Synthesis of Diketopyrrolopyrrole Containing Copolymers: A Study of Their Optical and Photovoltaic Properties

The diketopyrrolopyrrole-based copolymers PDPP-BBT and TDPP-BBT were synthesized and used as donor for bulk heterojunction photovoltaic devices. The photophysical properties of these polymers showed absorption in the range 500-600 nm with a maximum peak around 563 nm, while TDPP-BBT showed broadband absorption in the range 620 - 800 nm with a peak around 656 nm. The power conversion efficiencies (PCE) of the polymer solar cells based on these copolymers and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) were 0.68% (as cast PDPP-BBT:PCBM), 1.51% (annealed PDPP-BBT:PCBM), 1.57% (as cast TDPPBBT: PCBM), and 2.78% (annealed TDPP-BBT:PCBM), under illumination of AM 1.5 (100 mW/cm2). The higher PCE for TDPP-BBT-based polymer solar cells has been attributed to the low band gap of this copolymer as compared to PDPP-BBT, which increases the numbers of photogenerated excitons and corresponding photocurrent of the device. These results indicate that PDPP-BBT and TDPP-BBT act as excellent electron donors for bulk heterojunction devices.

Charge transfer complex states in diketopyrrolopyrrole polymers and fullerene blends: Implications for organic solar cell efficiency

The spectral photocurrent characteristics of two donor-acceptor diketopyrrolopyrrole (DPP)-based copolymers (PDPP-BBT and TDPP-BBT) blended with a fullerene derivative [6,6]-phenyl C-61-butyric acid methyl ester (PCBM) were studied using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) method. PDPP-BBT: PCBM shows the onset of the lowest charge transfer complex (CTC) state at 1.42 eV, whereas TDPP-BBT: PCBM shows no evidence of the formation of a midgap CTC state. The FTPS and PC spectra of P3HT:PCBM are also compared. The larger singlet state energy difference of TDPP-BBT and PCBM compared to PDPP-BBT/P3HT and PCBM obliterates the formation of a midgap CTC state resulting in an enhanced photovoltaic efficiency over PDPP-BBT: PCBM. (C) 2011 American Institute of Physics. [doi:10.1063/1.3670043]

Polymer blend based photovoltaic devices.

Solar cells on thin conformable substrates require conventional plastics such asPS and PMMA that provide better mechanical and environmental stability with cost reduction. We can also tune charge transfer between PPV derivatives and fullerene derivatives via morphology control of the plastics in the solar cells. Our group has conducted morphology evolution studies in nano- and microscale light emitting domains in poly (2-methoxy, 5-(2'-ethyl-hexyloxy)-p-phenylenevinylene) (MEH-PPV) and poly (methyl methacrylate) (PMMA) blends. Our current research has been focused on tricomponent-photoactive solar cells which comprise MEH-PPV, PMMA, and [6,6]-phenyl C61-butyric acid methyl ester (PCBM, Figure 1) in the photoactive layer. Morphology control of the photoactive materials and fine tuning of photovoltaic properties for the solar cells are our primary interest. Similar work has been done by the Sariciftci research group. Additionally, a study on inter- and intramolecular photoinduced charge transfer using MEH-PPV derivatives that have different conjugation lengths (Figure 1, n=1 and 0.85) has been performed.

Dithienylcyclopentadienone derivative-co-benzothiadiazole: An alternating copolymer for organic photovoltaics

Alternating copolymer of 7,9-di(thiophen-2-yl)-8H-cyclopenta[a]acenaphthylen-8-one-co-benzothia diazole was synthesized by palladium(0) catalyzed Stille coupling reaction. This solution processable copolymer shows an excellent thermal stability and has a broad absorption range from 300 to 800 nm with a band gap of about 1.51 eV. High LUMO energy level and low band gap of the synthesized copolymers suggest that, this copolymer will be a suitable donor material for use in an organic photovoltaic device. Photovoltaic devices were fabricated from the blend of copolymer and phenyl-C61-butyric acid methyl ester as the active material. (C) 2011 Elsevier By. All rights reserved.

Random copolymers consisting of dithienylcyclopentadienone, thiophene and benzothiadiazole for bulk heterojunction solar cells

Novel random copolymers containing dithienylcyclopentadienone, thiophene and benzothiadiazole were synthesized and photovoltaic properties of these materials were evaluated. Thermal, structural, optical and electrochemical characterization of the synthesized copolymers was carried out. These thermally stable copolymers are solution processable unlike the homopolymer. The absorption spectra indicated that with the incorporation of alkyl chains in the thiophene moiety, the onset of absorption increases and hence band gap decreases (1.47 eV to 1.41 eV). Bulk heterojunction solar cells were fabricated with the blend of copolymer and phenyl-C61-butyric acid methyl ester (PCBM) as the active material and device parameters were extracted. The copolymer consists of alkyl thiophene exhibit higher open circuit voltage than the copolymer consisting of thiophene moiety. (c) 2012 Elsevier B.V. All rights reserved.

Investigation of phase separation in bulk heterojunction solar cells via supramolecular chemistry

In this work, we have prepared two donor-acceptor-donor (D-A-D) pi-conjugated oligomers to investigate the effect of phase separation on the performance of bulk heterojunction (BHJ) solar cells. These charge transfer low band gap pi-conjugated oligomers (TTB and NMeTTB) were synthesized by Knoevenagel condensation of terthiophenecarbaldehyde and barbiturate appended pyran derivative. The thin film morphology of both the oligomers and along with electron acceptor 6,6]-phenyl-C60-butyric acid methyl ester (PC61BM) was investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The blend of NMeTTB and PC61BM thin film yield highly ordered thin film, whereas there was clear phase separation between TTB and PC61BM in thin film. The BHJ solar cell was fabricated using a blend of NMeTTB and TTB with PC61BM acceptor in 1:1 ratio as active layer, and a power conversion efficiency of 1.8% was obtained. This device characteristic was compared with device having TTB:PC61BM as active layer, and large difference is observed in photocurrents. This poor performance of TTB in BHJ devices was attributed to the difference in the nanoscale morphology of the corresponding derivatives. We rationalize our findings based on the low charge carrier mobility in organic field-effect transistors and miscibility/phase separation parameter of binary components (oligomers and PC61BM) in the active layer of bulk heterojunction solar cells.

Channel II photocurrent quantification in narrow optical gap polymer-fullerene solar cells with complimentary acceptor absorption

Most charge generation studies on organic solar cells focus on the conventional mode of photocurrent generation derived from light absorption in the electron donor component (so called channel I). In contrast, relatively little attention has been paid to the alternate generation pathway: light absorption in the electron acceptor followed by photo-induced hole transfer (channel II). By using the narrow optical gap polymer poly(3,6-dithieno3,2-b] thiophen-2-yl)-2,5-bis(2-octyldodecyl)-pyrrolo- 3,4-c]pyrrole-1,4-dione-5',5 `'-diyl-alt-4,8-bis(dodecyloxy) benzo1,2-b:4,5-b'] dithiophene-2,6-diyl with two complimentary fullerene absorbers; phenyl-C-61-butyric acid methyl ester, and phenyl-C-71-butyric acid methyl ester (70-PCBM), we have been able to quantify the photocurrent generated each of the mechanisms and find a significant fraction (>30%), which is derived in particular from 70-PCBM light absorption.

Algal biofuel: bountiful lipid from Chlorococcum sp proliferating in municipal wastewater

Algae biofuel have emerged as viable renewable energy sources and are the potential alternatives to fossil-based fuels in recent times. Algae have the potential to generate significant quantities of commercially viable biofuel apart from treating wastewater. Three algal species, viz. Chlorococcum sp., Microcystis sp. and Phormidium sp. proliferating in wastewater ponds were isolated and cultured in the laboratory myxotrophically under similar wastewater conditions. Chlorococcum sp. attained a mean biomass productivity of 0.09 g. I(-1)d(-1) with the maximum `biomass density of 1.33 g I-1 and comparatively higher lipid content of 30.55% (w/w) on the ninth day of the culture experiment. Under similar conditions Microcystis sp. and Phormidium sp. attained mean biomass productivities of 0.058 and 0.063 g I-1 d(-1) with a total lipid content of 8.88% and 18.66% respectively. Biochemical composition (carbohydrates, proteins, lipids and phosphates) variations and lipid accumulation studies were performed by comparison of the ratios of carbohydrate to protein; lipid to protein (L/P) and lipid to phosphates using attenuated total reflectance-Fourier transform infrared spectroscopy which showed higher L/P ratio during the stationary phase of algal growth. Composition analysis of fatty acid methyl ester has been performed using gas chromatography and mass spectrometry. Chlorococcum sp. with higher productivity and faster growth rate has higher lipid content with about 67% of saturated fatty acid dominated by palmitate (36.3%) followed by an unsaturate as linoleate (14%) and has proved to be an economical and viable feedstock for biofuel production compared to the other wastewater-grown species.

A promising ketone containing alternating copolymer for organic photovoltaics

An alternating copolymer containing dithienylcyclopentadienone, thiophene and benzothiadiazole was synthesized by palladium (0) catalyzed Stille coupling reaction. Structural characterization of the synthesized alternating copolymer was carried out by NMR and FTIR spectroscopy. This solution processable copolymer shows an excellent thermal stability and has a broad absorption range from 300-800 nm. High LUMO energy level and low band gap of the synthesized copolymers suggest that, this copolymer will be a better donor material for application in organic photovoltaics. Particle size analysis and molecular weight determination of the synthesized copolymer through dynamic light scattering experiment indicates that, high molecular weight copolymer was obtained by this polymerization route. Photovoltaic devices were fabricated from the blend of copolymer and phenyl-C61- butyric acid methyl ester as the active material. Fabricated photovoltaic device results show that this alternating copolymer is a promising candidate for use in organic photovoltaics.

Strategy for Enhancing the Dielectric Constant of Organic Semiconductors Without Sacrificing Charge Carrier Mobility and Solubility

Current organic semiconductors for organic photovoltaics (OPV) have relative dielectric constants (relative permittivities, epsilon(r)) in the range of 2-4. As a consequence, Coulombically bound electron-hole pairs (excitons) are produced upon absorption of light, giving rise to limited power conversion efficiencies. We introduce a strategy to enhance epsilon(r) of well-known donors and acceptors without breaking conjugation, degrading charge carrier mobility or altering the transport gap. The ability of ethylene glycol (EG) repeating units to rapidly reorient their dipoles with the charge redistributions in the environment was proven via density functional theory (DFT) calculations. Fullerene derivatives functionalized with triethylene glycol side chains were studied for the enhancement of epsilon(r) together with poly(p-phenylene vinylene) and diketo-pyrrolopyrrole based polymers functionalized with similar side chains. The polymers showed a doubling of epsilon(r) with respect to their reference polymers in identical backbone. Fullerene derivatives presented enhancements up to 6 compared with phenyl-C-61-butyric acid methyl ester (PCBM) as the reference. Importantly, the applied modifications did not affect the mobility of electrons and holes and provided excellent solubility in common organic solvents.

Zinc oxide nanostructures and high electron mobility nanocomposite thin film transistors

This paper reports on the synthesis of zinc oxide (ZnO) nanostructures and examines the performance of nanocomposite thin-film transistors (TFTs) fabricated using ZnO dispersed in both n- and p-type polymer host matrices. The ZnO nanostructures considered here comprise nanowires and tetrapods and were synthesized using vapor phase deposition techniques involving the carbothermal reduction of solid-phase zinc-containing compounds. Measurement results of nanocomposite TFTs based on dispersion of ZnO nanorods in an n-type organic semiconductor ([6, 6]-phenyl-C61-butyric acid methyl ester) show electron field-effect mobilities in the range 0.3-0.6 cm2V-1 s-1. representing an approximate enhancement by as much as a factor of 40 from the pristine state. The on/off current ratio of the nanocomposite TFTs approach 106 at saturation with off-currents on the order of 10 pA. The results presented here, although preliminary, show a highly promising enhancement for realization of high-performance solution-processable n-type organic TFTs. © 2008 IEEE.

Cooperative properties of lipid bilayers : collective director fluctuations and the effects of hydrophobic mismatch in protein/lipid membrane systems

Cooperative director fluctuations in lipid bilayers have been postulated for many years. ^2H-NMR T_1^(-1), T_(1P)^(-1) , and T_2^(-1); measurements have been used identify these motions and to determine the origin of increased slow bilayer motion upon addition of unlike lipids or proteins to a pure lipid bilayer.

The contribution of cooperative director fluctuations to NMR relaxation in lipid bilayers has been expressed mathematically using the approach of Doane et al.^1 and Pace and Chan.^2 The T_2^(-1)’s of pure dimyristoyllecithin (DML) bilayers deuterated at the 2, 9 and 10, and all positions on both lipid hydrocarbon chains have been measured. Several characteristics of these measurements indicate the presence of cooperative director fluctuations. First of all, T_2^(-1) exhibits a linear dependence on S2/CD. Secondly, T_2^(-1) varies across the ^2H-NMR powder pattern as sin^2 (2, β), where , β is the angle between the average bilayer director and the external magnetic field. Furthermore, these fluctuations are restricted near the lecithin head group suggesting that the head group does not participate in these motions but, rather, anchors the hydrocarbon chains in the bilayer.

T_2^(-1)has been measured for selectively deuterated liquid crystalline DML hilayers to which a host of other lipids and proteins have been added. The T_2^(-1) of the DML bilayer is found to increase drastically when chlorophyll a (chl a) and Gramicidin A' (GA') are added to the bilayer. Both these molecules interfere with the lecithin head group spacing in the bilayer. Molecules such as myristic acid, distearoyllecithin (DSL), phytol, and cholesterol, whose hydrocarbon regions are quite different from DML but which have small,neutral polar head groups, leave cooperative fluctuations in the DML bilayer unchanged.

The effect of chl a on cooperative fluctuations in the DML bilayer has been examined in detail using ^2H-NMR T_1^(-1), T_(1P)^(-1) , and T_2^(-1); measurements. Cooperative fluctuations have been modelled using the continuum theory of the nematic state of liquid crystals. Chl a is found to decrease both the correlation length and the elastic constants in the DML bilayer.

A mismatch between the hydrophobic length of a lipid bilayer and that of an added protein has also been found to change the cooperative properties of the lecithin bilayer. Hydrophobic mismatch has been studied in a series GA' / lecithin bilayers. The dependence of 2H-NMR order parameters and relaxation rates on GA' concentration has been measured in selectively deuterated DML, dipalmitoyllecithin (DPL), and DSL systems. Order parameters, cooperative lengths, and elastic constants of the DML bilayer are most disrupted by GA', while the DSL bilayer is the least perturbed by GA'. Thus, it is concluded that the hydrophobic length of GA' best matches that of the DSL bilayer. Preliminary Raman spectroscopy and Differential Scanning Calorimetry experiments of GA' /lecithin systems support this conclusion. Accommodation of hydrophobic mismatch is used to rationalize the absence of H_(II) phase formation in GA' /DML systems and the observation of H_(II) phase in GA' /DPL and GA' /DSL systems.

1. J. W. Doane and D. L. Johnson, Chem. Phy3. Lett., 6, 291-295 (1970). 2. R. J. Pace and S. I. Chan, J. Chem. Phy3., 16, 4217-4227 (1982).

Avaliação da acidez de bio-óleos obtidos pela pirólise de óleos vegetais pós-consumo

O descarte irregular do óleo vegetal pós-consumo diretamente na rede de esgoto vem causando grandes problemas para o meio ambiente. Atualmente, essa problemática tem se intensificado devido ao aumento de produção e consumo destes óleos, o que por conseqüência aumenta o despejo desordenado. No presente estudo foi realizada a obtenção do bio-óleo a partir da pirólise térmica em atmosfera de nitrogênio, a 400C, por 20 minutos, do óleo vegetal pós-consumo, provenientes das seguintes oleoginosas: soja, milho, girassol e canola. As pirólises não-catalíticas apresentaram uma geração média entre 40 e 50% de um bio-óleo, de elevado índice de acidez, 81,8 mg NaOH/g. Na pirólise catalítica, a argila ácida K10 foi o catalisador que apresentou melhor eficácia para geração de um bio-óleo de menor índice de acidez. A concentração ótima do catalisador foi de 5%(m/m), gerando 482 % de um bio-óleo com índice de acidez de 43,8 mg NaOH/g. A caracterização dos líquidos pirolíticos obtidos foi realizada através da técnica de espectrofotometria na região do infravermelho (FTIR) e cromatografia em fase gasosa acoplada a espectrômetro de massas (CG/EM) que monstraram que a trioleína, o triglicerídeo do ácido oléico, foi craqueado, gerando o hexadecanoato de octadecila e o oleato de eicosila, ésteres do respectivo ácido graxo

Avaliação da aspirina e do ácido cafeico fenetil estersobre o reparo tecidual cutâneo

Numerosos modelos in vitro e in vivo foram desenvolvidos para estudar o reparo de lesões e identificar os mecanismos chave deste processo. Visando avaliar o processo de cicatrização utilizamos um modelo de lesão excisional total e um modelo de queimadura promovida por escaldamento. No estudo utilizando o modelo de lesão excisional total, abordamos o uso da aspirina (um inibidor não seletivo da COX) e seu efeito diferenciado sobre os sexos na cicatrização cutânea de camundongos. Observamos que os grupos fêmea controle e tratado apresentaram contração atrasada comparado aos grupos macho controle e tratado, respectivamente. Entre os grupos fêmea e macho controles, as fêmeas apresentaram menor atividade da mieloperoxidase e menor quantidade de células MIF-positivas do que os machos controle. Já entre os grupos fêmea e macho tratados, foi observado que nas fêmeas tratadas, a atividade da mieloperoxidase e a quantidade de macrófagos F4/80-positivos estavam maiores do que no grupo macho tratado. Ainda entre os grupos tratados, as fêmeas apresentaram menores níveis de hidroxiprolina e maior expressão proteica de vWF e VEGF comparado aos machos. No estudo das lesões causadas por queimadura, avaliamos as propriedades anti- inflamatórias e antioxidantes do ácido cafeico fenetil ester (CAPE) no reparo destas lesões e observamos que em 7, 14, 21 e 70 dias após a queimadura, o grupo queimado+CAPE apresentou menor área lesada, além de menor atividade da mieloperoxidase e dos níveis de nitrito do que o grupo queimado. Também foi observado que no grupo queimado+CAPE a expressão proteica de CD68 e de PECAM-1 estava reduzida comparada ao grupo queimado. Analisando os parâmetros de dano oxidativo foi observado que os níveis de MDA e de proteínas carboniladas estavam menores no grupo queimado+CAPE do que no grupo queimado, tanto no plasma quanto na lesão. Em suma, nosso estudo avaliou o processo de cicatrização de dois modelos de lesão, em roedores de diferentes espécies e em abordagens distintas. No modelo de lesão excisional total em camundongos observamos que a administração da aspirina prejudicou o processo de cicatrização em camundongos Balb/c fêmeas, mas não afetou esse processo nos machos da mesma linhagem, o que pode ser explicado pela redução dos níveis de estrógenos nas fêmeas. A utilização do CAPE na cicatrização de queimaduras em ratas comprovou sua eficácia anti-inflamatória e antioxidante devido ao grupo queimado+CAPE ter apresentado maior taxa de cicatrização, redução da resposta inflamatória, além da redução do dano oxidativo em lipídeos e proteínas comparado ao grupo queimado.

Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.