Irradiation-induced degradation of PTB7 investigated by valence band and S 2p photoelectron spectroscopy.

Monochromatic radiation with known absolute radiant power from an undulator at the electron storage ring Metrology Light Source (MLS) was used to irradiate PTB7 (a thieno[3, 4-b]thiophene-alt-benzodithiophene polymer) thin films at wavelengths (photon energies) of 185 nm (6.70 eV), 220 nm (5.64 eV), 300 nm (4.13 eV), 320 nm (3.88 eV), 356 nm (3.48 eV) and 675 nm (1.84 eV) under ultra-high vacuum conditions for the investigation of radiation-induced degradation effects. The characterization of the thin films is focused at ultraviolet photoelectron spectroscopy (UPS) of valence bands and is complemented by S 2p x-ray photoelectron spectroscopy (S 2p XPS) before and after the irradiation procedure. The radiant exposure was determined for each irradiation by means of photodiodes traceably calibrated to the international system of units SI. The valence band spectra show the strongest changes for the shortest wavelengths and no degradation effect at 356 nm and 675 nm even with the highest radiant exposure applied. In the spectral range where the Sun appears bright on the Earth's surface, no degradation effects are observed.

Effect of Side Chains on Molecular Conformation of Anthracene-Ethynylene-Phenylene-Vinylene Oligomers: A Comparative Density Functional Study With and Without Dispersion Interaction.

Using density functional calculations with and without dispersion interaction, we studied the effects of linear octyl and branched 2-ethylhexyl side chains on the oligomer conformation of the conjugated copolymer poly(p-anthracene-ethynylene)-alt-poly(p-phenylene-vinylene). With dispersion included, the branched side chains can cause significant bending of the oligomer backbone, while without dispersion they induce mainly torsional disorder. The oligomers with mainly linear side chains keep good planarity when optimized with and without dispersion. Despite their dramatically different conformations, the calculated absorption spectra of the oligomers with various side chain combinations are very similar, indicating that the conformation of the copolymer is not the main reason for the experimentally observed different spectra of ordered and disordered phases.

Control of charge generation and recombination in ternary polymer/polymer:fullerene photovoltaic blends using amorphous and semi-crystalline copolymers as donors.

Charge generation and recombination processes occurring in ternary photoactive copolymer:copolymer:fullerene blends consisting of different mixing ratios between entirely amorphous and semi-crystalline PPE-PPV copolymers are investigated by transient absorption pump-probe and pump-push photocurrent spectroscopy. The experiments reveal that an excess of semi-crystalline polymer facilitates exciton dissociation into free charge carriers, slows down geminate recombination, and suppresses non-geminate recombination leading to increased short-circuit currents and high fill factors. In contrast, blends utilizing solely the amorphous polymer for their donor phase suffer from a large fraction of sub-nanosecond geminate recombination of interfacially bound charge-transfer states and also from fast non-geminate recombination of free charges, resulting in a significantly reduced photovoltaic performance. However, small fractions of the amorphous polymer blended into the semi-crystalline polymer increase the open-circuit voltage and the fill factor, while keeping the charge generation and recombination parameters largely unaltered in turn leading to an optimized device performance for the ternary PPE-PPV copolymer:copolymer:fullerene blends.

Sub-bandgap absorption in organic solar cells: experiment and theory.

Most high-performance organic solar cells involve bulk-heterojunctions in order to increase the active donor-acceptor interface area. The power conversion efficiency depends critically on the nano-morphology of the blend and the interface. Spectroscopy of the sub-bandgap region, i.e., below the bulk absorption of the individual components, provides unique opportunities to study interface-related properties. We present absorption measurements in the sub-bandgap region of bulk heterojunctions made of poly(3-hexylthiophene-2,5-diyl) as an electron donor and [6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as an electron acceptor and compare them with quantum-chemical calculations and recently published data on the external quantum efficiency (EQE). The very weak absorption of the deep sub-bandgap region measured by the ultra-sensitive Photothermal Deflection Spectroscopy (PDS) features Urbach tails, polaronic transitions, conventional excitons, and possibly charge-transfer states. The quantum-chemical calculations allow characterizing some of the unsettled spectral features.

Dual-Use Self-Assembled Monolayer Controlling Charge Carrier Extraction in Organic Solar Cells.

The development and use of interface materials are essential to the continued advancement of organic solar cells (OSCs) performance. Self-assembled monolayer (SAM) materials have drawn attention because of their simple structure and affordable price. Due to their unique properties, they may be used in inverted devices as a modification layer for modifying ZnO or as a hole transport layer (HTL) in place of typical poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) in conventional devices. In this work, zinc oxide (ZnO) is modified using five structurally similar SAM materials. This resulted in a smoother surface, a decrease in work function, a suppression of charge recombination, and an increase in device efficiency and photostability. In addition, they can introduced asfor hole extraction layer between the active layer and MoO3 , enabling the use of the same material at several functional layers in the same device. Through systematic orthogonal evaluation, it is shown that some SAM/active layer/SAM combinations still offered device efficiencies comparable to ZnO/SAM, but with improved device' photostability. This study may provide recommendations for future SAM material's design and development as well as a strategy for boosting device performance by using the same material across both sides of the photoactive layer in OSCs.

Absolute energy levels in nanodiamonds of different origins and surface chemistries.

Nanodiamonds (NDs) are versatile, broadly available nanomaterials with a set of features highly attractive for applications from biology over energy harvesting to quantum technologies. Via synthesis and surface chemistry, NDs can be tuned from the sub-micron to the single-digit size, from conductive to insulating, from hydrophobic to hydrophilic, and from positively to negatively charged surface by simple annealing processes. Such ND diversity makes it difficult to understand and take advantage of their electronic properties. Here we present a systematic correlated study of structural and electronic properties of NDs with different origins and surface terminations. The absolute energy level diagrams are obtained by the combination of optical (UV-vis) and photoelectron (UPS) spectroscopies, Kelvin probe measurements, and energy-resolved electrochemical impedance spectroscopy (ER-EIS). The energy levels and density of states in the bandgap of NDs are correlated with the surface chemistry and structure characterized by FTIR and Raman spectroscopy. We show profound differences in energy band shifts (by up to 3 eV), Fermi level position (from p-type to n-type), electron affinity (from +0.5 eV to -2.2 eV), optical band gap (5.2 eV to 5.5 eV), band gap states (tail or mid-gap), and electrical conductivity depending on the high-pressure, high-temperature and detonation origin of NDs as well as on the effects of NDs' oxidation, hydrogenation, sp2/sp3 carbon phases and surface adsorbates. These data are fundamental for understanding and designing NDs' optoelectrochemical functional mechanisms in diverse application areas.

Electronic and Photochemical Passivation by a Classic Sunscreen Material Leading to Reduced Voc Losses and Enhanced Stability in Organic Solar Cells.

Organic solar cells (OSCs) have been a popular topic of research for a long time. As a well-known electron transport layer (ETL) material for inverted device architecture, sol-gel-derived zinc oxide (ZnO) displays certain defective surfaces that cause excessive charge recombination and lower device performance. While ultraviolet (UV)-light soaking is sometimes necessary for the ZnO layer to function properly, the latter can also cause the photodegradation of conjugated organic semiconductors. The photostability of OSCs has always been a hot research topic, as the radiation of UV light may cause changes in the material's properties, and that, in turn, may cause rapid attenuation of the devices. Herein, ZnO is modified by inserting the commonly used sunscreen ingredient benzophenone-3 (BP-3) between the photoactive layer, consisting of a PM6:Y6 blend, and ZnO to reduce the impact of UV radiation on the photosensitive layer. The addition of BP-3 successfully enhances the photovoltaic parameters, and a remarkable open-circuit voltage (Voc) value of 0.887 V is obtained for PM6:Y6-based inverted solar cells, corresponding to a Voc loss as small as 0.547 V. Finally, the application of this strategy increases the device's power conversion efficiency from 12.44 to 13.71% and provides improved UV stability.

On the stability of a variety of organic photovoltaic devices by IPCE and in situ IPCE analyses--the ISOS-3 inter-laboratory collaboration.

This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPV) devices prepared by leading research laboratories. All devices have been shipped to and degraded at RISØ-DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work, we apply the Incident Photon-to-Electron Conversion Efficiency (IPCE) and the in situ IPCE techniques to determine the relation between solar cell performance and solar cell stability. Different ageing conditions were considered: accelerated full sun simulation, low level indoor fluorescent lighting and dark storage. The devices were also monitored under conditions of ambient and inert (N(2)) atmospheres, which allows for the identification of the solar cell materials more susceptible to degradation by ambient air (oxygen and moisture). The different OPVs configurations permitted the study of the intrinsic stability of the devices depending on: two different ITO-replacement alternatives, two different hole extraction layers (PEDOT:PSS and MoO(3)), and two different P3HT-based polymers. The response of un-encapsulated devices to ambient atmosphere offered insight into the importance of moisture in solar cell performance. Our results demonstrate that the IPCE and the in situ IPCE techniques are valuable analytical methods to understand device degradation and solar cell lifetime.

TOF-SIMS investigation of degradation pathways occurring in a variety of organic photovoltaic devices--the ISOS-3 inter-laboratory collaboration.

The present work is the fourth (and final) contribution to an inter-laboratory collaboration that was planned at the 3rd International Summit on Organic Photovoltaic Stability (ISOS-3). The collaboration involved six laboratories capable of producing seven distinct sets of OPV devices that were degraded under well-defined conditions in accordance with the ISOS-3 protocols. The degradation experiments lasted up to 1830 hours and involved more than 300 cells on more than 100 devices. The devices were analyzed and characterized at different points of their lifetimes by a large number of non-destructive and destructive techniques in order to identify specific degradation mechanisms responsible for the deterioration of the photovoltaic response. Work presented herein involves time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to study chemical degradation in-plane as well as in-depth in the organic solar cells. Various degradation mechanisms were investigated and correlated with cell performance. For example, photo-oxidation of the active material was quantitatively studied as a function of cell performance. The large variety of cell architectures used (some with and some without encapsulation) enabled valuable comparisons and important conclusions to be drawn on degradation behaviour. This comprehensive investigation of OPV stability has significantly advanced the understanding of degradation behaviour in OPV devices, which is an important step towards large scale application of organic solar cells.

How varying surface wettability of different PEDOT:PSS formulations and their mixtures affects perovskite crystallization and the efficiency of inverted perovskite solar cells.

The physico-chemical interaction, surface, and electrical properties of hole transport layers (HTLs) significantly affect the wettability and film crystallization of the deposited perovskite and the corresponding performance of inverted perovskite solar cells (PSCs). One of the most frequently used HTLs for inverted PSCs is poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). Various commercial PEDOT:PSS formulations have already been tested as HTLs. Until now mixtures of these remained rather unexplored. In this study, three commercially available PEDOT:PSS formulations (PH, PH1000, and AI4083), as well as three mixtures (PH:PH1000, PH:AI4083, and PH:PH1000:AI4083; in a 1 : 1 and 1 : 1 : 1 ratios) were used as HTLs to investigate the crystallization of perovskite films and the performance of associated PSCs. Of the three formulations, PEDOT:PSS PH showed better perovskite crystallization, resulting in better solar cell performance followed by both PH:AI4083 and PH:PH1000:AI4083 layers. The pioneering work on mixing PEDOT:PSS resulted in new combinations of PEDOT:PSS, with new properties (work function, surface wettability, and roughness) which are very important parameters for perovskite crystallization and corresponding device efficiencies and stabilities. All PSCs that use the mixed PEDOT:PSS as HTLs revealed higher fill factor and open-circuit voltage values above 900 mV, which is not the same except for PEDOT:PSS PH. As a result, we believe that such a mixing strategy could aid in the creation of various PEDOT:PSS combinations with tuneable properties for certain applications.

Electrode-free visual prosthesis/exoskeleton control using augmented reality glasses in a first proof-of-technical-concept study.

In the field of neuroprosthetics, the current state-of-the-art method involves controlling the prosthesis with electromyography (EMG) or electrooculography/electroencephalography (EOG/EEG). However, these systems are both expensive and time consuming to calibrate, susceptible to interference, and require a lengthy learning phase by the patient. Therefore, it is an open challenge to design more robust systems that are suitable for everyday use and meet the needs of patients. In this paper, we present a new concept of complete visual control for a prosthesis, an exoskeleton or another end effector using augmented reality (AR) glasses presented for the first time in a proof-of-concept study. By using AR glasses equipped with a monocular camera, a marker attached to the prosthesis is tracked. Minimal relative movements of the head with respect to the prosthesis are registered by tracking and used for control. Two possible control mechanisms including visual feedback are presented and implemented for both a motorized hand orthosis and a motorized hand prosthesis. Since the grasping process is mainly controlled by vision, the proposed approach appears to be natural and intuitive.

Non-contact visual control of personalized hand prostheses/exoskeletons by tracking using augmented reality glasses.

A new concept for robust non-invasive optical activation of motorized hand prostheses by simple and non-contact commands is presented. In addition, a novel approach for aiding hand amputees is shown, outlining significant progress in thinking worth testing. In this, personalized 3D-printed artificial flexible hands are combined with commercially available motorized exoskeletons, as they are used e.g. in tetraplegics.

Fast, robust, and accurate monocular peer-to-peer tracking for surgical navigation.

PURPOSE: This work presents a new monocular peer-to-peer tracking concept overcoming the distinction between tracking tools and tracked tools for optical navigation systems. A marker model concept based on marker triplets combined with a fast and robust algorithm for assigning image feature points to the corresponding markers of the tracker is introduced. Also included is a new and fast algorithm for pose estimation. METHODS: A peer-to-peer tracker consists of seven markers, which can be tracked by other peers, and one camera which is used to track the position and orientation of other peers. The special marker layout enables a fast and robust algorithm for assigning image feature points to the correct markers. The iterative pose estimation algorithm is based on point-to-line matching with Lagrange-Newton optimization and does not rely on initial guesses. Uniformly distributed quaternions in 4D (the vertices of a hexacosichora) are used as starting points and always provide the global minimum. RESULTS: Experiments have shown that the marker assignment algorithm robustly assigns image feature points to the correct markers even under challenging conditions. The pose estimation algorithm works fast, robustly and always finds the correct pose of the trackers. Image processing, marker assignment, and pose estimation for two trackers are handled in less than 18 ms on an Intel i7-6700 desktop computer at 3.4 GHz. CONCLUSION: The new peer-to-peer tracking concept is a valuable approach to a decentralized navigation system that offers more freedom in the operating room while providing accurate, fast, and robust results.

Projector-based augmented reality for intuitive intraoperative guidance in image-guided 3D interstitial brachytherapy.

PURPOSE: The aim of this study is to implement augmented reality in real-time image-guided interstitial brachytherapy to allow an intuitive real-time intraoperative orientation. METHODS AND MATERIALS: The developed system consists of a common video projector, two high-resolution charge coupled device cameras, and an off-the-shelf notebook. The projector was used as a scanning device by projecting coded-light patterns to register the patient and superimpose the operating field with planning data and additional information in arbitrary colors. Subsequent movements of the nonfixed patient were detected by means of stereoscopically tracking passive markers attached to the patient. RESULTS: In a first clinical study, we evaluated the whole process chain from image acquisition to data projection and determined overall accuracy with 10 patients undergoing implantation. The described method enabled the surgeon to visualize planning data on top of any preoperatively segmented and triangulated surface (skin) with direct line of sight during the operation. Furthermore, the tracking system allowed dynamic adjustment of the data to the patient's current position and therefore eliminated the need for rigid fixation. Because of soft-part displacement, we obtained an average deviation of 1.1 mm by moving the patient, whereas changing the projector's position resulted in an average deviation of 0.9 mm. Mean deviation of all needles of an implant was 1.4 mm (range, 0.3-2.7 mm). CONCLUSIONS: The developed low-cost augmented-reality system proved to be accurate and feasible in interstitial brachytherapy. The system meets clinical demands and enables intuitive real-time intraoperative orientation and monitoring of needle implantation.

Revelation of Interfacial Energetics in Organic Multiheterojunctions.

Efficient charge generation via exciton dissociation in organic bulk heterojunctions necessitates donor-acceptor interfaces, e.g., between a conjugated polymer and a fullerene derivative. Furthermore, aggregation and corresponding structural order of polymer and fullerene domains result in energetic relaxations of molecular energy levels toward smaller energy gaps as compared to the situation for amorphous phases existing in homogeneously intermixed polymer:fullerene blends. Here it is shown that these molecular energy level shifts are reflected in interfacial charge transfer (CT) transitions and depending on the existence of disordered or ordered interfacial domains. It can be done so by systematically controlling the order at the donor-acceptor interface via ternary blending of semicrystalline and amorphous model polymers with a fullerene acceptor. These variations in interfacial domain order are probed with luminescence spectroscopy, yielding various transition energies due to activation of different recombination channels at the interface. Finally, it is shown that via this analysis the energy landscape at the organic heterojunction interface can be obtained.

MITK-OpenIGTLink for combining open-source toolkits in real-time computer-assisted interventions.

PURPOSE: Due to rapid developments in the research areas of medical imaging, medical image processing and robotics, computer-assisted interventions (CAI) are becoming an integral part of modern patient care. From a software engineering point of view, these systems are highly complex and research can benefit greatly from reusing software components. This is supported by a number of open-source toolkits for medical imaging and CAI such as the medical imaging interaction toolkit (MITK), the public software library for ultrasound imaging research (PLUS) and 3D Slicer. An independent inter-toolkit communication such as the open image-guided therapy link (OpenIGTLink) can be used to combine the advantages of these toolkits and enable an easier realization of a clinical CAI workflow. METHODS: MITK-OpenIGTLink is presented as a network interface within MITK that allows easy to use, asynchronous two-way messaging between MITK and clinical devices or other toolkits. Performance and interoperability tests with MITK-OpenIGTLink were carried out considering the whole CAI workflow from data acquisition over processing to visualization. RESULTS: We present how MITK-OpenIGTLink can be applied in different usage scenarios. In performance tests, tracking data were transmitted with a frame rate of up to 1000 Hz and a latency of 2.81 ms. Transmission of images with typical ultrasound (US) and greyscale high-definition (HD) resolutions of [Formula: see text] and [Formula: see text] is possible at up to 512 and 128 Hz, respectively. CONCLUSION: With the integration of OpenIGTLink into MITK, this protocol is now supported by all established open-source toolkits in the field. This eases interoperability between MITK and toolkits such as PLUS or 3D Slicer and facilitates cross-toolkit research collaborations. MITK and its submodule MITK-OpenIGTLink are provided open source under a BSD-style licence ( http://mitk.org ).

Visualization of surgical 3D information with projector-based augmented reality.

For visualizing surgical information (operation plans) directly onto the patient a projector-based augmented reality system is used for cranio-maxillofacial surgery. A prototype is introduced which has been evaluated in the first clinical cases. In a new setup with a second video projector it is now possible to give additionally 3D information for localization and orientation (6DoF). With this method the repositioning of a bone segment is intuitive and exact applicable.

Intraoperative augmented reality: the surgeons view.

Augmented Reality (AR) is a promising tool for intraoperative visualization. Two different AR systems, one projector based, one based on see-through glasses were used on patients. The task was the transfer of preoperative planning into the intraoperative reality, or the visualization of space occupying lesions, respectively. The intraoperative application of both systems is discussed from the surgeons point of view.

Controlling Exciton Diffusion and Fullerene Distribution in Photovoltaic Blends by Side Chain Modification.

The influence of crystallinity on exciton diffusion and fullerene distribution was investigated by blending amorphous and semicrystalline copolymers. We measured exciton diffusion and fluorescence quenching in such blends by dispersing fullerene molecules into them. We find that the diffusion length is more than two times higher in the semicrystalline copolymer than in the amorphous copolymer. We also find that fullerene preferentially mixes into disordered regions of the polymer film. This shows that relatively small differences in molecular structure are important for exciton diffusion and fullerene distribution.