Unraveling efficiency-limiting processes in organic solar cells by ultrafast spectroscopy - impact of chemical structure and morphology on photophysics and efficiency

Diese Arbeit widmet sich der Untersuchung der photophysikalischen Prozesse, die in Mischungen von Elektronendonoren mit Elektronenakzeptoren zur Anwendung in organischen Solarzellen auftreten. Als Elektronendonoren werden das Copolymer PBDTTT-C, das aus Benzodithiophen- und Thienothiophene-Einheiten besteht, und das kleine Molekül p-DTS(FBTTh2)2, welches Silizium-überbrücktes Dithiophen, sowie fluoriertes Benzothiadiazol und Dithiophen beinhaltet, verwendet. Als Elektronenakzeptor finden ein planares 3,4:9,10-Perylentetracarbonsäurediimid-(PDI)-Derivat und verschiedene Fullerenderivate Anwendung. PDI-Derivate gelten als vielversprechende Alternativen zu Fullerenen aufgrund der durch chemische Synthese abstimmbaren strukturellen, optischen und elektronischen Eigenschaften. Das gewichtigste Argument für PDI-Derivate ist deren Absorption im sichtbaren Bereich des Sonnenspektrums was den Photostrom verbessern kann. Fulleren-basierte Mischungen übertreffen jedoch für gewöhnlich die Effizienz von Donor-PDI-Mischungen.rnUm den Nachteil der PDI-basierten Mischungen im Vergleich zu den entsprechenden Fulleren-basierten Mischungen zu identifizieren, werden die verschiedenen Donor-Akzeptor-Kombinationen auf ihre optischen, elektronischen und strukturellen Eigenschaften untersucht. Zeitaufgelöste Spektroskopie, vor allem transiente Absorptionsspektroskopie (TA), wird zur Analyse der Ladungsgeneration angewendet und der Vergleich der Donor-PDI Mischfilme mit den Donor-Fulleren Mischfilmen zeigt, dass die Bildung von Ladungstransferzuständen einen der Hauptverlustkanäle darstellt.rnWeiterhin werden Mischungen aus PBDTTT-C und [6,6]-Phenyl-C61-buttersäuremethylesther (PC61BM) mittels TA-Spektroskopie auf einer Zeitskala von ps bis µs untersucht und es kann gezeigt werden, dass der Triplettzustand des Polymers über die nicht-geminale Rekombination freier Ladungen auf einer sub-ns Zeitskala bevölkert wird. Hochentwickelte Methoden zur Datenanalyse, wie multivariate curve resolution (MCR), werden angewendet um überlagernde Datensignale zu trennen. Zusätzlich kann die Regeneration von Ladungsträgern durch Triplett-Triplett-Annihilation auf einer ns-µs Zeitskala gezeigt werden. Darüber hinaus wird der Einfluss des Lösungsmitteladditivs 1,8-Diiodooctan (DIO) auf die Leistungsfähigkeit von p-DTS(FBTTh2)2:PDI Solarzellen untersucht. Die Erkenntnisse von morphologischen und photophysikalischen Experimenten werden kombiniert, um die strukturellen Eigenschaften und die Photophysik mit den relevanten Kenngrößen des Bauteils in Verbindung zu setzen. Zeitaufgelöste Photolumineszenzmessungen (time-resolved photoluminescence, TRPL) zeigen, dass der Einsatz von DIO zu einer geringeren Reduzierung der Photolumineszenz führt, was auf eine größere Phasentrennung zurückgeführt werden kann. Außerdem kann mittels TA Spektroskopie gezeigt werden, dass die Verwendung von DIO zu einer verbesserten Kristallinität der aktiven Schicht führt und die Generation freier Ladungen fördert. Zur genauen Analyse des Signalzerfalls wird ein Modell angewendet, das den gleichzeitigen Zerfall gebundener CT-Zustände und freier Ladungen berücksichtigt und optimierte Donor-Akzeptor-Mischungen zeigen einen größeren Anteil an nicht-geminaler Rekombination freier Ladungsträger.rnIn einer weiteren Fallstudie wird der Einfluss des Fullerenderivats, namentlich IC60BA und PC71BM, auf die Leistungsfähigkeit und Photophysik der Solarzellen untersucht. Eine Kombination aus einer Untersuchung der Struktur des Dünnfilms sowie zeitaufgelöster Spektroskopie ergibt, dass Mischungen, die ICBA als Elektronenakzeptor verwenden, eine schlechtere Trennung von Ladungstransferzuständen zeigen und unter einer stärkeren geminalen Rekombination im Vergleich zu PCBM-basierten Mischungen leiden. Dies kann auf die kleinere Triebkraft zur Ladungstrennung sowie auf die höhere Unordnung der ICBA-basierten Mischungen, die die Ladungstrennung hemmen, zurückgeführt werden. Außerdem wird der Einfluss reiner Fullerendomänen auf die Funktionsfähigkeit organischer Solarzellen, die aus Mischungen des Thienothienophen-basierenden Polymers pBTTT-C14 und PC61BM bestehen, untersucht. Aus diesem Grund wird die Photophysik von Filmen mit einem Donor-Akzeptor-Mischungsverhältnis von 1:1 sowie 1:4 verglichen. Während 1:1-Mischungen lediglich eine co-kristalline Phase, in der Fullerene zwischen den Seitenketten von pBTTT interkalieren, zeigen, resultiert der Überschuss an Fulleren in den 1:4-Proben in der Ausbildung reiner Fullerendomänen zusätzlich zu der co kristallinen Phase. Transiente Absorptionsspektroskopie verdeutlicht, dass Ladungstransferzustände in 1:1-Mischungen hauptsächlich über geminale Rekombination zerfallen, während in 1:4 Mischungen ein beträchtlicher Anteil an Ladungen ihre wechselseitige Coulombanziehung überwinden und freie Ladungsträger bilden kann, die schließlich nicht-geminal rekombinieren.

Delayed gadolinium-enhanced magnetic resonance imaging of cartilage (dGEMRIC), after slipped capital femoral epiphysis

OBJECTIVE: The aim of this study was to assess the glycosaminoglycan (GAG) content in hip joint cartilage in mature hips with a history of slipped capital femoral epiphysis (SCFE) using delayed gadolinium-enhanced MRI of cartilage (dGEMRIC). METHODS: 28 young-adult subjects (32 hips) with a mean age of 23.8+/-4.0 years (range: 18.1-30.5 years) who were treated for mild or moderate SCFE in adolescence were included into the study. Hip function and clinical symptoms were evaluated with the Harris hip score (HHS) system at the time of MRI. Plain radiographic evaluation included Tonnis grading, measurement of the minimal joint space width (JSW) and alpha-angle measurement. The alpha-angle values were used to classify three sub-groups: group 1=subjects with normal femoral head-neck offset (alpha-angle <50 degrees ), group 2=subjects with mild offset decrease (alpha-angle 50 degrees -60 degrees ), and group 3=subjects with severe offset decrease (alpha-angle >60 degrees ). RESULTS: There was statistically significant difference noted for the T1(Gd) values, lateral and central, between group 1 and group 3 (p-values=0.038 and 0.041). The T1(Gd) values measured within the lateral portion were slightly lower compared with the T1(Gd) values measured within the central portion that was at a statistically significance level (p-value <0.001). HHS, Tonnis grades and JSW revealed no statistically significant difference. CONCLUSION: By using dGEMRIC in the mid-term follow-up of SCFE we were able to reveal degenerative changes even in the absence of joint space narrowing that seem to be related to the degree of offset pathology. The dGEMRIC technique may be a potential diagnostic modality in the follow-up evaluation of SCFE.

Factors affecting bony impingement in hip arthroplasty

Computer modeling of 10 patients' computed tomographic scans was used to study the variables affecting hip arthroplasty range of motion before bony impingement (ROMBI) including acetabular offset and height, femoral offset, height and anteversion, and osteophyte removal. The ROMBI was compared with the ROM before component impingement and the native hip ROM. The ROMBI decreased with decreased total offset and limb shortening. Acetabular offset and height had a greater effect on ROMBI than femoral offset and height. The ROMBI lost with decreased acetabular offset was not fully recoverable with an increase in femoral offset or osteophyte removal. Bony impingement increased and component impingement decreased with decreased acetabular offset and increased head diameter.

Prevalence of cam-type deformity on hip magnetic resonance imaging in young males: a cross-sectional study

Objective To determine the prevalence of cam-type deformities on hip magnetic resonance imaging (MRI) in young males. Methods This was a population-based cross-sectional study in young asymptomatic male individuals who underwent clinical examination and completed a self-report questionnaire. A random sample of participants was invited for MRI of the hip. We graded the maximal offset at the femoral head–neck junction on radial sequences using grades from 0 to 3, where 0 = normal, 1 = possible, 2 = definite, and 3 = severe deformity. The prespecified main analyses were based on definite cam-type deformity grades 2 or 3. We estimated the prevalence of the cam-type deformity adjusted for the sampling process overall and according to the extent of internal rotation. Then we determined the location of the deformity on radial MRI sequences. Results A total of 1,080 subjects were included in the study and 244 asymptomatic males with a mean age of 19.9 years attended MRI. Sixty-seven definite cam-type deformities were detected. The adjusted overall prevalence was 24% (95% confidence interval [95% CI] 19–30%). The prevalence increased with decreasing internal rotation (P < 0.001 for trend). Among those with a clinically decreased internal rotation of <30°, the estimated prevalence was 48% (95% CI 37–59%). Sixty-one of 67 cam-type deformities were located in an anterosuperior position. Conclusion Cam-type deformities can be found on MRI in every fourth young asymptomatic male individual and in every second male with decreased internal rotation. The majority of deformities are located in an anterosuperior position.

Fracture hospitalizations between years 2000 and 2007 in Switzerland: a trend analysis

In Switzerland, the total number and incidence of hospitalizations for major osteoporotic fractures increased between years 2000 and 2007, while hospitalizations due to hip fracture decreased. The cost impact of shorter hospital stays was offset by the increasing cost per day of hospitalization.

Do fungal pathogens drive density-dependent mortality in established seedlings of two dominant African rain forest trees?

Where one or a few tree species reach local high abundance, different ecological factors may variously facilitate or hinder their regeneration. Plant pathogens are thought to be one of those possible agents which drive intraspecific density-dependent mortality of tree seedlings in tropical forests. Experimental evidence for this is scarce, however. In an African rain forest at Korup, we manipulated the density of recently established seedlings (~5–8 wk old; low vs. high-density) of two dominant species of contrasting recruitment potential, and altered their exposure to pathogens using a broad-spectrum fungicide. Seedling mortality of the abundantly recruiting subcanopy tree Oubanguia alata was strongly density-dependent after 7 mo, yet fungicide-treated seedlings had slightly higher mortality than controls. By contrast, seedling mortality of the poorly recruiting large canopy-emergent tree Microberlinia bisulcata was unaffected by density or fungicide. Ectomycorrhizal colonization of M. bisulcata was not affected by density or fungicide either. For O. alata, adverse effects of fungicide on its vesicular arbuscular mycorrhizas may have offset any possible benefit of pathogen removal. We tentatively conclude that fungal pathogens are not a likely major cause of density dependence in O. alata, or of early post-establishment mortality in M. bisulcata. They do not explain the latter's currently very low recruitment rate at Korup.

Evolution of genuine cross-correlation strength of focal onset seizures

To quantify the evolution of genuine zero-lag cross-correlations of focal onset seizures, we apply a recently introduced multivariate measure to broad band and to narrow-band EEG data. For frequency components below 12.5 Hz, the strength of genuine cross-correlations decreases significantly during the seizure and the immediate postseizure period, while higher frequency bands show a tendency of elevated cross-correlations during the same period. We conclude that in terms of genuine zero-lag cross-correlations, the electrical brain activity as assessed by scalp electrodes shows a significant spatial fragmentation, which might promote seizure offset.

Computer-assisted femoral head-neck osteochondroplasty using a surgical milling device an in vitro accuracy study

Surgical navigation might increase the safety of osteochondroplasty procedures in patients with femoroacetabular impingement. Feasibility and accuracy of navigation of a surgical reaming device were assessed. Three-dimensional models of 18 identical sawbone femora and 5 cadaver hips were created. Custom software was used to plan and perform repeated computer-assisted osteochondroplasty procedures using a navigated burr. Postoperative 3-dimensional models were created and compared with the preoperative models. A Bland-Altmann analysis assessing α angle and offset ratio accuracy showed even distribution along the zero line with narrow confidence intervals. No differences in α angle and offset ratio accuracy (P = 0.486 and P = 0.2) were detected between both observers. Planning and conduction of navigated osteochondroplasty using a surgical reaming device is feasible and accurate.

Infrared Parallaxes of Young Field Brown Dwarfs and Connections to Directly Imaged Gas-Giant Exoplanets

We have measured high-precision infrared parallaxes with the Canada-France-Hawaii Telescope for a large sample of candidate young (approximate to 10-100 Myr) and intermediate-age (approximate to 100-600 Myr) ultracool dwarfs, with spectral types ranging from M8 to T2.5. These objects are compelling benchmarks for substellar evolution and ultracool atmospheres at lower surface gravities (i.e., masses) than most of the field population. We find that the absolute magnitudes of our young sample can be systematically offset from ordinary (older) field dwarfs, with the young late-M objects being brighter and the young/dusty mid-L (L3-L6.5) objects being fainter, especially at J band. Thus, we conclude the "underluminosity" of the young planetary-mass companions HR 8799b and 2MASS J1207-39b compared to field dwarfs is also manifested in young free-floating brown dwarfs, though the effect is not as extreme. At the same time, some young objects over the full spectral type range of our sample are similar to field objects, and thus a simple correspondence between youth and magnitude offset relative to the field population appears to be lacking. Comparing the kinematics of our sample to nearby stellar associations and moving groups, we identify several new moving group members, including the first free-floating L dwarf in the AB Dor moving group, 2MASS J0355+11. Altogether, the effects of surface gravity (age) and dust content on the magnitudes and colors of substellar objects appear to be degenerate. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

A Near-Infrared Spectroscopic Study of Young Field Ultracool Dwarfs

We present a near-infrared (0.9-2.4 mu m) spectroscopic study of 73 field ultracool dwarfs having spectroscopic and/or kinematic evidence of youth (approximate to 10-300 Myr). Our sample is composed of 48 low-resolution (R approximate to 100) spectra and 41 moderate-resolution spectra (R greater than or similar to 750-2000). First, we establish a method for spectral typing M5-L7 dwarfs at near-IR wavelengths that is independent of gravity. We find that both visual and index-based classification in the near-IR provides consistent spectral types with optical spectral types, though with a small systematic offset in the case of visual classification at J and K band. Second, we examine features in the spectra of similar to 10 Myr ultracool dwarfs to define a set of gravity-sensitive indices based on FeH, VO, Ki, Nai, and H-band continuum shape. We then create an index-based method for classifying the gravities of M6-L5 dwarfs that provides consistent results with gravity classifications from optical spectroscopy. Our index-based classification can distinguish between young and dusty objects. Guided by the resulting classifications, we propose a set of low-gravity spectral standards for the near-IR. Finally, we estimate the ages corresponding to our gravity classifications.

Electrolyte Depletion in White-nose Syndrome Bats

The emerging wildlife disease white-nose syndrome is causing widespread mortality in hibernating North American bats. White-nose syndrome occurs when the fungus Geomyces destructans infects the living skin of bats during hibernation, but links between infection and mortality are underexplored. We analyzed blood from hibernating bats and compared blood electrolyte levels to wing damage caused by the fungus. Sodium and chloride tended to decrease as wing damage increased in severity. Depletion of these electrolytes suggests that infected bats may become hypotonically dehydrated during winter. Although bats regularly arouse from hibernation to drink during winter, water available in hibernacula may not contain sufficient electrolytes to offset winter losses caused by disease. Damage to bat wings from G. destructans may cause life-threatening electrolyte imbalances.

Insight into the mechanism of transient trapping in micellar electrokinetic chromatography

Transient trapping is a new mechanism of on-line sample concentration and separation that has recently been presented. It involves the injection of a short length of micellar solution in front of the sample, making it similar to sweeping in partial-filling MEKC. Here, we examine the mechanism of transient trapping by the use of computer simulations and compare it to sweeping in MEKC for the two analytes, sulforhodamine B and 101. The simulation results confirm the mechanism for concentration and separation originally proposed. The mechanism for concentration is similar to sweeping since the analytes are picked and accumulated by the micelles that penetrate the sample zone. The mechanism for separation is however quite unique since the concentrated analytes are trapped for a few seconds on the sample/micelle boundary before they are released as the concentration of micelle is reduced as it undergoes electromigration dispersion and the analytes separate down a micelle gradient. Simulation results suggested that a significant contribution of band broadening arises from the micelle gradient, with shallower gradients resulting in broader peaks. However, this is offset by an increase in selectivity, such that resolution was enhanced even though the peaks are broader. Transient trapping analysis with similar resolution to those obtained by sweeping MEKC could be achieved in 1/10 of the time and 1/4 of the capillary length, which results in a 2-3 times increase in sensitivity.

A sublimation technique for high-precision measurements of d13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2) from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS). In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used). A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

Rationales for the Bernese approaches in acetabular surgery

PURPOSE: To present two new approaches to acetabular surgery that were established in Berne, and which aim at enhanced visualization and anatomical reconstruction of acetabular fractures. METHOD: The trochanteric flip osteotomy allows for surgical hip dislocation, and was introduced as a posterior approach for acetabular fracture management involving the posterior column and wall. For acetabular fractures predominantly involving the anterior column and the quadrilateral plate, the Pararectus approach is described. RESULTS: Full exposure of the hip joint, as provided by the trochanteric flip osteotomy, facilitates anatomical reduction of acetabular or femoral head fractures and safe positioning of the anterior column screw in transverse or T-shaped fractures. Additionally, the approach enables osteochondral transplantation as a salvage procedure for severe chondral femoral head damage and osteoplasty of an associated inadequate offset at the femoral head-neck junction. The Pararectus approach allows anatomical restoration with minimal access morbidity, and combines advantages of the ilioinguinal and modified Stoppa approaches. CONCLUSIONS: Utilization of the trochanteric flip osteotomy eases visualization of the superior aspect of the acetabulum, and enables the evaluation and treatment of chondral lesions of the femoral head or acetabulum and labral tears. Displaced fractures of the anterior column with a medialized quadrilateral plate can be addressed successfully through the Pararectus approach, in which surgical access is associated with minimal morbidity. However, long-term results following the two presented Bernese approaches are needed to confirm that in the treatment of complex acetabular fractures the rate of poor results in almost one-third of all cases (as currently yielded using traditional approaches) might be reduced by the utilization of the presented novel approaches.

A physics-based correction model for homogenizing sub-daily temperature series

A new physics-based technique for correcting inhomogeneities present in sub-daily temperature records is proposed. The approach accounts for changes in the sensor-shield characteristics that affect the energy balance dependent on ambient weather conditions (radiation, wind). An empirical model is formulated that reflects the main atmospheric processes and can be used in the correction step of a homogenization procedure. The model accounts for short- and long-wave radiation fluxes (including a snow cover component for albedo calculation) of a measurement system, such as a radiation shield. One part of the flux is further modulated by ventilation. The model requires only cloud cover and wind speed for each day, but detailed site-specific information is necessary. The final model has three free parameters, one of which is a constant offset. The three parameters can be determined, e.g., using the mean offsets for three observation times. The model is developed using the example of the change from the Wild screen to the Stevenson screen in the temperature record of Basel, Switzerland, in 1966. It is evaluated based on parallel measurements of both systems during a sub-period at this location, which were discovered during the writing of this paper. The model can be used in the correction step of homogenization to distribute a known mean step-size to every single measurement, thus providing a reasonable alternative correction procedure for high-resolution historical climate series. It also constitutes an error model, which may be applied, e.g., in data assimilation approaches.