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The effect of altering the acceptor and exchanging a key atom in the polymer structure on the extent of non-Langevin (suppressed) recombination has been examined using the polymer/fullerene photovoltaic blend PDTSiTTz:PC60BM. Time-of-flight data show that changing the acceptor from PC60BM to PC70BM maintains the non-Langevin recombination. In contrast, altering the donor polymer by exchanging the silicon bridging atom for a carbon considerably reduces the non-Langevin behavior. Importantly, the addition of a processing additive, diiodooctane (DIO), allows a partial recovery of this non-Langevin recombination. The addition of DIO also decreases the ionization potential of the polymer, which not only explains the drop in open circuit voltage but may also contribute to the partial recovery of non-Langevin behavior observed. It is proposed that localized, more crystalline areas of lower ionization potential (or higher electron affinity) within a mixed/amorphous phase may act as energy sinks for the holes (ele...

The role of charge transfer (CT) states in organic photovoltaic systems has been debated in the recent literature. In this paper the device performances of two structurally analogous polymers PDTSiTTz (also known as KP115) and PCPDTTTz blended with PCBM are investigated, focusing on the effect the processing additive diiodooctane (DIO) has on morphology, charge photogeneration, and, in particular, the CT state characteristics. While DIO has a considerable beneficial effect for PCPDTTTz: PCBM photovoltaic devices, negligible effects are observed for PDTSiTTz: PCBM devices. An emissive CT state able to be quenched by DIO was observed for PCPDTTTz: PCBM, despite relatively small morphological changes. This is only the second instance of CT state quenching by a processing additive to be reported. Formation of an emissive CT state is therefore a loss pathway for PCPDTTTz: PCBM, which can be alleviated through the use of DIO to increase the proportion of CT states that dissociate into free charges. Conversely, the CT state of PDTSiTTZ:PCBM is weak and short-lived, with the DIO having little effect. The CT state dissociates more efficiently for this higher crystallinity system, leading to less evidence of emissive CT state recombination, and high charge photogeneration yields and device efficiencies.

A critical problem in the design of materials for organic photovoltaics is quantifying the driving force needed for efficient charge separation without losses associated with a large overpotential. Here, we directly measured the effect of the molecular driving force on the charge transfer rate in films of low-bandgap push–pull type polymers mixed with a series of fullerene-based molecular acceptors using broadband near-infrared transient absorption spectroscopy. By systematically tuning the absolute energy levels of the donor and acceptor, as well as the relative offset between them, we determine the minimum voltage loss required to achieve a high short circuit current. A molecular donor–acceptor framework provides a quantitative description of the charge transfer rate constants in our system and describes the scaling of the photogenerated current with S1–LUMO energy offset. These results point to potential efficiency gains for high performing polymer devices through recovery of additional voltage without...

Light induced degradation has been observed in the performance of organic solar cells in the absence of oxygen and a detailed analysis of the effect of this photodegradation on optical and electrical features has been accomplished. This photodegradation study has been performed on encapsulated photovoltaic blend devices comprised of the silole-based donor–acceptor polymer KP115 blended with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). Photodegradation induces an almost 20% decrease in power conversion efficiency, primarily as a result of a reduction in short circuit current, JSC. The initial burn-in phase of the photodegradation has been examined using a combination of transient absorption spectroscopy and charge extraction measurements, including photo-CELIV (charge extraction by linearly increasing voltage) and time-resolved charge extraction using a nanosecond switch. These measurements reveal a bimodal KP115 polaron population, comprised of both delocalised and localised/trapped charge carriers. The photodegradation results are consistent with an alteration of this bimodal KP115 polaron population, with the polarons becoming trapped in a broader, deeper density of localised states. Under laser illumination and at open circuit conditions, this enhanced trapping after light soaking inhibits charges from undergoing bimolecular recombination, leading to higher extracted charge densities at long times. At the lower charge densities operating at short circuit conditions and under continuous white light illumination, where bimolecular recombination is much less significant, the JSC decreases after light soaking due to a reduction in the efficiency of trapped charge carrier extraction.

Organic photovoltaic devices based on the donor:acceptor blend of poly[ N -9″-heptadecanyl-2,7-carbazole- alt -5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) and [6,6]-phenyl C 61 butyric acid methyl ester (PCBM) have received considerable attention in recent years due to their high power conversion efficiencies and the ability to achieve close to 100% internal quantum efficiency. However, the highest efficiencies were all attained using active layers of less than 100 nm, which is not ideal for either maximised potential performance or commercial viability. Furthermore, more recent reports have documented significant charge carrier trapping in these devices. In this paper two charge extraction techniques (photo-CELIV and time-of-flight) have been used to investigate the mobility and recombination behaviour in a series of PCDTBT:PCBM devices. The results not only confirm significant charge carrier trapping in this system, but also reveal close to Langevin-type bimolecular recombination. The Langevin recombination causes a short charge carrier lifetime that results in a short drift length. The combination of these two characteristics (trapping and fast bimolecular recombination) has a detrimental effect on the charge extraction efficiency when active layers greater than ∼100 nm are used. This accounts for the pronounced decrease in fill factor with increasing active layer thickness that is typically observed in PCDTBT:PCBM devices.

The transparent top contact layer of a solar cell is a distributed resistance that cannot be easily represented mathematically. We have used a finite element model to calculate the current distribution in this transparent layer. The calculation gives the voltage drop along the layer as well as the resulting reduction in the current generated in the active layer of the solar cell. IV curves generated by the model are used to investigate various methods of experimentally determining series resistance. It is found that the suns- V oc method is the most accurate. A fit of the finite element model to experimental IV data from an organic solar cell is used as an example of obtaining solar cell model parameters.

The UV–Vis absorption spectra and the luminescence properties of poly(N-octyl-2,7-carbazole) (POC) and poly(N-octyl-2,7-carbazole-alt-9,9-dioctyl-2,7-fluorene) PCF have been investigated in solution and in the solid state (thin films). No aggregate and/or excimer formation has been detected in these polymeric systems. From time-resolved fluorescence measurements in solution and in the solid state, the fluorescence efficiencies of the thin films have been estimated. It is found that the fluorescence efficiencies of these polycarbazoles in the solid state are quenched, as compared to those measured in fluid solutions, but remain relatively high (φF≅0.40), making them promising materials for electroluminescent devices.

A detailed analysis of the optical and photophysical properties of 2,7-bis(phenylene)-9,9-dioctylfluorene (PFP), 2,7-bis(biphenylene)-9,9-dioctylfluorene (BPFBP), 2,7-bis(2-thienyl)-9,9-dioctylfluorene (TFT), and 2,7-bis-(2,2'-bithien-5-yl)-9,9-dioctylfluorene (BTFBT) in various environments are reported. The optical properties of the free molecules isolated in an alkane matrix are obtained and discussed in terms of the conformation adopted by each derivative in the electronic ground and first excited states. Also, conformational changes are responsible for the optical changes observed at high concentrations in an isopentane glass at 77 K. High quantum yields of all the oligofluorenes at 77 K indicate the absence of quenching effects such as excitonic or aggregation effects. The similar spectral and photophysical properties in matrix and glass environments are explained by the disorder introduced in oligofluorenes by long octyl chains at the C-9 position of the fluorene moiety. To study the effect of intermolecular interactions in the solid state, we recorded the spectra of thin films of these derivatives. The much red-shifted emission band in the solid state cannot be explained by conformational changes and has its origin in the π-stacking of conjugated oligomers in their relaxed S 1 state. As an evidence to show the importance of the role played by octyl chains at the C-9 position of the fluorene moiety, we synthesized two new model compounds: one, without octyl chains at the C-9 position of the fluorene moiety, 2,7-bis(2-thienyl)fluorene (TFTWC) and another with more octyl chains, 1,4-bis(9,9-dioctylfluoren-2-yl)phenyl (FPF). The spectral properties of these derivatives have been studied at room temperature and at 77 K. These systems serve as excellent examples to show the effect of intermolecular interactions on optical properties of oligofluorenes.

Objectives: Clinicians have reported that their patients complain that their mandibular two-implant overdentures (IOD) rotate. Therefore, we studied the frequency and severity of rotation of IODs with two-ball attachments, how rotation may influence perceived satisfaction ratings of chewing ability, and the factors that are involved in the rotation of IODs. Material and methods: Seventy-nine participants were recruited and asked to rate their general satisfaction of their IODs, as well as their ability to chew foods, the existence of any mandibular denture rotation, and to what degree denture rotation bothered them. Data on participant sociodemographic, anatomical, and prosthesis characteristics were also collected. Student’s t-test and logistic regression analyses were performed to analyze the differences between participants who did (R group) and did not report (NR group) denture rotation. Results: Thirty-seven of 79 participants were aware of rotational movement in their IODs. These patients were significantly less satisfied with their chewing ability than those who felt no rotation (69.1mm R group vs. 82.9mm), and discomfort caused by the rotation bothered them moderately (39/100mm). The multivariate logistic regression analysis revealed that the arrangement of the anterior teeth and the length of the denture are significantly associated with awareness of denture rotation. Thirty-eight percent in the R group and 31% in the NR group had non-scheduled visits. Conclusions: Rotational movement with a mandibular two-IOD has a negative effect on perceived chewing ability and is associated with anterior tooth arrangement and denture length.

A low band-gap alternating copolymer of indolocarbazole and benzothiadiazole-cored oligothiophene demonstrated balanced crystallinity and solubility; a solar cell combining this polymer with PC(61)BM in a preliminary test demonstrated power conversion efficiencies of 3.6%.

Bulk heterojunction organic solar cells based on conjugated polymers and soluble fullerene derivatives have been intensively studied due to their simple device structure, easy thin-film casting process, low fabrication cost, and high power conversion efficiency. To further enhance the efficiency, it is of paramount importance to develop new p-type polymeric semiconductors with high charge mobility and narrow energy band gaps. In this paper, we report on an innovative way to synthesize low band-gap conjugated polymers with high crystallinity and reasonable solubility for wet process by using electron-acceptor cored regioregular oligothiophenes as building blocks. These novel building blocks can copolymerize with coplanar fused aromatic compounds, such as indolo[3,2-b]carbazole, to form crystalline polymers with enhanced interchain interaction. Two alternating copolymers P(InCzThnBTD) (n = 2-3) synthesized in this work show much narrower optical band gaps than widely used regioregular P3HT. In addition, the first ionization energy of both synthesized polymers remains high at ~5.17 eV, which is important to achieve large open-circuit voltage (Voc) and improve air stability. Remarkably, the bulk heterojunction photovoltaic (PV) cells fabricated from P(InCzTh2BTD) and PC61BM exhibited a promising PV performance with a PCE = 3.6 %, Voc = 0.69 V, Jsc = 9.17 mA/cm2, and FF = 0.57.

Recruitment of older adults into research studies is challenging and, as a consequence, the recruitment period is often extended and more expensive than planned. This study monitored the effectiveness (number of subjects attracted) and cost of different recruitment strategies when recruiting edentulous elderly adults. Socio-demographic data were gathered and compared to 2001 Canadian census data. Advertisements in major Montreal newspapers attracted the most people (24.3%). However, the most economical recruitment method proved to be placement of ads in senior newspapers (dollar 73.74 per subject). The information gathered in this study will assist others in planning recruitment strategies for edentulous elderly populations.

We have fabricated organic field-effect transistors based on thin films of 2,7-carbazole oligomeric semiconductors 1,4-bis(vinyl-ene-(N-hexyl-2-carbazole))phenylene (CPC),1,4-bis(vinylene-(N'-methyl-7'-hexyl-2'-carbazole))benzene (RCPCR),N-hexyl-2,7-bis(vinylene-(N-hexyl-2-carbazole))carbazole (CCC), and N-methyl-2,7-bis(vinylene-(7-hexyl-N-methyl-2-carbazole))carbazole (RCCCR). The organic semiconductors are deposited by thermal evaporation on bare and chemically modified silicon dioxide surfaces (SiO 2 /Si) held at different temperatures varying from 25 to 200 °C during deposition. The resulting thin films have been characterized using UV-vis and Fourier-transform infrared spectroscopies, scanning electron microscopy, and X-ray diffraction, and the observed top-contact transistor performances have been correlated with thin-film properties. We found that these new it-conjugated oligomers can form highly ordered structures and reach high hole mobilities. Devices using CPC as the active semiconductor have exhibited mobilities as high as 0.3 cm 2 V - 1 s - 1 with on/off current ratios of up to 10 7 . These features make CPC and 2,7-carbazolenevinylene-based oligomers attractive candidates for device applications.

6,12-Dimethylindolo[3,2-b]carbazoles were prepared by Cadogan ring closure using N-alkyl-2-substituted carbazole precursor. X-ray analyses on 5,11-dioctyl-6,12-dimethylindolo[3,2-b]carbazole have demonstrated a coplanar molecular structure with an interesting π-stacking of the molecules. Organic field-effect transistor using the same molecule as an active layer has revealed promising features.

This study reports the first syntheses and characterization of 2,7-carbazolenevinylene-based oligomers and polymers. Their relatively straightforward syntheses are mainly based on Horner−Emmons or Knoevenagel coupling reaction leading to well-defined oligomers and polymers. As expected, introduction of vinylene and cyanovinylene unit into the polymer backbone decreases the band gap allowing a fine-tuning of the optical and electrical properties. These electroactive and photoactive organic materials exhibit promising performances in light-emitting devices and field-effect transistors. For instance, preliminary measurements using poly(N-(2-ethylhexyl)-2,7-carbazolenecyanovinylene-alt-2,5-dioctyloxy-1,4-phenylenevinylene) (PCCVP) have revealed orange-red emission with an intensity of 245 cd/m2 at 10 V, whereas p-type mobility of about 3.7 × 10-2 cm2/V·s and an on/off ratio as high as 106 were reached with 1,4-bis(vinylene-(N-hexyl-2-carbazole))phenylene (CPC).

This paper reports the fabrication and evaluation of light-emitting diodes using polyfluorene derivatives as emitter, which cover the entire visible spectral range. Depending on the composition of the copolymers, red (emission peak at 656 nm), green (488 nm) and blue (428 nm) emission was obtained without any excimer formation. The optimization of the device performances has been realized using a multilayered configuration which involves a spin-coated poly(ethylenedioxythiophene) doped with poly(styrene sulfonic acid) (PEDT–PSS) thin film on the ITO anode and an ultrathin lithium fluoride layer next to the Al cathode. These two layers improve the efficiency of the charge injection. Combining this device configuration with some additional charge-transporting molecules, luminances in the range of 50–300 cd m−2 have been obtained.

It is important to accurately measure the charge carrier lifetime, a crucial parameter that influences the collection efficiency in organic solar cells. Five transient and small perturbation experimental techniques that measure charge carrier lifetime are applied to a device composed of the polymer PDTSiTTz blended with the fullerene PCBM: time-resolved charge extraction (TRCE), transient absorption spectroscopy (TAS), photoinduced charge extraction by linearly increasing voltage (photo-CELIV), transient photovoltage, and electrochemical impedance spectroscopy. The motivation is to perform a comprehensive comparison of several different lifetime measurement techniques on the same device in order to assess their relative accuracy, applicability to operational devices, and utility in data analysis. The techniques all produce similar charge carrier lifetimes at high charge densities, despite previous suggestions that transient methods are less accurate than small perturbation ones. At lower charge densities an increase in the apparent reaction order is observed. This may be related to surface recombination at the contacts beginning to dominate, or an inhomogeneous charge distribution. A combination of TAS and TRCE appears suitable. TAS enables the investigation of recombination mechanisms at early times since it is not limited by RC (resistance-capacitance product) or charge extraction losses. Conversely, TRCE is useful particularly at low densities when other mechanisms, such as surface recombination, may occur.

A push-pull copolymer is presented which can be used in bulk heterojunction (BHJ) solar cells with active layers greater than 200 nm and fill factors above 60%. The efficiencies of most BHJ solar cells are limited by the fact that they have active layers which are between 60 and 110 nm. While this thickness regime enables peak quantum efficiencies (EQE) of 60%–70%, the ability to fabricate thicker devices would increase average EQE values and thus device efficiencies. Discovery of materials which can maintain high performance at large thicknesses will enable higher performance in BHJ hero cells and increase the commercial viability of this technology.

The electron transport properties in various poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) blend films, prepared by various process conditions, were investigated by admittance spectroscopy at different temperatures. It was found that the electron mobility and the dispersive transport behavior showed a strong dependence on the thermal treatment condition; the blend with the fastest growth rate had orders of magnitude reduction in the mobility and a much more dispersive transport. Using the Gaussian disorder model, it was found that the energetic disorder of the density-of-states between blends plays a significant role in the observed phenomena. It is proposed that the difference in the energetic disorder is due to the interfacial dipole effect at the P3HT/PC61BM heterojunctions in the various blend films.