]pyrrole-4,6-dione as acceptors (P1–P4) are synthesized by Stille coupling polymerization. All polymers show strong absorption in the visible region, for P2 and P4 possessing thieno[3,4-c]pyrrole-4,6-dione as an acceptor, their film absorption covers the region of 500–800 nm and 500–750 nm respectively, which makes them attractive as low band gap polymer solar cell (PSC) materials. With the incorporation of thiophene bridges, P3 and P4 have 0.24 and 0.21 eV higher HOMO energy levels than P1 and P2, respectively. A bandgap as low as 1.66 eV is obtained for P2. An up-scaling experiment is performed on bulk-heterojunction PSCs with an inverted device geometry fabricated on a small scale by spin coating and on a large scale using roll-to-roll (R2R) slot-die coating and screen printing. In both cases the best performing polymer is P2 with a Voc of 0.56 V, a Jsc of −12.6 mA cm−2, a FF of 40.3%, and a PCE of 2.84% for small spin coated devices, and a Voc of 0.56 V, a Jsc of −8.18 mA cm−2, a FF of 30.7%, and a PCE of 1.40% are obtained for R2R-fabricated devices with a significantly better performance than a standard P3HT/PCBM driven device.

Influence of film thickness and nanograting period on color-filter behaviors of plasmonic metal Ag films

The effects of film thickness and nanograting period on color filter behaviors of the device, fabricated by sub-micrometers patterning on plasmonic silver thin films, have been studied. It is found that color filter properties strongly correlate with film thickness and nanograting period. Based on obtained results, the relationship of the wavelength of transmission minima with film thickness and nanograting period was derived. This equation can predict the transmission minima for a given thickness and period in one-dimensional Ag metallic film nanograting on glass substrate, which could guide to design color filter device with desirable wavelength.

Effect of relative nanohole position on colour purity of ultrathin plasmonic subtractive colour filters

Plasmonic subtractive color filters through patterning periodic nanostructures on ultrathin Ag films deposited on a glass substrate, exhibiting good durability, simple fabrication, and flexible color tunability, have attracted considerable attention due to their tremendous potential applications. While previous studies have mainly focused on their extraordinary physical mechanisms, color purity, which is another key parameter for high quality imaging applications, has been much less investigated. In this work, we demonstrate that the relative position of nanoholes patterned on ultrathin Ag films can largely affect the color purity of plasmonic subtractive color filters. The calculated results agree reasonably well with the experimental data, revealing that the purity of subtractive colors can be improved by changing the nanohole arrays from square lattice to triangular lattice without reducing transmission at visible frequencies. In addition, underlying mechanisms are clarified by systematically analyzing the dominant valley in transmission spectra.

Immerse precipitation as an efficient protocol to optimize morphology and performance of organic solar cells

We developed a film-forming processing method for morphology control and organic solar cells (OSCs) optimization. In this protocol, the processing solvent inside a wet active layer is removed by dripping a soaking solvent that is selectively soluble for the processing solvents onto the wet active layer film. By this method, OSCs based on diketopyrrolopyrrole containing copolymers: [6,6]-phenyl-C61-butyric acid methyl ester blend were fabricated. Devices processed by this treatment show a significantly increased efficiency by a factor of 3 compared to devices fabricated by the traditional spin-coating method (from 1.03% to 3.2%), which is mainly attributed to morphology improvements.

Plasmonic reflection color filters with metallic random nanostructures

We develop reflective color filters with randomly distributed nanodisks and nanoholes fabricated with hydrogen silsesquioxane and Ag films on silicon substrate. They exhibit high resolution, angle-independence and easily up-scalable fabrication, which are the most important factors for color filters for industrial applications. We uncover the underlying mechanism after systematically analyzing the localized surface plasmon polariton coupling in the electric-field distribution. The agreement of the experimental results with those from the simulation indicates that tunable colors across the visible spectrum can be obtained by simply varying the diameter of the nanodisks, promoting their applications.

Broad band optical band-reject filters in near-infrared regime utilizing bilayer Ag metasurface

A band-reject filter working in a near-infrared regime employing a bilayer Ag metasurface was demonstrated numerically and experimentally. This band-reject filter exhibited a broad rejection band (more than 500 nm), simple structure (including an ultrathin metal film, a dielectric layer, and substrate), and high tunability in the near-infrared spectral region, superior to previously reported filters with band-reject features. Simulations of optical reflection spectra under different conditions were carried out and revealed that the filtering behavior strongly depends on structural parameters. Three band-reject filters were experimentally fabricated and proved to be in good agreement with simulations.