Spin Dynamics in Organic Semiconductors

Organic semiconductors exhibit exceptionally long spin lifetimes, and recent observations of the inverse spin hall effect as well as micrometer spin diffusion lengths in conjugated polymers have spiked interest in employing such carbon-based materials in spintronics applications. The charge transport and photophysics of organic semiconductors have been intensely studied for optoelectronic applications, revealing subtle relationships between molecular geometry, morphology and physical properties. Similar structure-property relationships remain mostly unknown for spin dynamics, where the charge carrier spins couple to their environment through hyperfine (HFI) and spin-orbit interactions (SOC). HFIs provide a pathway for spin relaxation while SOC plays a dual role in such materials: it couples the spin to its angular momentum and therefore enables both spin-to-charge conversion and spin relaxation. Understanding the molecular SOC, and finding a means to tune its strength, therefore is fundamentally important for materials design and selection. However, quantifying SOC strengths indirectly through spin relaxation effects has proven difficult due to competing relaxation mechanisms. We initially present a systematic study of the g-tensor shift in molecular semiconductors and establish it as a probe for the SOC strength in a series of high mobility molecular semiconductors. The results demonstrate a rich variability of molecular g-shifts with the effective SOC, depending on subtle aspects of molecular composition and structure. We then correlate the above g-shifts to spin-lattice relaxation times over four orders of magnitude, from 200 µs to 0.15 µs, for isolated molecules in solution and relate our findings to the spin relaxation mechanisms that are likely to be relevant in solid state systems. Isolated molecules provide an ideal model system to investigate a spin’s interactions with its environment but device applications commonly employ thin films. The second half of this thesis investigates polaron spin lifetimes in field effect transistors with high-mobility conjugated polymers as active layers. We use field-induced electron spin resonance measurements to demonstrate that spin relaxation is governed by the charges' hopping motion at low temperatures while Elliott-Yafet-like relaxation due to short-range, rapid spin density dynamics likely dominates high temperature spin lifetimes. Such a microscopic relaxation mechanism is highly sensitive to the local conformation of polymer backbones and we show its dependence on the degree of crystallinity in a polymer film

Charge-Transport Anisotropy in a Uniaxially Aligned Diketopyrrolopyrrole-Based Copolymer.

Aligned films of a semiconducting DPP-based copolymer exhibit highly anisotropic charge transport with a band-like temperature dependence along the alignment direction and hole mobilities of up to 6.7 cm(2) V(-1) s(-1) . X-ray diffraction measurements reveal an exceptional degree of in-plane alignment, high crystallinity, and a dominant face-on orientation of the polymer backbones. The surprising charge-transport properties are interpreted in a tie-chain model consistent with anisotropic activation energies.The authors gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) through a program grant (EP/G060738/1). C.R.M. acknowledges support from the Australia Research Council (FT100100275 and DP130102616). This work was performed in part at the SAXS/WAXS[59] and soft X-ray[60] beam lines at the Australian Synchrotron. C.R.M. and E.G. thank Nigel Kirby of the Australian Synchrotron for technical assistance.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/adma.20150243

Room-temperature optically detected magnetic resonance of single defects in hexagonal boron nitride

Optically addressable spins in materials are important platforms for quantum technologies, such as repeaters and sensors. Identification of such systems in two-dimensional (2d) layered materials offers advantages over their bulk counterparts, as their reduced dimensionality enables more feasible on-chip integration into devices. Here, we report optically detected magnetic resonance (ODMR) from previously identified carbon-related defects in 2d hexagonal boron nitride (hBN). We show that single-defect ODMR contrast can be as strong as 6% and displays a magnetic-field dependence with both positive or negative sign per defect. This bipolarity can shed light into low contrast reported recently for ensemble ODMR measurements for these defects. Further, the ODMR lineshape comprises a doublet resonance, suggesting either low zero-field splitting or hyperfine coupling. Our results offer a promising route towards realising a room-temperature spin-photon quantum interface in hexagonal boron nitride

Polaron spin dynamics in high-mobility polymeric semiconductors

Polymeric semiconductors exhibit exceptionally long spin lifetimes, and recently observed micrometre spin diffusion lengths in conjugated polymers demonstrate the potential for organic spintronics devices. Weak spin–orbit and hyperfine interactions lie at the origin of their long spin lifetimes, but the coupling mechanism of a spin to its environment remains elusive. Here, we present a systematic study of polaron spin lifetimes in field-effect transistors with high-mobility conjugated polymers as an active layer. We demonstrate how spin relaxation is governed by the charges’ hopping motion at low temperatures, whereas an Elliott–Yafet-like relaxation due to a transient localization of the carrier wavefunctions is responsible for spin relaxation at high temperatures. In this regime, charge, spin and structural dynamics are intimately related and depend sensitively on the local conformation of polymer backbones and the crystalline packing of the polymer chains.* ERC Synergy grant SC2 (no. 610115) * Alexander von Humboldt Foundation * Transregional Collaborative Research Center (SFB/TRR) 173 SPIN+X * Winton Programme for the Physics of Sustainability * Engineering and Physical Sciences Research Council (EPSRC) * Excellence Initiative by the Graduate School Materials Science in Mainz (GSC 266) * European Commission/Région Wallonne (FEDER–BIORGEL project), the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds National de la Recherche Scientifique (FRS-FNRS) under grant no. 2.5020.11 * Tier-1 supercomputer of the Fédération Wallonie-Bruxelles, infrastructure funded by the Walloon Region under grant agreement n111754

Varied patterns of catch-up in child growth: Evidence from Young Lives

The development of human capabilities for many disadvantaged children around the world depends on growth recovery ('catch-up growth'). Here we develop a novel framework that allows different types of catch-up growth to be classified and estimated. We distinguish between catch-up in the mean of a group toward that of a healthy reference population versus catch-up within the group. We show these different growth types can be tested in a unified setting using a latent growth framework. We apply the results to four developing countries, using longitudinal data on 7641 children collected over the period 2002-2013. The results show catch-up growth rates are generally modest but vary significantly between countries, and that local environmental factors are material to variation in child growth trajectories. The paper discusses the benefits of the new framework versus current methods, shows that the method is feasible, and suggests they call for intervention designs that are sensitive to community and country contexts

Search for new phenomena in final states with an energetic jet and large missing transverse momentum in pp collisions at √ s = 8 TeV with the ATLAS detector

Results of a search for new phenomena in final states with an energetic jet and large missing transverse momentum are reported. The search uses 20.3 fb−1 of √ s = 8 TeV data collected in 2012 with the ATLAS detector at the LHC. Events are required to have at least one jet with pT > 120 GeV and no leptons. Nine signal regions are considered with increasing missing transverse momentum requirements between Emiss T > 150 GeV and Emiss T > 700 GeV. Good agreement is observed between the number of events in data and Standard Model expectations. The results are translated into exclusion limits on models with either large extra spatial dimensions, pair production of weakly interacting dark matter candidates, or production of very light gravitinos in a gauge-mediated supersymmetric model. In addition, limits on the production of an invisibly decaying Higgs-like boson leading to similar topologies in the final state are presente

Chemotherapy induces Notch1-dependent MRP1 up-regulation, inhibition of which sensitizes breast cancer cells to chemotherapy

Background Multi-drug Resistance associated Protein-1 (MRP1) can export chemotherapeutics from cancer cells and is implicated in chemoresistance, particularly as is it known to be up-regulated by chemotherapeutics. Our aims in this study were to determine whether activation of Notch signalling is responsible for chemotherapy-induced MRP1 expression Notch in breast cancers, and whether this pathway can be manipulated with an inhibitor of Notch activity. Methods MRP1 and Notch1 were investigated in 29 patients treated with neoadjuvant chemotherapy (NAC) for breast cancer, using immunohistochemistry on matched biopsy (pre-NAC) and surgical samples (post-NAC). Breast epithelial cell cultures (T47D, HB2) were treated with doxorubicin in the presence and absence of functional Notch1, and qPCR, siRNA, Western blots, ELISAs and flow-cytometry were used to establish interactions. Results In clinical samples, Notch1 was activated by neoadjuvant chemotherapy (Wilcoxon signed-rank p < 0.0001) and this correlated with induction of MRP1 expression (rho = 0.6 p = 0.0008). In breast cell lines, doxorubicin induced MRP1 expression and function (non-linear regression p < 0.004). In the breast cancer line T47D, doxorubicin activated Notch1 and, critically, inhibition of Notch1 activation with the γ-secretase inhibitor DAPT abolished the doxorubicin-induced increase in MRP1 expression and function (t-test p < 0.05), resulting in enhanced cellular retention of doxorubicin and increased doxorubicin-induced apoptosis (t-test p = 0.0002). In HB2 cells, an immortal but non-cancer derived breast cell line, Notch1-independent MRP1 induction was noted and DAPT did not enhance doxorubicin-induced apoptosis. Conclusions Notch inhibitors may have potential in sensitizing breast cancer cells to chemotherapeutics and therefore in tackling chemoresistance

Juxtaposing BTE and ATE – on the role of the European insurance industry in funding civil litigation

One of the ways in which legal services are financed, and indeed shaped, is through private insurance arrangement. Two contrasting types of legal expenses insurance contracts (LEI) seem to dominate in Europe: before the event (BTE) and after the event (ATE) legal expenses insurance. Notwithstanding institutional differences between different legal systems, BTE and ATE insurance arrangements may be instrumental if government policy is geared towards strengthening a market-oriented system of financing access to justice for individuals and business. At the same time, emphasizing the role of a private industry as a keeper of the gates to justice raises issues of accountability and transparency, not readily reconcilable with demands of competition. Moreover, multiple actors (clients, lawyers, courts, insurers) are involved, causing behavioural dynamics which are not easily predicted or influenced. Against this background, this paper looks into BTE and ATE arrangements by analysing the particularities of BTE and ATE arrangements currently available in some European jurisdictions and by painting a picture of their respective markets and legal contexts. This allows for some reflection on the performance of BTE and ATE providers as both financiers and keepers. Two issues emerge from the analysis that are worthy of some further reflection. Firstly, there is the problematic long-term sustainability of some ATE products. Secondly, the challenges faced by policymakers that would like to nudge consumers into voluntarily taking out BTE LEI

Penilaian Kinerja Keuangan Koperasi di Kabupaten Pelalawan

This paper describe development and financial performance of cooperative in District Pelalawan among 2007 - 2008. Studies on primary and secondary cooperative in 12 sub-districts. Method in this stady use performance measuring of productivity, efficiency, growth, liquidity, and solvability of cooperative. Productivity of cooperative in Pelalawan was highly but efficiency still low. Profit and income were highly, even liquidity of cooperative very high, and solvability was good

Search for stop and higgsino production using diphoton Higgs boson decays

Results are presented of a search for a "natural" supersymmetry scenario with gauge mediated symmetry breaking. It is assumed that only the supersymmetric partners of the top-quark (stop) and the Higgs boson (higgsino) are accessible. Events are examined in which there are two photons forming a Higgs boson candidate, and at least two b-quark jets. In 19.7 inverse femtobarns of proton-proton collision data at sqrt(s) = 8 TeV, recorded in the CMS experiment, no evidence of a signal is found and lower limits at the 95% confidence level are set, excluding the stop mass below 360 to 410 GeV, depending on the higgsino mass