Structure control of poly(p-phenylene vinylene) in layer-by-layer films by deposition on a charged poly(o-methoxyaniline) cushion

In this paper, we demonstrate that the intrinsic electric field created by a poly(o-methoxyaniline) (POMA) cushion layer hinders the changes in molecular conformation of poly(p-phenylenevinylene) (PPV) in layer-by-layer with dodecylbenzene sulfonic acid (DBS). This was modeled with density functional theory (DFT) calculations where an energy barrier hampered molecular movements of PPV segments when they were subjected to an electric field comparable to that caused by a charged POMA layer. With restricted changes in molecular conformation, the PPV film exhibited Franck-Condon transitions and the photoexcitation spectra resembled the absorption spectra, in contrast to PPV/DBS films deposited directly on glass, with no POMA cushion. Other effects from the POMA cushion were the reduced number of structural defects, confirmed with Raman spectroscopy, and an enhanced PPV emission at high temperatures (300 K) in comparison with the films on bare glass. The positive effects from the POMA cushion may be exploited for enhanced opto-electronic devices, especially as the intrinsic electric field may assist in separating photoexcited electron-hole pairs in photovoltaic devices. © 2013 American Institute of Physics.

Effects of thermal annealing on polymer photovoltaic cells with buffer layers and in situ formation of interfacial layer for enhancing power conversion efficiency

We have investigated the effects of thermal annealing before and after cathode deposition on poly(3-hexylthiophene)(P3HT)/[6,6]-phenyl C61-butyric acid methyl ester (PCBM) blend photovoltaic cells with different cathode buffer layers. The introduction of cathode buffer layer such as lithium fluoride (LiF) and calcium oxide (CaO) in pre-annealing cells can increase the open-circuit voltage (V-oc) and the power conversion efficiency (PCE). Post thermal annealing after cathode deposition further enhanced the PCE of the cells with LiF/Al cathode.

Effects of fullerene solubility on the crystallization of poly(3-hexylthiophene) and performance of photovoltaic devices

The substantial crystallization suppression of poly(3-hexylthiophene) (P3HT) in the untreated P3HT:C60 composite film prepared from o-dichlorobenzene (ODCB) solution has been revealed. Besides, the effective conjugation length of P3HT in this composite has been nearly maintained to that in the solution. The different crystallization behaviors of P3HT in its composites with C60 and [6,6]-phenyl C-61 butyric acid methyl ester (PCBM) are mainly attributed to the relative solubility of C60 and PCBM with respect to P3HT in ODCB. The solution to overcome this disadvantage of chain conformation and crystallinity of P3HT in the composite with C60 is thus proposed and finalized by resorting to the addition of low volatile solvent with much higher solubility of C60 than P3HT into the main solvent used, so as P3HT can crystallize before C60 forms crystallites in the solution. The feasibility of this approach has been proven by the improved efficiency of devices based on composites of P3HT and the low cost C60 without resorting to post-treatments.

On the Analytical Approach to Present Engineering Problems: Photovoltaic Systems Behavior, Wind Speed Sensors Performance, and High-Speed Train Pressure Wave Effects in Tunnels

At present, engineering problems required quite a sophisticated calculation means. However, analytical models still can prove to be a useful tool for engineers and scientists when dealing with complex physical phenomena. The mathematical models developed to analyze three different engineering problems: photovoltaic devices analysis; cup anemometer performance; and high-speed train pressure wave effects in tunnels are described. In all cases, the results are quite accurate when compared to testing measurements.

Ultrafast charge-transfer in organic photovoltaic interfaces: geometrical and functionalization effects

Understanding the microscopic mechanisms of electronic excitation in organic photovoltaic cells is a challenging problem in the design of efficient devices capable of performing sunlight harvesting. Here we develop and apply an ab initio approach based on time-dependent density functional theory and Ehrenfest dynamics to investigate photoinduced charge transfer in small organic molecules. Our calculations include mixed quantum–classical dynamics with ions moving classically and electrons quantum mechanically, where no experimental external parameter other than the material geometry is required. We show that the behavior of photocarriers in zinc phthalocyanine (ZnPc) and C60 systems, an effective prototype system for organic solar cells, is sensitive to the atomic orientation of the donor and the acceptor units as well as the functionalization of covalent molecules at the interface. In particular, configurations with the ZnPc molecules facing on C60 facilitate charge transfer between substrate and molecules that occurs within 200 fs. In contrast, configurations where ZnPc is tilted above C60 present extremely low carrier injection efficiency even at longer times as an effect of the larger interfacial potential level offset and higher energetic barrier between the donor and acceptor molecules. An enhancement of charge injection into C60 at shorter times is observed as binding groups connect ZnPc and C60 in a dyad system. Our results demonstrate a promising way of designing and controlling photoinduced charge transfer on the atomic level in organic devices that would lead to efficient carrier separation and maximize device performance.

New insights into rebound effects : theory and empirical evidence

The main objective of the thesis is to seek insights into the theory, and provide empirical evidence of rebound effects. Rebound effects reduce the environmental benefits of environmental policies and household behaviour changes. In particular, win-win demand side measures, in the form of energy efficiency and household consumption pattern changes, are seen as ways for households and businesses to save money and the environment. However, these savings have environmental impacts when spent, which are known as rebound effects. This is an area that has been widely neglected by policy makers. This work extends the rebound effect literature in three important ways, (1) it incorporates the potential for variation of rebound effects with household income level, (2) it enables the isolation of direct and indirect effects for cases of energy efficient technology adoption, and examines the relationship between these two component effects, and (3) it expands the scope of rebound effect analysis to include government taxes and subsidies. MACROBUTTON HTMLDirect Using a case study approach it is found that the rebound effect from household consumption pattern changes targeted at electricity is between 5 and 10%. For consumption pattern changes with reduced vehicle fuel use, the rebound effect is in the order of 20 to 30%. Higher income households in general are found to have a lower total rebound effect; however the indirect effect becomes relatively more significant at higher household income levels. In the win-lose case of domestic photovoltaic electricity generation, it is demonstrated that negative rebound effects can occur, which can potentially amplify the environmental benefits of this action. The rebound effect from a carbon tax, which occurs due to the re-spending of raised revenues, was found to be in the range of 11-32%. Taxes and transfers between households of different income levels also have environmental implications. For example, a more progressive tax structure, with increased low income welfare payments is likely to increase greenhouse gas emissions. Subsidies aimed at encouraging environmentally friendly consumption habits are also subject to rebound effects, as they constitute a substitution of government expenditure for household expenditure. For policy makers, these findings point to the need to incorporate rebound effects in the environmental policy evaluation process.’

Bias-dependent effects in planar perovskite solar cells based on CH3NH3PbI3−xClx films

A unique bias-dependent phenomenon in CH3NH3PbI3−xClx based planar perovskite solar cells has been demonstrated, in which the photovoltaic parameters derived from the current–voltage (I–V) curves are highly dependent on the initial positive bias of the I–V measurement. In FTO/CH3NH3PbI3−xClx/Au devices, the open-circuit voltage and short-circuit current increased by ca. 337.5% and 281.9% respectively, by simply increasing the initial bias from 0.5 V to 2.5 V.

About the transparent electrode of the organic photovoltaic cells

Electrodes and the nature of their contact with organic materials play a crucial role in the realization of efficient optoelectronic components. Whether the injection (organic light-emitting diodes - OLEDs) or collection (organic photovoltaic cells - OPV cells) of carriers, contacts must be as efficient as possible. To do this, it is customary to refer to electrode surface treatment and/or using a buffer layer all things to optimize the contact. Efficiency of organic photovoltaic cells based on organic electron donor/organic electron acceptor junctions can be strongly improved when the transparent conductive anode is coated with a buffer layer (ABL). We show that an ultra-thin gold (0.5 nm) or a thin molybdenum oxide (3-5 nm) can be used as efficient ABL. However, the effects of these ABL depend on the highest occupied molecular orbital (HOMO) of different electron donors of the OPV cells. The results indicate that, in the case of metal ABL, a good matching between the work function of the anode and the highest occupied molecular orbital of the donor material is the major factor limiting the hole transfer efficiency. Indeed, gold is efficient as ABL only when the HOMO of the organic donor is close to its work function Phi(Au). MoO3 has a wider field of application as ABL than gold. The role of the oxide is not so clearly understood than that of Au, different models proposed to interpret the experimental results are discussed.

Physics and chemistry of CdTe/CdS thin film heterojunction photovoltaic devices: fundamental and critical aspects

Among the armoury of photovoltaic materials, thin film heterojunction photovoltaics continue to be a promising candidate for solar energy conversion delivering a vast scope in terms of device design and fabrication. Their production does not require expensive semiconductor substrates and high temperature device processing, which allows reduced cost per unit area while maintaining reasonable efficiency. In this regard, superstrate CdTe/CdS solar cells are extensively investigated because of their suitable bandgap alignments, cost effective methods of production at large scales and stability against proton/electron irradiation. The conversion efficiencies in the range of 6-20% are achieved by structuring the device by varying the absorber/window layer thickness, junction activation/annealing steps, with more suitable front/back contacts, preparation techniques, doping with foreign ions, etc. This review focuses on fundamental and critical aspects like: (a) choice of CdS window layer and CdTe absorber layer; (b) drawbacks associated with the device including environmental problems, optical absorption losses and back contact barriers; (c) structural dynamics at CdS-CdTe interface; (d) influence of junction activation process by CdCl2 or HCF2Cl treatment; (e) interface and grain boundary passivation effects; (f) device degradation due to impurity diffusion and stress; (g) fabrication with suitable front and back contacts; (h) chemical processes occurring at various interfaces; (i) strategies and modifications developed to improve their efficiency. The complexity involved in understanding the multiple aspects of tuning the solar cell efficiency is reviewed in detail by considering the individual contribution from each component of the device. It is expected that this review article will enrich the materials aspects of CdTe/CdS devices for solar energy conversion and stimulate further innovative research interest on this intriguing topic.

Design and synthesis of new low band gap organic semiconductors for photovoltaic applications

Donor-acceptor (D-A) conjugated polymers have attracted a good deal of attention in recent years. In D-A systems, the introduction of electron withdrawing groups reduces E-g by lowering the LUMO levels whereas, the introduction of electron donating groups reduces E-g by raising the HOMO levels. Also, conjugated polymers with desired HOMO and LUMO energy levels could be obtained by the proper selection of donor and acceptor units. Because of this reason, D-A conjugated polymers are emerging as promising materials particularly for polymer light emitting diodes (PLEDs) and polymer solar cells (PSCs). We report the design and synthesis of four new narrow band gap donor-acceptor (D-A) conjugated polymers, PTCNN, PTCNF, PTCNV and PTCNO, containing electron donating 3,4-didodecyloxythiophene and electron accepting cyanovinylene units. The effects of further addition of electron donating and electron withdrawing groups to the repeating unit of a D-A conjugated polymer (PTCNN) on its optical and electrochemical properties are discussed. The studies revealed that the nature of D and A units as well as the extent of alternate D-A structure influences the optical and the electrochemical properties of the polymers. All the polymers are thermally stable up to a temperature of 300 degrees C under nitrogen atmosphere. The electrochemical studies revealed that the polymers possess low-lying HOMO energy levels and low-lying LUMO energy levels. In the UV-Vis absorption study, the polymer films displayed broad absorption in the wavelength region of 400-700 nm. The polymers exhibited low optical band gaps in the range 1.70 - 1.77 eV.

Modelling of optical transport behavior of organic photovoltaic devices with nano-pillar transparent conducting electrodes

Optical transport behavior of organic photo-voltaic devices with nano-pillar transparent electrodes is investigated in this paper in order to understand possible enhancement of their charge-collection efficiency. Modeling and simulations of optical transport due to this architecture show an interesting regime of length-scale dependent optical characteristics. An electromagnetic wave propagation model is employed with simulation objectives toward understanding the mechanism of optical scattering and waveguide effects due to the nano-pillars and effective transmission through the active layer. Partial filling of gaps between the nano-pillars due to the nano-fabrication process is taken into consideration. Observations made in this paper will facilitate appropriate design rules for nano-pillar electrodes. (C) 2014 AIP Publishing LLC.

One-dimensional modulation instability of broad optical beams in biased photorefractive-photovoltaic crystals under steady-state conditions

We present a comprehensive study of the one-dimensional modulation instability of broad optical beams in biased photo refractive-photovoltaic crystals under steady-state conditions. We obtain the one-dimensional modulation instability growth rate by globally treating the space-charge field and by considering distinction between values of Eo in nonlocal effects and local effects in the space-charge field, where Eo is the field constant correlated with terms in the space-charge field, which depends on the external bias field, the bulk photovoltaic effect, and the ratio of the optical beam's intensity to that of the dark irradiance. The one-dimensional modulation instability growth rate in local effects can be determined from that in nonlocal effects. When the bulk photovoltaic effect is neglectable, irrespective of distinction between values of Eo in nonlocal effects and local effects in the space-charge field, the one-dimensional modulation instability growth rates in nonlocal effects and local effects are those of broad optical beams studied previously in biased photorefractive-nonphotovoltaic crystals. When the external bias field is absent, the one-dimensional modulation instability growth rates in nonlocal effects and local effects predict those of broad optical beams in open- and closed-circuit photorefractive-photovoltaic crystals. (c) 2004 Elsevier B.V. All rights reserved.

Controlled phase separation for efficient energy conversion in dye/polymer blend bulk heterojunction photovoltaic cells

Low-cost photovoltaic energy conversion using conjugated polymers has achieved great improvement due to the invention of organic bulk heterojunction. in which the nanoscale phase separation of electron donor and acceptor favors realizing efficient charge separation and collection. We investigated the polymer photovoltaic cells using N, N'-bis(1-ethylpropyl)-3,4,9,10-perylene bis(tetracarboxyl diimide)/poly(3-hexyl thiophene) blend as an active layer. It is found that processing conditions for the blend films have major effects on its morphology and hence the energy conversion efficiency of the resulting devices. By optimizing the processing conditions, the sizes of donor/acceptor phase separation can be adjusted for realizing efficient charge separation and collection. The overall energy conversion efficiency of the photovoltaic cell processed with optimized conditions increases by nearly 40% compared to the normally spin-coated and annealed cell.

An Extremely High Molar Extinction Coefficient Ruthenium Sensitizer in Dye-Sensitized Solar Cells: The Effects of pi-Conjugation Extension

We report a heteroleptic ruthenium complex (007) featuring the electron-rich 5-octyl-2,2'-bis(3,4-ethylenedioxythiophene) moiety conjugated with 2,2-bipyridine and exhibiting 10.7% power conversion efficiency measured at the AM1.5G conditions, thanks to the enhanced light-harvesting that is closely related to photocurrent. This C107 sensitizer has an extremely high molar extinction coefficient,of 27.4 x 10(3) M-1 cm(-1) at 559 nm in comparison to its analogue C103 (20.5 x 10(3) M-1 cm(-1) at 550 nm) or Z907 (12.2 x 10(3) M(-1)cm(-1) at 521 nm) with the corresponding 5-hexyl-3,4-ethylenedioxythiopliene- or nonyl-substituted bipyridyl unit. The augmentation of molar extinction coefficients and the bathochromic shift of low-energy absorption peaks along with the pi-conjugation extension are detailed by TD-DFT calculations. The absorptivity of mesoporous titania films grafted with Z907, C103, or C107 sublinearly increases with the molar extinction coefficient of sensitizers, which is consistent with the finding derived from the surface coverage measurements that the packing density of those sensitizers decreases with the geometric enlargement of ancillary ligands.