Optical activation of material properties illustrates the potentials held by tuning light-matter interactions with impacts ranging from basic science to technological applications. Here, we demonstrate for the first time that composite nanostructures providing nonlocal environments can be engineered to optically trigger photoinduced charge-transfer-dynamic modulations in the solid state. The nanostructures explored herein lead to out-of-phase behavior between charge separation and recombination dynamics, along with linear charge-transfer-dynamic variations with the optical-field intensity. Using transient absorption spectroscopy, up to 270% increase in charge separation rate is obtained in organic semiconductor thin films. We provide evidence that composite nanostructures allow for surface photovoltages to be created, which kinetics vary with the composite architecture and last beyond optical pulse temporal characteristics. Furthermore, by generalizing Marcus theory framework, we explain why charge-transfer-dynamic modulations can only be unveiled when optic-field effects are enhanced by nonlocal image-dipole interactions. Our demonstration, that composite nanostructures can be designed to take advantage of optical fields for tuneable charge-transfer-dynamic remote actuators, opens the path for their use in practical applications ranging from photochemistry to optoelectronics.

Materials with hyperbolic dispersion are the key to a variety of photonic applications involving nanoimaging, hyper-lensing, and spontaneous emission engineering, due to the availability of high k modes. Here we demonstrate that spin-coated polycrystalline organic semiconducting films with a layered molecular packing structure can exhibit a hyperbolic dispersion over a wide spectral range and support the presence of surface excitonic polaritons. This was evidenced from 670 to 920 nm and is related to the negative real part of the dielectric permittivity of the selected quinoidal organic semiconductor. In addition, the accessible high k modes lead to changes in the spontaneous emission decay rate and photoluminescence quantum yield of emitters placed nearby the organic monolithic (composed of only one molecule and not necessitating an alternating multilayer structure) natural hyperbolic material. This study opens a new route toward single-step solution manufacturing of large-area, low-cost, and flexible organic photonic metadevices with hyperbolic dispersion.

Surface plasmon polariton (SPP), hyperbolic dispersion of energy and momentum, and emission interference provide opportunities to control photoluminescence properties. However, the interplays between these regimes need to be understood to take advantage of them in optoelectronic applications. Herein, broadband variations induced by hyperbolic metamaterial (HMM) multilayer nanostructures on the spontaneous emission of selected organic chromophores are investigated. Experimental and calculated spontaneous emission lifetimes are shown to vary nonmonotonously near HMM interfaces. With the HMM number of pairs used as the analysis parameter, the lifetime is shown to be independent of the number of pairs in the surface plasmon polaritons, and emission interference dominant regimes, while it decreases in the hyperbolic dispersion dominant regime. It is also shown that the spontaneous emission lifetime is similarly affected by transverse positive and transverse negative HMMs. This work has broad implications on the rational design of functional photonic surfaces to control the luminescence of semiconductor chromophores.

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is widely used to build optoelectronic devices. However, as a hygroscopic water-based acidic material, it brings major concerns for stability and degradation, resulting in an intense effort to replace it in organic photovoltaic (OPV) devices. In this work, we focus on the perfluorinated ionomer (PFI) polymeric additive to PEDOT:PSS. We demonstrate that it can reduce the relative amplitude of OPV device burn-in, and find two distinct regimes of influence. At low concentrations there is a subtle effect on wetting and work function, for instance, with a detrimental impact on the device characteristics, and above a threshold it changes the electronic and device properties. The abrupt threshold in the conducting polymer occurs for PFI concentrations greater than or equal to the PSS concentration and was revealed by monitoring variations in transmission, topography, work-function, wettability and OPV device characteristics. Below this PFI concentration threshold, the power conversion efficiency (PCE) of OPVs based on poly(3-hexylthiophene-2,5-diyl):[6,6]-phenyl-C-61-butyric acid methyl ester (P3HT:PCBM) are impaired largely by low fill-factors due to poor charge extraction. Above the PFI concentration threshold, we recover the PCE before it is improved beyond the pristine PEDOT:PSS layer based OPV devices. Supplementary to the performance enhancement, PFI improves OPV device stability and lifetime. Our degradation study leads to the conclusion that PFI prevents water from diffusing to and from the hygroscopic PEDOT:PSS layer, which slows down the deterioration of the PEDOT:PSS layer and the aluminum electrode. These findings reveal mechanisms and opportunities that should be taken into consideration when developing components to inhibit OPV degradation.

Charge transfer (CT) is a fundamental and ubiquitous mechanism in biology, physics and chemistry. Here, we evidence that CT dynamics can be altered by multi-layered hyperbolic metamaterial (HMM) substrates. Taking triphenylene:perylene diimide dyad supramolecular self-assemblies as a model system, we reveal longer-lived CT states in the presence of HMM structures, with both charge separation and recombination characteristic times increased by factors of 2.4 and 1.7-that is, relative variations of 140 and 73%, respectively. To rationalize these experimental results in terms of driving force, we successfully introduce image dipole interactions in Marcus theory. The non-local effect herein demonstrated is directly linked to the number of metal-dielectric pairs, can be formalized in the dielectric permittivity, and is presented as a solid analogue to local solvent polarity effects. This model and extra PH3T:PC60BM results show the generality of this non-local phenomenon and that a wide range of kinetic tailoring opportunities can arise from substrate engineering. This work paves the way toward the design of artificial substrates to control CT dynamics of interest for applications in optoelectronics and chemistry.

Charge transfer (CT) is an essential phenomenon relevant to numerous fields including biology, physics and chemistry.1-5 Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter organic semiconductor CT dynamics.6 With triphenylene:perylene diimide dyad supramolecular self-assemblies prepared on HMM substrates, we show that both charge separation (CS) and charge recombination (CR) characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalize the experimental data by extending Marcus theory framework with dipole image interactions tuning the driving force. The number of metal-dielectric pairs alters the HMM interfacial effective dielectric constant and becomes a solid analogue to solvent polarizability. Based on the experimental results and extended Marcus theory framework, we find that CS and CR processes are located in normal and inverted regions on Marcus parabola diagram, respectively. The model and further PH3T:PCBM data show that the phenomenon is general and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics, organic solar cells and chemistry. 1. Marcus, Rev. Mod. Phys., 1993, 65, 599. 2. Marcus, Phys. Chem. Chem. Phys., 2012, 14, 13729. 3. Lambert, et al., Nat. Phys., 2012, 9, 10. 4. C. Clavero, Nat. Photon., 2014, 8, 95. 5. A. Canaguier-Durand, et al., Angew. Chem. Int. Ed., 2013, 52, 10533. 6. K. J. Lee, et al., Submitted, 2015, arxiv.org/abs/1510.08574.

OPV HTL fluorination alters not only the HTL electronic properties but also the complex refractive indices.

Plasmonic nanostructures have recently been shown to alter the photonic density of states and to provide opportunities to control semiconductor photophysical properties.1-4 Experimentally and theoretically,5 we investigated the effects of a range of hyperbolic metamaterial (HMM) lamellar structures consisting of metal and dielectric multilayers on the photoluminescence (PL) lifetime of several organic chromophores which emission range from UV to visible. These molecules were immersed in a polymeric matrix spin-coated on top of the HMM substrates and streak camera measurements were completed to monitor the evolution of the chromophores spontaneous emission. The ratio of the PL lifetimes of chromophores located on top of HMM nanostructures and on top of fused silica was shown to vary in a non-monotonous way. We then showed that normalized PL lifetime of the chromophore strongly depends on the HMM phase and the number of metal-dielectric pairs. To analyze systematically this behavior and fully understand the involved mechanisms, we also developed a theoretical analysis and took advantage of both invariant imbedding method and FDTD simulation as computational tools to quantitatively explain the experimental results and predict the responses, which could be observed when varying further the HMM nanostructures. 1. M. A. Noginov, et al., Opt. Lett., 2010, 35, 1863. 2. T. U. Tumkur, , et al., Appl. Phys. Lett., 2012, 100, 161103. 3. P. Shekhar, , et al., Phys. Rev. B, 2014, 90, 045313. 4. H. N. Krishnamoorthy, , et al., Science, 2012, 336, 205. 5. K. J. Lee, , et al. In preparation, 2016.

Department of Physics, CNRS-Ewha Intern University, Seoul 120-750, Korea. E-mail: ri Center for Length, Division of Physical Standards and Science (KRISS), 267 Gaj South Korea Sorbonne Universités, UPMC Univ Paris Moléculaire, UMR 8232, Chimie des Pol France. E-mail: fabrice.mathevet@upmc.fr Advanced Materials Engineering and Model and Technology, 50-370 Wroclaw, Poland Institut de Physique et Chimie des Matéri Université de Strasbourg, 23 Rue du Loess, Aix Marseille Université, CNRS, CINaM UM 13288 Marseille, France Elements Chemistry Laboratory, RIKEN, W riken.jp † Contributed equally to this work. ‡ Present Address: Center for Organic (OPERA), Kyushu University, Fukuoka, Jap Cite this: RSC Adv., 2016, 6, 57811

Dynamics of the photo-induced charge transfer are correlated with the structural properties of self-assembled discotic donor–acceptor dyad and triad films.

Magnetic nanoparticles (MnPs) are relevant to a wide range of applications including high density information storage and magnetic resonance imaging to name but a few. Among the materials available to prepare MnPs, FePt is attracting growing attention. However, to harvest the strongest magnetic properties of FePt MnPs, a thermal annealing is often required to convert face-centered cubic as synthesized nPs into its tetragonal phase. Rarely addressed are the potential side effects of such treatments on the magnetic properties. In this study, we focus on the impact of silica shells often used in strategies aiming at overcoming MnP coalescence during the thermal annealing. While we show that this shell does prevent sintering, and that fcc-to-fct conversion does occur, we also reveal the formation of silicide, which can prevent the stronger magnetic properties of fct-FePt MnPs from being fully realised. This report therefore sheds lights on poorly investigated and understood interfacial phenomena occurring during the thermal annealing of MnPs and, by doing so, also highlights the benefits of developing new strategies to avoid silicide formation.

A simple and versatile solution-processing method based on molecular self-assembly is used to fabricate organic single crystal microwires of a low bandgap quinoidal oligothiophene derivative. Individual single crystal microwire transistors present well-balanced ambipolar behaviour with hole and electron mobilities as high as 0.4 and 0.5 cm(2) V-1 s(-1), respectively.

Charge transfer (CT) is essential to numerous fields including biology, physics and chemistry. Here, we demonstrate that multi-layered hyperbolic metamaterial (HMM) substrates alter CT dynamics. With triphenylene:perylene diimide dyad supramolecular self-assemblies, we show that both charge separation and recombination characteristic times are increased by factors of 2.5 and 1.6, respectively, resulting in longer-lived CT states. We successfully rationalise the experimental data by introducing dipole image interactions in Marcus theory to tune the driving force. The number of metal-dielectric pairs induces a non-local effect near the HMM structure formalised in the dielectric permittivity, and is presented as a solid analogue to local solvent polarizability effects. The model and PH3T:PCBM data show the phenomenon generality and that molecular and substrate engineering offer a wide range of kinetic tailoring opportunities. This work opens the path toward novel artificial substrates designed to control CT dynamics with potential applications in fields including optoelectronics and chemistry.

Nanostructured composites of inorganic and organic materials are attracting extensive interest for electronic and optoelectronic device applications. Here we report a novel method for the fabrication and patterning of metal selenide nanoparticles in organic semiconductor films that is compatible with solution processable large area device manufacturing. Our approach is based upon the controlled in situ decomposition of a cadmium selenide precursor complex in a film of the electron transporting material 1,3,5-tris(N-phenyl-benzimidazol-2-yl)-benzene (TPBI) by thermal and optical methods. In particular, we show that the photoluminescence quantum yield (PLQY) of the thermally converted CdSe quantum dots (QDs) in the TPBI film is up to 15%. We also show that laser illumination can form the QDs from the precursor. This is an important result as it enables direct laser patterning (DLP) of the QDs. DLP was performed on these nanocomposites using a picosecond laser. Confocal microscopy shows the formation of emissive QDs after laser irradiation. The optical and structural properties of the QDs were also analysed by means of UV-Vis, PL spectroscopy and transmission electron microscopy (TEM). The results show that the QDs are well distributed across the film and their emission can be tuned over a wide range by varying the temperature or irradiated laser power on the blend films. Our findings provide a route to the low cost patterning of hybrid electroluminescent devices.

Feasibility studies are needed to demonstrate that safe and effective manipulation of bowel during Minimal Access Surgery (MAS) can be obtained by use of magnetic force. This paper characterises two classes of magnetic particles: stainless steel microparticles (SS-μPs) and iron oxide nanoparticles (IO-nPs) in terms of their magnetisation, chemical composition, crystallinity, morphology and size distribution. Both magnetic particles were dispersed in a high viscosity biological liquid for intraluminal injection of bowel. Ex vivo porcine bowel segments were then retracted by permanent magnetic probes of 5.0 and 10mm diameter. Strong retraction forces reaching 6N maximum were obtained by magnetic fluid based on dispersion of SS-μPs. In contrast, the IO-nP-based magnetic liquid generated less attraction force, due to both lower magnetic and solution properties of the IO-nPs. The comparison of the two particles allowed the identification of the rules to engineer the next generation of particles. The results with SS-μPs provide proof on concept that intraluminal injection of magnetic fluid can generate sufficient force for efficient bowel retraction. Thereafter we shall carry out in vivo animal studies for efficacy and safety of both types of ferrofluids.

Thiel-embalmed human cadaveric specimens are used widely for biomedical scientific investigation. This Letter reports electrical impedance measurements of Thiel-embalming solutions from 1 Hz to 32 MHz. Compared with other solutions studied, Thiel solution has the lowest impedance throughout the test spectrum. The electrical conductivity of a Thiel-embalmed liver sample exhibited a relatively flat frequency response from 100 to 500 kHz, which is the frequency range used for electro-surgery and radiofrequency tumour ablation (RFA). It measured 5 Sm−1 compared with 0.22 Sm−1 obtained from ex-vivo fresh pig liver. Using finite element modelling and experimental evaluation, the ablation zone obtained from the Thiel-embalmed liver sample was extremely small due to its much higher conductivity. Hence, it is concluded that Thiel-embalmed tissue cannot be used as a reliable model for RFA evaluation.

Safe and effective manipulation of soft tissue during laparoscopic procedures can be achieved by the use of mucoadhesive polymer films. A series of novel adhesive polymer films were formulated in house based on either Carbopol or Chitosan modified systems. The mechanical properties of the polymers and their adherence to bowel were evaluated using ex-vivo pig bowel immersed in 37°C water bath and connected to an Instron tensiometer. Young's modulus was 300 kPa for the Carbopol-polymer and 5 kPa for the Chitosan-polymer. The Chitosan-polymer exhibited much larger shear adhesion than its tensile adhesion: 3.4 N vs. 1.2. Both tensile and shear adhesions contributed to the large retraction force (2.6 N) obtained during l polymer-bowel retraction testing. Work of adhesion at the polymer/serosa interface, defined as the area under the force curve, was 64 mJ, which is appreciably larger than that reported with existing polymers. In conclusion, adhesive polymers can stick to the serosal side of the bowel with an adhesive force, which is sufficient to lift the bowel, providing a lower retraction stress than that caused by laparoscopic grasping which induces high localized pressures on the tissue.