Abstract  Several electron accepting polymers having weak accepting strong accepting (WA-SA) and strong accepting strong accepting (SA-SA) monomer alternation were synthesized for studies of structure/property relationship in all-polymer solar cells. Two kinds of cyclic amide monomers, 4,10-bis (2-butyloctyl)-thieno [2',3':5,6]pyrido [3,4-g]thieno-[3,2-c]isoquinoline-5,11-dione (TPTI) and 5,11-bis-(2-butyloctyl)-thieno [2',3':4,5] pyrido [2,3-g] thieno [3,2-c] quinoline-4,10-dione (TPTQ), were synthesized as weak accepting monomers (WA). Difluorinated TPTQ (FTPTQ) and well-known perylene diimide (PDI) monomers were synthesized as strong electron accepting monomers (SA). By using 1-chloronaphthalene (CN) as a cosolvent, the morphology of the polymer blended films can be finely tuned to achieve better ordering toward face-on mode and favorable phase separation between electron donor and acceptor, resulting in significant enhancement of short circuit current (J(sc)) and fill factor (FF). The fluorination in the TPTQ unit reduced the dipole moment of the D-A complex and gave a negative effect on a polymer system. PFP showed worse electron accepting property with lower electron mobility than PQP. It is reasoned that the internal polarization plays an important role in the design of electron accepting polymers. As a result, PQP having TPTQ monomer exhibited the best photovoltaic performance with power conversion efficiency (PCE) of 3.52% (V-oc = 0.71 V, J(sc), = 8.57 mA/cm(2), FF = 0.58) at a weight ratio of PTB7-Th:PQP = 1:1, under AM 1.5G.

Abstract  A novel copolymer based on fluorene and perylene diimide with pendent amino groups, namely poly[2,9-bis(3-(dimethylamino)propyl)-5-methyl-12-(7-methyl-9,9-dioctyl-9H-fluoren-2-yl)anthra(2,1,9-def:6,5,10-d'e'f')diisoquinoline-1,3,8,10(2H,9H)-tetraone] (PF-PDIN), has been synthesized and developed as a cathode interlayer for inverted polymer solar cells (I-PSCs). PF-PDIN shows good alcohol solubility and uniform film morphology. The device with the configuration of ITO/PF-PDIN/P3HT:PC61BM/MoO3/Ag exhibits a power conversion efficiency (PCE) of 3.54%. The resulting device shows higher efficiency and better stability relative to the device using an organic small-molecule analogue, 2,9-bis(3-(dimethylamino)propyl)anthrax(2,1,9-def:6,5,10-d'e'f')diisoquinoline-1,3,8,10(2H,9H)-tetraone (PDIN), as the cathode interlayer. This work indicates that PF-PDIN is a new promising candidate cathode interlayer for highly efficient and stable PSCs.

Abstract  All-polymer solar cells composed of binary blends of donor poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene-)-2-6-diyl)] (PBDTTT-CT), and acceptor polymers naphthalene diimide-selenophene copolymer (PNDIS-HD) and perylene diimide-selenophene copolymer (PPDIS) had power conversion efficiencies (PCEs) of 1.3 and 2.1%, respectively. Ternary blend solar cells composed of [PBDTTT-CT][PNDIS-HD](1-x)[PPDIS](x) at 75 wt% PPDIS had a PCE of 3.2%, which is about a 50%-140% enhancement compared with the binary blend devices. Equality of the ternary blend short-circuit current to the sum of those of the binary blend devices, among other results, provided evidence of a parallel-like bulk heterojunction mechanism in the ternary blend solar cells. These results provide the first example of enhanced performance in ternary blend all-polymer solar cells.

Abstract  A small molecule and a polymer based on perylene diimide and thienylenevinylene were designed and synthesized. Both small molecule and polymer exhibited excellent thermal stability with decomposition temperatures of >400 degrees C and strong absorption in the visible region (300-800 nm). These two compounds showed highest occupied molecular orbital levels of -5.57 and -5.70 eV and lowest unoccupied molecular orbital levels of -3.72 and -3.67 eV, respectively. Solution processed fullerene-free polymer solar cells based on the small molecule acceptor and the polymer acceptor afforded power conversion efficiencies of up to 0.69% and 1.00%, respectively. Comparative studies of the absorption, energy levels, charge transport, morphology and photovoltaic properties of the small molecule and polymer were carried out. (C) 2014 Elsevier Ltd. All rights reserved.

Abstract  Motivated by the results obtained from the investigation of singlet-singlet annihilation in a linear multichromophore comprising terrylene diimides (TDI) and perylene diimide (PDI) in 2010, we report the detailed process toward the successful synthesis of a TDI-PDI-TDI dyad. Ineffective synthetic pathways, which were necessary for the understanding of the step-by-step construction of the complex multichromophore, are described, leading toward a universal synthetic plan for multicomponent systems containing rylene diimides separated by rigid oligophenylene spacers.

Abstract  Graphitic carbon nitride (g-C3N4) is among the most promising metal-free photocatalysts for H-2 production from solar-driven water reduction. However, the photocatalytic efficiency of bulk g-C3N4 powders is limited. In this work, molecular aggregates of perylene tetracarboxylic diimides (PTCDIs, a robust class of air-stable n-type organic semiconductor) were loaded via solution processing on the surface of g-C3N4, which is pre-deposited with cocatalyst Pt nanoparticles. The PTCDIs/Pt/g-C3N4 composites thus fabricated exhibit broader visible-light response than Pt/g-C3N4, and possess excellent photochemical stability. The initial intramolecular charge transfer features of the PTCDIs, as well as their energy levels being matched to g-C3N4, ensure subsequent charge separation in the PTCDIs/Pt/g-C3N4 composites. When the composites are dispersed into aqueous solutions containing triethanolamine as a sacrificial electron donor, a tenfold enhancement of H-2 evolution activity (similar to 0.375 mu mol h(-1)) is achieved compared to bare Pt/g-C3N4 under visible-light (lambda >= 420 nm) irradiation. (C) 2015 Elsevier B.V. All rights reserved.

Abstract  Organic Na-host materials have are now actively pursued as an attractive alternative to conventional transition-metal compounds for development of sustainable sodium ion batteries; however, most of the organic compounds reported so far suffer from their low reversible capacity and poor cyclability. Here, we report a simple perylene diimide, 3,4,9,10-perylene-bis(dicarboximide) (PTCDI), which demonstrates remarkable electrochemical performances as an organic cathode for Na-ion batteries. With the high density of redox-active carbonyl groups in a stable π-conjugated structure, the PTCDI molecule can undergo a two-electron redox reaction with reversible insertion/extraction of 2 Na(+) ions per molecular unit, demonstrating a high capacity of 140 mAh g(-1), a strong rate performance with a reversible capacity of 103 mAh g(-1) at 600 mA g(-1) (5 C,1 C = 120 mA g(-1)) and a long-term cyclability with 90% capacity retention over 300 cycles. Because this PTCDI material is commercially available and nontoxic, it may serve as a new alternative cathode for Na-ion battery applications.

Abstract  A series of new perylene diimide derivatives as acceptors for organic solar cell are built to improve the efficiency. The geometry structures, frontier molecular orbital energies, absorption spectra and charge transport properties of derivatives were predicted by the density functional theory methods. The calculated results revealed that the cinnamenyl and phenylethynyl affect the electronic density contours of frontier molecular orbitals significantly. The cinnamenyl substituent shows a small highest occupied molecular orbital-lowest unoccupied molecular orbital gap corresponding to red shifts of the absorption spectra. The phenylethynyl substituent displays the smallest reorganisation energy among these designed molecules.

Abstract  In recent years, a large library of n-type polymers have been developed and widely used as acceptor materials to replace fullerene derivatives in polymer solar cells (PSCs), stimulating the rapid expansion of research on so-called all-polymer solar cells (aPSCs). In particular, rylene diimide-based n-type polymer acceptors have attracted broad research interest due to their high electron mobility, suitable energy levels, and strong light-harvesting ability in the visible region. Among various polymer acceptors, rylene diimide-based polymers presented best performances when served as the acceptor materials in aPSCs. Typically, a record power conversion efficiency (PCE) of 7.7% was very recently achieved from an aPSC with a rylene diimide polymer derivative as the acceptor component. In this review, we highlight recent progress of n-type polymers originated from two significant classes of rylene diimide units, namely naphthalene diimide (NDI) and perylene diimide (PDI), as well as their derivatives for aPSC applications. (C) 2015 Science Press and Dalian Institute of Chemical Physics. All rights reserved.

Abstract  In this paper, one methacrylate monomer contaming naphthalimide as electron acceptor and aromatic hydrazone as electron donor was designed and synthesized. Its copolymer with styrene has been incorporated into sandwiched memory devices which show dynamic random access memory, characteristics with highest ON/OFF current ratio up to 10(6) and a long retention time. Moreover, it was observed that switch threshold voltage of the device varied almost linearly with functional moiety content in the copolymer. The photoluminescence spectra and X-ray diffraction of the copolymer's film were investigated and the results showed that the functional moieties in the pendant chains occurred as pi-pi stacking and the distance between each other became closer as the functional moieties content in the copolymer increased The mechanisms associated with dram characteristics were elucidated from molecular simulation results that the slight electron density transition from the HOMO to LUMO surfaces would easily revert to original state once the external electric field was removed.

Abstract  Treatment of sandwich-type mixed (phthalocyaninato)( porphyrinato) metal complex [HEu(III){Pc(alpha-3-OC(5)H(11))(4)}{TriBPP( NH(2))}] (3) [Pc(alpha-3-OC(5)H(11))(4)=1,8,15,22-tetrakis(3-Pentyloxy)-phthalocyaninate, TriBPP(NH(2))=5,10,15-tris(4-tert-butylphenyl)-20-(4-aminophenyl)porphyrinate] with N-n-butyl-1,6,7,12-tetra(4-rert-butylphenoxyl)perylene-3,4-dicarboxylate anhydride-9,10-dicarboxylate imide (2) in the presence of imidazole in toluene afforded the novel perylene diimide-appended mixed (phthalocyaninato)(porphyrinato) europium(III) double-decker complex (5). Porphyrin-PDI dyad 4 was also obtained by similar method. The electronic absorption spectroscopic and electrochemical properties of PDI-appended double-decker sand the model compounds 2, 3, and 4 were studied, the results indicated that there was no considerable ground-state interaction between the double-decker unit and the PDI unit in 5. The fluorescence measurements revealed that the emission of PDI unit was effectively quenched by the double-decker unit, suggesting remarkable intramolecular interaction in 5 under excited state. (C) 2011 Elsevier Ltd. All rights reserved.

Abstract  A new diamine with phthalic diimide moiety, i.e. N,N'-bis(4-amino-2,3,5,6-tetramethylphenyl)phthalene-1,4-dicarboxyimide was synthesized and applied for condensation with 4-(4,4,5,5,6,6,7,7,8,8,9,9,10, 10,11,11,11-heptadecafluoroundecyloxy)benzaldehyde and 4-octadecyloxybenzaldehyde, which resulted in two new azomethine-phthalic diimides (AZ-PDIs). Thermal, optical and electrochemical properties of AZ-PDIs were discussed in relation to their analogous containing instead of five-membered six-membered imide rings (AZ-NDIs) described in our previous work. The phase behavior of AZ-PDIs examined by differential scanning calorimetry (DSC) and polarized optical microscopy (POM) confirms their liquid crystalline properties in wide range of temperatures. AZ-PDIs do not show decomposition below 400 degrees C as was found based on thermogravimetric analyses (TGA). Optical properties of the prepared compounds were investigated by UV-vis and photoluminescence (PL) measurements. Azomethine-phthalic diimides emitted blue light with emission maximum (lambda(em)) at ca. 446-492 nm contrary to azomethine-naphthalene diimides which emitted green light and lambda(em) was at 536 and 540 nm. The obtained compounds are electrochemically active and undergo reversible reduction and oxidation as evidenced by differential pulse voltammetry (DPV). The azomethine-phthalic diimides exhibited low electrochemical band gap ca. 1.68 eV being promising for optoelectronic applications. (c) 2013 Elsevier B.V. All rights reserved.

Abstract  Phenol substituted 1,8-naphthalimide derivatives acting as a donor and an iridium(III) complex which emits orange light acting as an acceptor were synthesized to fabricate a novel white-light-emitting two-component gel. The intermolecular energy transfer between the two components plays a crucial role in providing the tuneable emission in the mixed gels. The emission of white light can be obtained by carefully tuning the ratio of the two components. These gels are ideal constituents for the design of supramolecular light-harvesting materials, which afford a novel approach to displaying information in soft materials with tuneable optical properties. Furthermore, the two-component gel can respond to cysteine with an obvious change in luminescence that is visible to the naked eye.

Abstract  Chemical vapor deposition-grown graphene has been an attractive electrode material for organic electronic devices, such as organic field-effect transistors (OFETs), because it is highly conductive and provides good oxidation and thermal stability properties. However, it still remains a challenge to demonstrate organic complementary circuits using graphene electrodes because of the relatively poor performance of n-type OFETs. Here, we report the development of high-performance organic complementary inverters using graphene as source/drain electrodes and N, N'-ditridecyl-3,4,9,10-perylenetetracarboxylic diimide (PTCDI-C13) and pentacene as n- and p-type organic semiconductors, respectively. Graphene electrodes were n-doped via the formation of NH2-terminated self-assembled monolayers that lowered the work function and the electron injection barrier between the graphene and PTCDI-C13. Thermal annealing improved the molecular packing among PTCDI-C13 groups on the graphene surface, thereby increasing the crystallinity and grain size. The thermally annealed PTCDI-C13 OFETs prepared using n-doped graphene electrodes exhibited a good field-effect mobility of up to 0.43 cm2/(V s), which was comparable to the values obtained from other p-type pentacene OFETs. By integrating p- and n-type OFETs, we successfully fabricated organic complementary inverters that exhibited highly symmetric operation with an excellent voltage gain of up to 124 and good noise margin.

Abstract  We prepared a solution-processed film comprising a drop-casted mixture of melamine-diacetylene and perylene bis(dicarboximide) (PDI). We show that the diacetylene monomers adopt distinct crystalline organization in the presence of the PDI residues. Importantly, the drop-casted diacetylene/PDI film exhibits ultraviolet light-induced conductivity, ascribed to effective transport of charge carriers in the conjugated polymerized network.

Abstract  Most polymers employed in organic photovoltaic cells have pi-conjugated backbones Here we investigate the physical and optoelectionic properties of three nonconjugated polymers based on perylene diimides The optical properties. exciton diffusion length, band edge positions, conductivity, and carrier mobility of these polymers are described They are electron-conducting and highly photostable The film structure and optoelectronic properties vary with deposition conditions and annealing procedures One of the polymers has an unusually long exciton diffusion length of 22 nm. The free electron density resulting from n-type charged defects is similar to 3 x 10(15) cm(-3) in one polymer and is even lower in the others Simple bilayer solar cells are limited by their series resistance suggesting that these semiconductor films would benefit from doping

Abstract  Fluorescent monodisperse polystyrene microspheres were prepared by two-stage dispersion polymerization, which successfully covalently labeled microspheres with two dyes without disturbing the final particle size and size distribution. By varying the dye concentrations, microspheres show tuned colors with different fluorescent intensity under a single wavelength excitation. Fluorescence resonance energy transfer (FRET) between two labeled dyes was proved to contribute to the emission of the longer-wavelength dye at a shorter-wavelength excitation. There is no dye leakage for microspheres because of the covalent incorporation of dye molecules. The microsphere matrix provides good protection of dye molecules and blocks the influence of media outside on the fluorescence of microspheres. Single microsphere shows intense fluorescence due to a large number of encapsulated dye molecules. These uniform barcoding fluorescent microspheres have potential application in multiplexed bioanalysis. (c) 2007 Elsevier B.V. All rights reserved.

Abstract  A new class of polyelectrolyte-surfactant (PE-surf) composites having potential applications as thin film organic semiconductors is introduced. These materials are comprised of cationic asymmetrically substituted perylene diimides and oppositely charged poly(acrylate) polyanions. Thin films of the composite materials are prepared by mixing and drop casting aqueous solutions of the two precursors onto appropriate substrates. The resulting materials yield photovoltages of >140 mV for approximately equal to 0.6 W/cm(2) illumination intensities, when incorporated in p-n heterojunction devices. Solution-phase spectra obtained from the PE-surf complexes exhibit excimer-like emission and evidence for formation of weakly coupled aggregates in the ground state. Wide-angle X-ray scattering data show the composite films are locally amorphous, while small-angle X-ray data are consistent with a mixture of polymorphic structures that incorporate planar PE-surf bilayers of 3.9-nm repeat distances. Images obtained by conventional far-field light microscopy and multiphoton-excited fluorescence microscopy (MPEFM) indicate that the films are heterogeneous, incorporating submicrometer sized clusters dispersed among much thinner film regions that also incorporate dye. Polarization-dependent MPEFM studies prove the clusters are semiorganized, yielding order parameters (s and P(4)) of 0.09 and 0.01 for in-plane alignment of the chromophores, consistent with a relatively high degree of disorder.

Abstract  In this study, a solution-processed n-type photo-sensing organic thin film transistor was investigated using polymeric dielectric under different white light illuminations. N, N'-di (2-ethylhexyl)-3,4,9,10-perylene diimide and divinyl tetramethyl disiloxane-bis (benzo-cyclobutene) were used as a soluble active organic semiconductor and as a dielectric material, respectively. Stable amplification was observed in the visible region without gate bias by the device. The electrical characterization results showed that an n-type phototransistor with a saturated electron mobility of 0.6 x 10(-3) cm(2)/V.s and a threshold voltage of 1.8 V was obtained. The charge carrier density of the channel of the device exhibited photo-induced behaviors that strongly affected the electrical properties of the transistor. The photosensitivity and photoresponsivity values of the device were 63.82 and 24 mA/W, respectively. These findings indicate that perylene diimide is a promising material for use on organic based phototransistors. (C) 2014 Elsevier B.V. All rights reserved.

Abstract  Several new 1,8-naphthalimide dyad compounds connected with 1,3,4-oxadiazole at different substitution positions were synthesized, in which there are two compounds to be copolymerized with N-vinyl carbazole to form a single-layer electroluminescence (EL) device film, which consists of electron-transporting unit (oxadiazole), hole-transporting unit (PVK) and emitting unit. The photoemission and electroemission of these dyad compounds are near 540 nm, with a maximum luminance of 350 cd/m(2) and luminous efficiency of 3.02 lm/W at 14 V. (C) 1998 Elsevier Science S.A. All rights reserved.

Abstract  The reduction of the two 3,4,9,10-perylene diimide (PDI) derivatives in the mixture of hydrazine hydrate and N, N-dimethylformamide was investigated by the UV-vis absorption spectra, fluorescence spectra (FL) and electron spin resonance spectroscopy (ESR). The time dependence of the PDI content, as well as the structure of PDI aggregates were also investigated and discussed. Combining the electro-migration behavior of PDI- with the molecular self-assembly properties, the films of two PDI derivatives (PDI-32 and PDI-123) were successfully fabricated via anode electro-deposition (AED). The difference of aggregation state between the two PDI films was studied by UV-vis absorption spectra, XRD and SEM. Based on these, the formation mechanism of PDI films was also deduced.

Abstract  We report the interface properties of a perylene-diimide thin film between Au and n-Si substrate fabricated by the spin coating method. The relaxation time (tau) and interface trap density (D (it)) characteristics of the fabricated structure were obtained across various voltage ranges (0.0 V-300 mV) and various frequency ranges (1 kHz-1 MHz). We observed a peak in G (it)/omega versus log (f) plots from 0.0 V to 300 mV. This peak shows the presence of the interface state and its relaxation time. We observed a decrease in values at the same time as an increase in N (ss) values with the increasing applied voltage for the sample. The N (ss) and tau values found to be in the ranges 1.50 x 10(12) eV(-1) cm(-2)-2.83 x 10(12) eV(-1) cm(-2) and 2.83 x 10(-6) s-4.82 x 10(-7) s between 0.0 V and 0.3 V, respectively.

Abstract  We report herein that a mixed layer of the electron-donating copper phthalocyanine (CuPc) and electron-accepting N,N'-ditridecyl perylene diimide (PTCDI-C13) can be an efficient hole injection layer (HIL) for high-performance organic light-emitting diodes (OLEDs). From photophysical, morphological, and structural studies combined with electrical analysis based on the Mott-Schottky model, we conclude that the excellent miscibility between CuPc and PTCDI-C13 enables highly efficient charge transfer, and thus effective p-doping of CuPc, leading to increased hole conductivity of the HIL. As a result, turn-on voltages as low as 2.45 V and greatly improved thermal stabilities as compared to those of OLEDs with conventional CuPc HILs are observed.

Abstract  Two different organic molecules with similar structure, 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and N,N'-dimethyl-3,4,9, 10-perylenetetracarboxylic diimide (DiMe-PTCDI), were used for the modification of Ag Schottky contacts on sulphur passivated GaAs(I 0 0) (S-GaAs). Such diodes were investigated recording in situ current-voltage (I-V) characteristics. As a function of the PTCDA thickness the effective barrier height of Ag/PTCDA/S-GaAs contacts initially increases from 0.59 +/- 0.01 to 0.72 +/- 0.01 eV, and then decreases to 0.54 +/- 0.01 eV, while only a decrease in barrier height from 0.54 +/- 0.01 to 0.45 +/- 0.01 eV is observed for DiMe-PTCDI interlayers. The initial increase and decrease in effective barrier height for PTCDA and DiMe-PTCDI respectively, is correlated with the energy level alignment of the lowest unoccupied molecular orbital (LUMO) with respect to the conduction band minimum (CBM) of S-GaAs at the organic/inorganic semiconductor interface. Whilst there is an additional barrier for electrons at the PTCDA/S-GaAs interface of about 150 meV, i.e. the LUMO lies above CBM, the LUMO is aligned or below CBM in the DiMe-PTCDI case. The results also shine light on the important issue of the transport gap in organic semiconductors for which an estimation can be obtained. (C) 2003 Elsevier Science B.V. All rights reserved.

Abstract  A series of sulfonated poly(p-phenylene-co-aryl ether ketone) (SPP-co-PAEK) membranes are successfully prepared from 2,5-dichloro-3'-sulfobenzophenone and 2,2'-bis[4-(4-chlorobenzoyl)] phenoxyl perfluoropropane through Ni(0)-catalyzed copolymerization for polymer electrolyte membrane fuel cell (PEFC) applications. The obtained SPP-co-PAEKs have fairly high reduced viscosities and give ductile and transparent membranes with good mechanical strength. All the membranes exhibit comparable or even better proton conductivities than that of Nafion 112 in the full hydrate state. In addition, the membranes showed almost isotropic proton conductive behavior with a sigma(perpendicular to)/sigma(parallel to) values in the range of 0.85-0.92. Fuel cell operation using SPP-co-PAEK(3/1) (IEC = 2.0 meq g(-1), thickness of 38 mu m, feed gases: H-2/air) exhibited rather good performances: open circuit voltage of 0.94 V. cell voltage at 1.0 A cm(-2) of 0.61 V. and output at 1.7 A cm(-2) of 0.85W cm(-2) under 90 degrees C and 82/68% relative humidity condition. The results suggested that these SPP-co-PAEK membranes are promising candidates for PEFC applications. (c) 2012 Elsevier B.V. All rights reserved.