Photocurrent spectroscopic studies of diketopyrrolopyrrole-based statistical copolymers

Diketopyrrolopyrrole (DPP) containing copolymers have gained a lot of interest in organic optoelectronics with great potential in organic photovoltaics. In this work, DPP based statistical copolymers, with slightly different bandgap energies and a varying fraction of donor-acceptor ratio are investigated using monochromatic photocurrent spectroscopy and Fourier-transform photocurrent spectroscopy (FTPS). The statistical copolymer with a lower DPP fraction, when blended with a fullerene derivative, shows the signature of an inter charge transfer complex state in photocurrent spectroscopy. Furthermore, the absorption spectrum of the blended sample with a lower DPP fraction is seen to change as a function of an external bias, qualitatively similar to the quantum confined Stark effect, from where we estimate the exciton binding energy. The statistical copolymer with a higher DPP fraction shows no signal of the inter charge transfer states and yields a higher external quantum efficiency in a photovoltaic structure. In order to gain insight into the origin of the observed charge transfer transitions, we present theoretical studies using density-functional theory and time-dependent density-functional theory for the two pristine DPP based statistical monomers.

Photocurrent spectroscopic studies of diketopyrrolopyrrole-based statistical copolymers

Diketopyrrolopyrrole (DPP) containing copolymers have gained a lot of interest in organic optoelectronics with great potential in organic photovoltaics. In this work, DPP based statistical copolymers, with slightly different bandgap energies and a varying fraction of donor-acceptor ratio are investigated using monochromatic photocurrent spectroscopy and Fourier-transform photocurrent spectroscopy (FTPS). The statistical copolymer with a lower DPP fraction, when blended with a fullerene derivative, shows the signature of an inter charge transfer complex state in photocurrent spectroscopy. Furthermore, the absorption spectrum of the blended sample with a lower DPP fraction is seen to change as a function of an external bias, qualitatively similar to the quantum confined Stark effect, from where we estimate the exciton binding energy. The statistical copolymer with a higher DPP fraction shows no signal of the inter charge transfer states and yields a higher external quantum efficiency in a photovoltaic structure. In order to gain insight into the origin of the observed charge transfer transitions, we present theoretical studies using density-functional theory and time-dependent density-functional theory for the two pristine DPP based statistical monomers.

Electronic structure of Nd1-xYxMnO3 from Mn K edge absorption spectroscopy and DFT methods

The electronic structure of Nd1-xYxMnO3 (x-0-0.5) is studied using x-ray absorption near-edge structure (XANES) spectroscopy at the Mn K-edge along with the DFT-based LSDA+U and real space cluster calculations. The main edge of the spectra does not show any variation with doping. The pre-edge shows two distinct features which appear well-separated with doping. The intensity of the pre-edge decreases with doping. The theoretical XANES were calculated using real space multiple scattering methods which reproduces the entire experimental spectra at the main edge as well as the pre-edge. Density functional theory calculations are used to obtain the Mn 4p, Mn 3d and O 2p density of states. For x=0, the site-projected density of states at 1.7 eV above Fermi energy shows a singular peak of unoccupied e(g) (spin-up) states which is hybridized Mn 4p and O 2p states. For x=0.5, this feature develops at a higher energy and is highly delocalized and overlaps with the 3d spin-down states which changes the pre-edge intensity. The Mn 4p DOS for both compositions, show considerable difference between the individual p(x), p(y) and p(z)), states. For x=0.5, there is a considerable change in the 4p orbital polarization suggesting changes in the Jahn-Teller effect with doping. (C) 2013 Elsevier Ltd. All rights reserved.

Carbohydrate-Appended Tumor Targeting Iron(III) Complexes Showing Photocytotoxicity in Red Light

Glucose-appended photocytotoxic iron(III) complexes of a tridentate Schiff base phenolate ligand Fe(bpyag) (L)] (NO3) (1-3), where bpyag is N,N-bis(2- pyridylmethyl)-2-aminoethyl-beta-D-glucopyranoside and H2L is 3-(2-hydroxyphenylimino)-1-phenylbutan-1-one (H(2)phap) in 1, 3-(2-hydroxyphenylimino)-9-anthrylbutan-1-one (H(2)anap) 2, and 3- (2-hydroxyphenylimino)-1-pyrenylbutan-1-one (H(2)pyap) in 3, were synthesized and characterized. The complex Fe(dpma)(anapn(NO3) (4), having bis-(2-pyridylmethyl)benzylamine (dpma), in which the glucose moiety of bpyag is substituted by a phenyl group, was used as a control, and the complex Fe(dpma)(anap)](PF6) (4a) was structurally characterized by X-ray crystallography. The structure shows a FeN4O2 core in a distorted octahedral geometry. The high-spin iron(III) complexes with magnetic moment value of similar to 5.9 mu(B) showed a low-energy phenolate-to-Fe(III) charge-transfer (CT) absorption band as a shoulder near 500 nm with a tail extending to 700 nm and an irreversible Fe(III)-Fe(II) redox couple near -0.6 V versus saturated calomel electrode. The complexes are avid binders to calf thymus DNA and showed photocleavage of supercoiled pUC19 DNA in red (647 nm) and green (532 nm) light. Complexes 2 and 3 displayed significant photocytotoxicity in red light, with an IC50 value of similar to 20 mu M in HeLa and HaCaT cells, and no significant toxicity in dark. The cell death is via an apoptotic pathway, by generation of reactive oxygen species. Preferential internalization of the carbohydrate-appended complexes 2 and 3 was evidenced in HeLa cells as compared to the control complex 4. A 5-fold increase in the cellular uptake was observed for the active complexes in HeLa cells. The photophysical properties of the complexes are rationalized from the density functional theory calculations.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.

Electronic band Structure and Photoemission Spectra of Graphene on Silicon Substrate

Synergizing graphene on silicon based nanostructures is pivotal in advancing nano-electronic device technology. A combination of molecular dynamics and density functional theory has been used to predict the electronic energy band structure and photo-emission spectrum for graphene-Si system with silicon as a substrate for graphene. The equilibrium geometry of the system after energy minimization is obtained from molecular dynamics simulations. For the stable geometry obtained, density functional theory calculations are employed to determine the energy band structure and dielectric constant of the system. Further the work function of the system which is a direct consequence of photoemission spectrum is calculated from the energy band structure using random phase approximations.

Energy funneling and macromolecular conformational dynamics: a 2D Raman correlation study of PEG melting

Cascading energy landscapes through funneling has been postulated as a mechanistic route for achieving the lowest energy configuration of a macromolecular system (such as proteins and polymers). In particular, understanding the molecular mechanism for the melting and crystallization of polymers is a challenging fundamental question. The structural modifications that lead to the melting of poly(ethylene glycol) (PEG) are investigated here. Specific Raman bands corresponding to different configurations of the PEG chain have been identified, and the molecular structural dynamics of PEG melting have been addressed using a combination of Raman spectroscopy, 2D Raman correlation and density functional theory (DFT) calculations. The melting dynamics of PEG have been unambiguously explained along the C-O bond rotation coordinate.

First-Principles Study of Structure, Vibrational, and Elastic Properties of Stoichiometric and Calcium-Deficient Hydroxyapatite

Hydroxyapatite (HAp), a primary constituent of human bone, is usually nonstoichiometric with varying Ca/P molar ratios, with the well-known fact that Ca deficiency can cause marked reductions in its mechanical properties. To gain insights into the mechanism of this degradation, we employ first-principles calculations based on density functional theory and determine the effects of Ca deficiency on structure, vibrational, and elastic properties of HAp. Our simulation results confirm a considerable reduction in the elastic constants of HAp due to Ca deficiency, which was experimentally reported earlier. Stress-induced transformation of the Ca-deficient defected structure into a metastable state upon the application of stress could be a reason for this. Local structural stability of HAp and Ca-deficient HAp structures is assessed with full phonon dispersion studies. Further, specific signatures in the computed vibrational spectra for Ca deficiency in HAp can be utilized in experimental characterization of different types of defected HAp.

New 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles: synthesis, liquid crystalline behavior and photo physical properties

A new series of luminescent 4-(2-(4-alkoxyphenyl)-6-methoxypyridin-4-yl) benzonitriles containing three ring systems, viz. methoxy pyridine, benzonitrile and alkoxy benzene with variable alkoxy chain length, with bent-core structures were synthesized as potential mesogens and characterized by spectral techniques. Their liquid crystalline behavior was investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and variable temperature powder X-ray diffraction (PXRD) measurements. The study reveals that compounds with shorter chain lengths i.e. m = 4] exclusively exhibit the nematic phase while compounds with longer chain lengths i.e. m = 6-14 (only even)] show predominantly the orthorhombic columnar phase. Single crystal X-ray analysis of 4-(2-(4-butyloxy/octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitriles reveals that they possess slightly non-planar unsymmetrical bent structures and their molecular packing consists of nonconventional H-bond interactions; it also explains the observed liquid crystalline phase. An optical study indicates that the title compounds are good blue emitting materials showing absorption and emission bands in the range 335-345 nm and 415-460 nm, respectively. An electrochemical study of 4-(2-(4-octyloxyphenyl)-6-methoxypyridin-4-yl) benzonitrile shows a band gap of 1.89 eV with HOMO and LUMO energy levels of -5.06 and -3.17 eV, respectively. Also, density functional theory (DFT) calculations confirm its optimized geometry, electronic absorption and frontier molecular orbital distributions.

Germanane: a Low Effective Mass and High Bandgap 2-D Channel Material for Future FETs

We investigate the electronic properties of Germanane and analyze its importance as 2-D channel material in switching devices. Considering two types of morphologies, namely, chair and boat, we study the real band structure, the effective mass variation, and the complex band structure of unstrained Germanane by density-functional theory. The chair morphology turns out to be a more effective channel material for switching devices than the boat morphology. Furthermore, we study the effect of elastic strain, van der Waals force, and vertical electric field on these band structure properties. Due to its very low effective mass with relatively high-energy bandgap, in comparison with the other 2-D materials, Germanane appears to provide superior performance in switching device applications.

Selenium in Diketopyrrolopyrrole-based Polymers: Influence on Electronic Properties and Charge Carrier Mobilities

Diketopyrrolopyrrole (DPP)-based pi-conjugated copolymers with thiophene have exceptionally high electron mobilities. This paper investigates electronic properties and charge carrier mobilities of selenophene containing analogues. Two new copolymers, with alternating thiophene DPP (TDPP) and selenophene DPP (SeDPP) units, were synthesized. Two side-chains, hexyl (Hex) and triethylene glycol (TEG) were employed, yielding polymers designated as PTDPPSeDPP-Hex and PTDPPSeDPP-TEG. Selenophene systems have smaller band gaps, with concomitant enhancement of the stability of the reduced state. For both polymers, ambipolar mobilities were observed in organic field-effect transistors (OFET). Grazing incidence X-ray diffraction (GIXD) data indicates preferential edge-on orientation of PTDPPSeDPP-TEG, which leads to superior charge transport properties of the TEG substituted polymer, as compared to its Hex analogue. Time-dependent-density functional theory (TDDFT) calculations corroborate the decrease in the optical band gap with the inclusion of selenophene. Ambipolar charge transport is rationalized by exceptionally wide conduction bands. Delta SCF calculations confirm the larger electron affinity, and therefore the greater stability, of the reduced form of the selenophene-containing DPP polymer in presence of chloroform.

Boron doped defective graphene as a potential anode material for Li-ion batteries

Graphene with large surface area and robust structure has been proposed as a high storage capacity anode material for Li ion batteries. While the inertness of pristine graphene leads to better Li kinetics, poor adsorption leads to Li clustering, significantly affecting the performance of the battery. Here, we show the role of defects and doping in achieving enhanced adsorption without compromising on the high diffusivity of Li. Using first principles density functional theory (DFT) calculations, we carry out a comprehensive study of diffusion kinetics of Li over the plane of the defective structures and calculate the change in the number of Li atoms in the vicinity of defects, with respect to pristine graphene. Our results show that the Li-C interaction, storage capacity and the energy barriers depend sensitively on the type of defects. The un-doped and boron doped mono-vacancy, doped di-vacancy up to two boron, one nitrogen doped di-vacancy, and Stone-Wales defects show low energy barriers that are comparable to pristine graphene. Furthermore, boron doping at mono-vacancy enhances the adsorption of Li. In particular, the two boron doped mono-vacancy graphene shows both a low energy barrier of 0.31 eV and better adsorption, and hence can be considered as a potential candidate for anode material.

Semiconductor-like Sensitivity in Metallic Ultrathin Gold Nanowire-Based Sensors

Due to the ease of modification of electronic structure upon analyte adsorption, semiconductors have been the preferred materials as chemical sensors. At reduced dimension, however, the sensitivity of semiconductor-based sensors deteriorates significantly due to passivation, and often by increased band gap caused by quantum confinement. Using first-principles density functional theory combined with Boltzmann transport calculations, we demonstrate semiconductor-like sensitivity toward chemical species in ultrathin gold nanowires (AuNWs). The sensing mechanism is governed by the modification of the electronic structure of the AuNW as well as scattering of the charge carriers by analyte adsorption. Most importantly, the sensitivity exhibits a linear relationship with the electron affinities of the respective analytes. Based on this relationship, we propose an empirical parameter, which can predict an analyte-specific sensitivity of a AuNW, rendering them as effective sensors for a wide range of chemical an alytes.

Temperature-dependent stability of stacking faults in Al, Cu and Ni: first-principles analysis

We present comparative analysis of microscopic mechanisms relevant to plastic deformation of the face-centered cubic (FCC) metals Al, Cu, and Ni, through determination of the temperature-dependent free energies of intrinsic and unstable stacking faults along 1 (1) over bar 0] and 1 (2) over bar 1] on the (1 1 1) plane using first-principles density-functional-theory-based calculations. We show that vibrational contribution results in significant decrease in the free energy of barriers and intrinsic stacking faults (ISFs) of Al, Cu, and Ni with temperature, confirming an important role of thermal fluctuations in the stability of stacking faults (SFs) and deformation at elevated temperatures. In contrast to Al and Ni, the vibrational spectrum of the unstable stacking fault (USF1 (2) over bar 1]) in Cu reveals structural instabilities, indicating that the energy barrier (gamma(usf)) along the (1 1 1)1 (2) over bar 1] slip system in Cu, determined by typical first-principles calculations, is an overestimate, and its commonly used interpretation as the energy release rate needed for dislocation nucleation, as proposed by Rice (1992 J. Mech. Phys. Solids 40 239), should be taken with caution.

Pressure induced manifold enhancement of Li-kinetics in FCC fullerene

The reduction of the diffusion energy barrier for Li in electrodes is one of the required criteria to achieve better performances in Li ion batteries. Using density functional theory based calculations, we report a pressure induced manifold enhancement of Li-kinetics in bulk FCC fullerene. Scanning of the potential energy surface reveals a diffusion path with a low energy barrier of 0.62 eV, which reduces further under the application of hydrostatic pressure. The pressure induced reduction in the diffusion barrier continues till a uniform volume strain of 17.7% is reached. Further enhancement of strain increases the barrier due to the repulsion caused by C-C bond formation between two neighbouring fullerenes. The decrease in the barrier is attributed to the combined effect of charge transfer triggered by the enhanced interaction of Li with the fullerene as well as the change in profile of the local potential, which becomes more attractive for Li. The lowering of the barrier leads to an enhancement of two orders of magnitude in Li diffusivity at room temperature making pressurized bulk fullerene a promising artificial solid electrolyte interface (SEI) for a faster rechargeable battery.