Samarendra P. Singh

A High Mobility P‐Type DPP‐Thieno[3,2‐b]thiophene Copolymer for Organic Thin‐Film Transistors

A copolymer comprising 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) and thieno[3,2-b]thiophene moieties, PDBT-co-TT, shows high hole mobility of up to 0.94 cm2 V-1 s-1 in organic thin-film transistors. The strong intermolecular interactions originated from π-π stacking and donor-acceptor interaction lead to the formation of interconnected polymer networks having an ordered lamellar structure, which have established highly efficient pathways for charge carrier transport.

A Low‐Bandgap Diketopyrrolopyrrole‐Benzothiadiazole‐Based Copolymer for High‐Mobility Ambipolar Organic Thin‐Film Transistors

A new, solution-processable, low-bandgap, diketopyrrolopyrrole- benzothiadiazole-based, donor-acceptor polymer semiconductor (PDPP-TBT) is reported. This polymer exhibits ambipolar charge transport when used as a single component active semiconductor in OTFTs with balanced hole and electron mobilities of 0.35 cm2 V-1s-1 and 0.40 cm 2 V-1s-1, respectively. This polymer has the potential for ambipolar transistor-based complementary circuits in printed electronics.

Annealing-Free High-Mobility Diketopyrrolopyrrole−Quaterthiophene Copolymer for Solution-Processed Organic Thin Film Transistors

A donor-acceptor polymer semiconductor, PDQT, comprising diketopyrrolopyrrole (DPP) and β-unsubstituted quaterthiophene (QT) for organic thin film transistors (OTFTs) is reported. This polymer forms ordered layer-by-layer lamellar packing with an edge-on orientation in thin films even without thermal annealing. The strong intermolecular interactions arising from the fused aromatic DPP moiety and the DPP-QT donor-acceptor interaction facilitate the spontaneous self-assembly of the polymer chains into close proximity and form a large π-π overlap, which are favorable for intermolecular charge hopping. The well-interconnected crystalline grains form efficient intergranular charge transport pathways. The desirable chemical, electronic, and morphological structures of PDQT bring about high hole mobility of up to 0.97 cm(2)/(V·s) in OTFTs with polymer thin films annealed at a mild temperature of 100 °C and similarly high mobility of 0.89 cm(2)/(V·s) for polymer thin films even without thermal annealing.

High mobility organic thin film transistor and efficient photovoltaic devices using versatile donor–acceptor polymer semiconductor by molecular design

In this work, we report a novel donor–acceptor based solution processable low band gap polymer semiconductor, PDPP–TNT, synthesized via Suzuki coupling using condensed diketopyrrolopyrrole (DPP) as an acceptor moiety with a fused naphthalene donor building block in the polymer backbone. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The hole mobilities of 0.65 cm2 V−1s−1 and 0.98 cm2 V−1s−1 are achieved respectively in bottom gate and dual gate OTFT devices with on/off ratios in the range of 105 to 107. Additionally, due to its appropriate HOMO (5.29 eV) energy level and optimum optical band gap (1.50 eV), PDPP–TNT is a promising candidate for organic photovoltaic (OPV) applications. When this polymer semiconductor is used as a donor and PC71BM as an acceptor in OPV devices, high power conversion efficiencies (PCE) of 4.7% are obtained. Such high mobility values in OTFTs and high PCE in OPV make PDPP–TNT a very promising polymer semiconductor for a wide range of applications in organic electronics.

Furan containing diketopyrrolopyrrole copolymers: synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

A furan-containing conjugated polymer for high mobility ambipolar organic thin film transistors.

Furan substituted diketopyrrolopyrrole (DBF) combined with benzothiadiazole based polymer semiconductor PDPP-FBF has been synthesized and evaluated as an ambipolar semiconductor in organic thin-film transistors. Hole and electron mobilities as high as 0.20 cm(2) V(-1) s(-1) and 0.56 cm(2) V(-1) s(-1), respectively, are achieved for PDPP-FBF.

Synthesis of thieno[3,2-b]thiophene derived conjugated oligomers for field-effect transistors applications

A novel series of soluble thieno[3,2-b]thiophene (TT) oligomers with alternating TT and bithiophene or fluorene triad architectures have been synthesized for field-effect transistor (FET) applications. Their optical, thermal and electronic properties were investigated using UV-Vis and photoluminescence spectroscopy, thermal gravimetric analysis, and cyclic voltammetry. Compared with α,α′-dihexylsexithiophene (D6HT), these oligomers exhibit blue-shifted absorption spectra, 0.1 eV to 0.3 eV lower than the highest occupied molecular orbital (HOMO) energy levels and accordingly higher ambient stability. Their crystallinity and morphology features of these oligomers were further investigated with X-ray diffraction and atomic force microscopy using vacuum-deposited thin film on Si/SiO2 substrate. Symmetrically structured TT-oligomers including HT2TT, HTTT2, HTTTT and DDFTT exhibit ordered film morphology and promising FET performance with devices fabricated by either vacuum deposition or solution processing techniques. Interestingly, HTTT2 shows interconnected terrace island morphology, which is often observed for pentacene. All p-type transistors show promising performance, with HT2TT demonstrating a hole mobility up to 0.025 cm2V−1s−1 and an on/off current ration ∼1.2 × 103 with vacuum sublimated film deposited on 70 °C substrate.

Thiophene–benzothiadiazole–thiophene (D–A–D) based polymers: effect of donor/acceptor moieties adjacent to D–A–D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Electrical characteristics of zinc oxide-organic semiconductor lateral heterostructure based hybrid field-effect bipolar transistors

Zinc oxide-organic semiconductor lateral heterostructure based field-effect bipolar transistors (FEBTs) having heterointerfaces approximately midway between the source and drain electrodes are fabricated and characterized. These hybrid FEBTs comprise zinc oxide (ZnO) and p-channel organic semiconductors [Pentacene and α-sexithiophene (6T)] supporting electron transport and hole transport on either side of the heterojunction, respectively. Current flow in the transistor channel is established as a result of carrier injection across the heterointerface followed by recombination. In steady state, such devices possess significant populations of holes and electrons in the transistor channel and operate in bipolar mode.

Electron transport in copper phthalocyanines

Charge transport in copper phthalocyanine (CuPc), partially fluorinated CuPc (F4CuPc), and fluorinated CuPc (F16CuPc) based organic thin film transistors is studied using dual SiO2/polymethylmethacrylate gate dielectrics. We demonstrate the strong influence of air/moisture induced electron traps on electron transport when the lowest unoccupied molecular orbital is close to the vacuum irrespective of hydroxyl-free dielectrics used in the devices.