Kion Norrman

Technical University of Denmark, København, Capital Region, Denmark

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Publications (68)167.23 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The photo-oxidation mechanism of thin-film blends based on poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) upon irradiation with ultraviolet–visible light (UV-Vis) was studied. The use of deuterated P3HT, i.e., poly(3-hexyl-d13-thiophene) (P3HdT), permitted discrimination of carbon originating from the hexyl-d13 chain and carbon originating from PCBM and the nondeuterated thiophene unit. The photo-oxidation of both components of the blend was monitored using the combination of various analytical techniques to probe the bulk and the surface of the deposits. The results show that the stabilization of P3HT by PCBM is due to a morphological reorganization between P3HT and PCBM. This change occurs at a low temperature (ca. 42 °C) and increases the lifetime of the primary property, i.e., the ability of the active layer to absorb light. However, this is counterbalanced by the enhanced formation of oxidized PCBM molecules, which may act as electrons traps. It is shown that UV light is harmful for P3HT, PCBM, and P3HT:PCBM blend stabilities, even if PCBM provides a filter effect that is strongest at short wavelengths. It is proposed that the photochemical behavior of the chromophoric species involved in the chain radical oxidation of P3HT is a key characteristic in the underlying mechanism. The results obtained in this work advance the understanding of active layer stability and will help improve the design of long lifetime organic solar cells thanks to the use of cutoff filter in the substrate or encapsulation of the devices.
    Chemistry of Materials. 11/2013; 25(22):4522–4528.
  • Advanced Energy Materials 04/2013; 3(4). · 10.04 Impact Factor
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    ABSTRACT: Efficient and stable polymer bulk-heterojunction solar cells based on regioregular poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) blend active layer have been fabricated with a MoO3–Au co-evaporation composite film as the anode interfacial layer (AIL). The optical and electrical properties of the composite MoO3–Au film can be tuned by altering the concentration of Au. A composite film with 30% (weight ratio) Au was used as the AIL and showed a better performance than both pure MoO3 and PEDOT:PSS as AIL. The surface morphology of the MoO3–Au composite film was investigated by atomic force microscopy (AFM) and showed that the originally rough ITO substrate became smooth after depositing the composite film, with the root mean square roughness (RMS) decreased from 4.08 nm to 1.81 nm. The smooth surface reduced the bias-dependent carrier recombination, resulting in a large shunt resistance and thus improving the fill factor and efficiency of the devices. Additionally, the air stability of devices with different AILs (MoO3–Au composite, MoO3 and PEDOT:PSS) were studied and it was found that the MoO3–Au composite layer remarkably improved the stability of the solar cells with shelf life-time enhanced by more than 3 and 40 times compared with pure MoO3 layer and PEDOT:PSS layer, respectively. We argue that the stability improvement might be related with the defect states in MoO3 component.
    Organic Electronics 03/2013; 14(3):797–803. · 3.84 Impact Factor
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    ABSTRACT: We are here presenting a comparative study between four different types of functionalities for cross-linking. With relatively simple means bromine, azide, vinyl and oxetane could be incorporated into the side chains of the low band-gap polymer TQ1. Cross-linking of the polymers was achieved by UV-light illumination to give solvent resistant films and reduced phase separation and growth of PCBM crystallites in polymer:PCBM films. The stability of solar cells based on the cross-linked polymers was tested under various conditions. This study showed that cross-linking can improve morphological stability but that it has little influence on the photochemical stability which is also decisive for stable device operation under constant illumination conditions.
    Journal of Materials Chemistry 11/2012; 22(46):24417-24423. · 5.97 Impact Factor
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    ABSTRACT: Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored. The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head-to-tail connected thiophene units. Annealing was found to relax the P3HT films and increase conjugation length and, in turn, increase stability observed as a delayed spectral blueshift caused by photochemical degradation. Crystallinity was found to play a minor role in terms of stability. Oxygen diffusion and light shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push the technology closer to large-scale applications.
    Polymer Degradation and Stability 11/2012; 97(11):2412–2417. · 2.77 Impact Factor
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    ABSTRACT: Here we show polymer solar cells manufactured using only printing and coating of abundant materials directly on flexible plastic substrates or barrier foil using only roll-to-roll methods. Central to the development is a particular roll-to-roll compatible post-processing step that converts the pristine and non-functional multilayer-coated stack into a functional solar cell through formation of a charge selective interface, in situ, following a short electrical pulse with a high current density. After the fast post-processing step the device stack becomes active and all devices are functional with a technical yield and consistency that is compelling.
    Energy & Environmental Science 10/2012; 5(11):9467-9471. · 11.65 Impact Factor
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    ABSTRACT: This work is part of the inter-laboratory collaboration to study the stability of seven distinct sets of state-of-the-art organic photovoltaic (OPVs) devices prepared by leading research laboratories. All devices have been shipped to and degraded at the Danish Technical University (DTU, formerly RISO-DTU) up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. In this work we present a summary of the degradation response observed for the NREL sample, an inverted OPV of the type ITO/ZnO/P3HT:PCBM/PEDOT:PSS/Ag/Al, under full sun stability test. The results reported from the combination of the different characterization techniques results in a proposed degradation mechanism. The final conclusion is that the failure of the photovoltaic response of the device is mainly due to the degradation of the electrodes and not to the active materials of the solar cell.
    Proc SPIE 10/2012;
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    ABSTRACT: 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.
    Physical Chemistry Chemical Physics 07/2012; 14(33):11780-99. · 3.83 Impact Factor
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    ABSTRACT: 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.
    Physical Chemistry Chemical Physics 07/2012; 14(33):11824-45. · 3.83 Impact Factor
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    ABSTRACT: The investigation of degradation of seven distinct sets (with a number of individual cells of n >= 12) of state of the art organic photovoltaic devices prepared by leading research laboratories with a combination of imaging methods is reported. All devices have been shipped to and degraded at Riso DTU up to 1830 hours in accordance with established ISOS-3 protocols under defined illumination conditions. Imaging of device function at different stages of degradation was performed by laser-beam induced current (LBIC) scanning; luminescence imaging, specifically photoluminescence (PLI) and electroluminescence (ELI); as well as by lock-in thermography (LIT). Each of the imaging techniques exhibits its specific advantages with respect to sensing certain degradation features, which will be compared and discussed here in detail. As a consequence, a combination of several imaging techniques yields very conclusive information about the degradation processes controlling device function. The large variety of device architectures in turn enables valuable progress in the proper interpretation of imaging results-hence revealing the benefits of this large scale cooperation in making a step forward in the understanding of organic solar cell aging and its interpretation by state-of-the-art imaging methods.
    Energy & Environmental Science 01/2012; 5(4):6521-6540. · 11.65 Impact Factor
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    ABSTRACT: Double slot-die coating using aqueous inks was employed for the simultaneous coating of the active layer and the hole transport layer (HTL) in fully roll-to-roll (R2R) processed polymer solar cells. The double layer film was coated directly onto an electron transport layer (ETL) comprising doped zinc oxide that was processed by single slot-die coating from water. The active layer comprised poly-3-hexylthiophene:Phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as a dispersion of nanoparticles with a radius of 46nm in water characterized using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The HTL was a dispersion of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) in water. The films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) as chemical probe and X-ray reflectometry as physical probe, confirming the identity of the layered structure. The devices were completed with a back electrode of either Cu tape or evaporated Ag. Under standard solar spectrum irradiation (AM1.5G), current–voltage characterization (J–V) yielded an open-circuit voltage (Voc), short-circuit current (Jsc), fill factor (FF), and power conversion efficiency (PCE) of 0.24V, 0.5mAcm−2, 25%, and 0.03%, respectively, for the best double slot-die coated cell. A single slot-die coated cell using the same aqueous inks and device architecture yielded a Voc, Jsc, FF, and PCE of 0.45V, 1.95mAcm−2, 33.1%, and 0.29%, respectively.
    Solar Energy Materials and Solar Cells - SOLAR ENERG MATER SOLAR CELLS. 01/2012;
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    ABSTRACT: Solubility switching of polymers is very useful in thin layer processing of conjugated polymers, as it allows for multilayer processing and increases the stability of the polymer. Acid catalyzed thermocleavage of ester groups from thiophene polymers carrying primary, secondary, and tertiary substituents have been examined by TGA-MS using different sulphonic acids. A substantial lowering of the cleavage temperature is observed, and the ester cleavage can even be performed in situ on roll-to-roll-coated films on polyethylene terephthalate (PET). -¬ 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012
    Journal of Polymer Science Part A Polymer Chemistry 01/2012; 50(6):1127-1132. · 3.54 Impact Factor
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    ABSTRACT: Light induced thermocleaving of a thermally reactive copolymer based on dithienylthiazolo[5,4-d]thiazole (DTZ) and silolodithiophene (SDT) in contact with the heat sensitive substrate the heat sensitive substrate polyethyleneterphthalate (PET) was effectively demonstrated with the use of high intensity pulsed light, delivered by a commercial photonic sintering system. Thermally labile ester groups are positioned on the DTZ unit of the copolymer that can be eliminated thermally for enhanced photochemical stability and advantages in terms of processing (solubility/insolubility switching). The photonic sintering system was successfully implemented in a full roll-to-roll process on flexible PET substrates and large-area polymer solar cell modules were prepared by solution processing of five layers under ambient conditions using the photonic sintering system for thermocleaving of the active layer. The PET foil did not show any deformation after exposure to the high intensity light only leaving the insoluble thermocleaved active layer. The active layer remained planar after light exposure thereby allowing the coating of supplementary material on top.
    Polymer Chemistry. 01/2012; 3(9):2649-2655.
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    ABSTRACT: Seven distinct sets (n >= 12) of state of the art organic photovoltaic devices were prepared by leading research laboratories in a collaboration planned at the Third International Summit on Organic Photovoltaic Stability (ISOS-3). All devices were shipped to DTU and characterized simultaneously up to 1830 h in accordance with established ISOS-3 protocols under three distinct illumination conditions: accelerated full sun simulation; low level indoor fluorescent lighting; and dark storage with daily measurement under full sun simulation. Three nominally identical devices were used in each experiment both to provide an assessment of the homogeneity of the samples and to distribute samples for a variety of post soaking analytical measurements at six distinct laboratories enabling comparison at various stages in the degradation of the devices. Characterization includes current-voltage curves, light beam induced current (LBIC) imaging, dark lock-in thermography (DLIT), photoluminescence (PL), electroluminescence (EL), in situ incident photon-to-electron conversion efficiency (IPCE), time of flight secondary ion mass spectrometry (TOF-SIMS), cross sectional electron microscopy (SEM), UV visible spectroscopy, fluorescence microscopy, and atomic force microscopy (AFM). Over 100 devices with more than 300 cells were used in the study. We present here design of the device sets, results both on individual devices and uniformity of device sets from the wide range of characterization methods applied at different stages of aging under the three illumination conditions. We will discuss how these data can help elucidate the degradation mechanisms as well as the benefits and challenges associated with the unprecedented size of the collaboration.
    ORGANIC PHOTOVOLTAICS XIII; 01/2012
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    ABSTRACT: Electrode materials are primarily chosen based on their work function to suit the energy levels of the absorber materials. In this paper, we focus on the modification of aluminum cathodes with a thin silver interlayer (2 nm) in copper indium sulfide/poly[(2,7-silafluorene)-alt-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)] (PSiF-DBT) nanocomposite solar cells, which improves the fill factor compared to pure aluminum electrodes. A comprehensive structural investigation was performed by means of transmission electron microscopy and time-of-flight secondary ion mass spectrometry revealing the presence of silver nanoparticles in an aluminum oxide matrix between the absorber layer and the aluminum cathode. In combination with complementary optical investigations, the origin of the improvement is ascribed to a facilitated charge extraction.
    Journal of Physical Chemistry C. 01/2012; 116(36):19191-19196.
  • Polymers. 01/2012; 4(2):1242-1258.
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    ABSTRACT: Organic photovoltaics (OPVs) evolve in an exponential manner in the two key areas of efficiency and stability. The power conversion efficiency (PCE) has in the last decade been increased by almost a factor of ten approaching 10%. A main concern has been the stability that was previously measured in minutes, but can now, in favorable circumstances, exceed many thousands of hours. This astonishing achievement is the subject of this article, which reviews the developments in stability/degradation of OPVs in the last five years. This progress has been gained by several developments, such as inverted device structures of the bulk heterojunction geometry device, which allows for more stable metal electrodes, the choice of more photostable active materials, the introduction of interfacial layers, and roll-to-roll fabrication, which promises fast and cheap production methods while creating its own challenges in terms of stability.
    Advanced Materials 12/2011; 24(5):580-612. · 14.83 Impact Factor
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    ABSTRACT: A glass-fibre-reinforced polyester (GFRP) plate was treated with dielectric barrier discharge (DBD) at atmospheric pressure in air for adhesion improvement. The effects of ultrasonic irradiation using a high-power gas-jet generator during the treatment were investigated. The optical emission spectrum of the discharge remained almost unchanged by the ultrasonic irradiation, indicating that the bulk property of the discharge was not significantly influenced by the ultrasound. However, the ultrasonic irradiation during the plasma treatment suppressed occasional arcing in the DBD, preventing damage of the GFRP plates. The polar component of the surface energy of the polyester plate was 21 mJ/m2 before the treatment, increased markedly to 52 mJ/m2 after 2-s plasma treatment without ultrasonic irradiation, and further increased slightly after longer treatments. In addition, the polar component of the surface energy increased due to the simultaneous ultrasonic irradiation, indicating that the adhesive property would be further improved. This result shows a good agreement with surface characterization by X-ray photoelectron spectroscopy. Time-of-flight secondary ion mass spectrometry ion images show that nitrogen-containing functional groups were uniformly attached after the treatments. The roughness of the GFRP surfaces increased after the plasma treatment, but the ultrasonic irradiation did not enhance surface roughening.
    The Journal of Adhesion 07/2011; 87(7-8):720-731. · 0.86 Impact Factor
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    ABSTRACT: Aqueous nanoparticle dispersions of a series of three low-band-gap polymers poly[4,8-bis(2-ethylhexyloxy)benzo(1,2-b:4,5-b')dithiophene-alt-5,6-bis(octyloxy)-4,7-di(thiophen-2-yl)(2,1,3-benzothiadiazole)-5,5'-diyl] (P1), poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diyl] (P2), and poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (P3) were prepared using ultrasonic treatment of a chloroform solution of the polymer and [6,6]-phenyl-C(61)-butyric acid methyl ester ([60]PCBM) mixed with an aqueous solution of sodium dodecylsulphate (SDS). The size of the nanoparticles was established using small-angle X-ray scattering (SAXS) of the aqueous dispersions and by both atomic force microscopy (AFM) and using both grazing incidence SAXS (GISAXS) and grazing incidence wide-angle X-ray scattering (GIWAXS) in the solid state as coated films. The aqueous dispersions were dialyzed to remove excess detergent and concentrated to a solid content of approximately 60 mg mL(-1). The formation of films for solar cells using the aqueous dispersion required the addition of the nonionic detergent FSO-100 at a concentration of 5 mg mL(-1). This enabled slot-die coating of high quality films with a dry thickness of 126 ± 19, 500 ± 25, and 612 ± 22 nm P1, P2, and P3, respectively for polymer solar cells. Large area inverted polymer solar cells were thus prepared based on the aqueous inks. The power conversion efficiency (PCE) reached for each of the materials was 0.07, 0.55, and 0.15% for P1, P2, and P3, respectively. The devices were prepared using coating and printing of all layers including the metal back electrodes. All steps were carried out using roll-to-roll (R2R) slot-die and screen printing methods on flexible substrates. All five layers were processed using environmentally friendly methods and solvents. Two of the layers were processed entirely from water (the electron transport layer and the active layer).
    ACS Nano 05/2011; 5(5):4188-96. · 12.03 Impact Factor
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    ABSTRACT: We show that it is possible to perform ellipsometry on large area roll-to-roll (R2R) coated solar cells on flexible substrates and further demonstrate that the slot-die coating technique employed yields the same bulk heterojunction (BHJ) film morphology and vertical phase separation as laboratory samples prepared by the spin coating technique. The solar cell device geometry was Kapton/Al/Cr/P3HT:PCBM/PEDOT:PSS/Ag. Variable angle ellipsometry was used to determine the optical dispersions of the pure phases of P3HT and PCBM allowing an effective medium approximation model to be employed. It was found that a top layer phase separation of P3HT and a vertical linear gradient of P3HT and PCBM best described the BHJ layer. The model was tested for samples of varying thickness and blend composition, model parameters including thickness (AFM), vertical composition (XPS depth profiling), and optical transmission (optical simulation and UV–visible spectroscopy comparisons) was confirmed to comply with the model. A means of quality testing and optimization of the coating procedure line scans across a R2R slot-die-coated sample over large distances (8 cm) was made giving insight into thickness and composition uniformity.
    The Journal of Physical Chemistry C. 05/2011; 115(21).