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p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane
(2016)
State-of-the-art p-type doping of organic semiconductors is usually achieved by employing strong -electron acceptors, a prominent example being tetrafluorotetracyanoquinodimethane (F(4)TCNQ). Here, doping of the semiconducting model polymer poly(3-hexylthiophene), P3HT, using the strong Lewis acid tris(pentafluorophenyl)borane (BCF) as a dopant, is investigated by admittance, conductivity, and electron paramagnetic resonance measurements. The electrical characteristics of BCF- and F(4)TCNQ-doped P3HT layers are shown to be very similar in terms of the mobile hole density and the doping efficiency. Roughly 18% of the employed dopants create mobile holes in either F-4 TCNQ- or BCF-doped P3HT, while the majority of doping-induced holes remain strongly Coulomb-bound to the dopant anions. Despite similar hole densities, conductivity and hole mobility are higher in BCF-doped P3HT layers than in F(4)TCNQ-doped samples. This and the good solubility in many organic solvents render BCF very useful for p-type doping of organic semiconductors.
A dual-characteristic polymer field-effect transistor has markedly different characteristics in low and high voltage operations. In the low-voltage range (<5 V) it shows sharp subthreshold slopes (0.3–0.4 V dec−1), using which a low-voltage inverter with gain 8 is realized, while high-voltage (>5 V) induces symmetric current with regard to drain and gate voltages, leading to discrete differential (trans) conductances.
The competition between charge extraction and nongeminate recombination critically determines the current-voltage characteristics of organic solar cells (OSCs) and their fill factor. As a measure of this competition, several figures of merit (FOMs) have been put forward; however, the impact of space charge effects has been either neglected, or not specifically addressed. Here we revisit recently reported FOMs and discuss the role of space charge effects on the interplay between recombination and extraction. We find that space charge effects are the primary cause for the onset of recombination in so-called non-Langevin systems, which also depends on the slower carrier mobility and recombination coefficient. The conclusions are supported with numerical calculations and experimental results of 25 different donor/acceptor OSCs with different charge transport parameters, active layer thicknesses or composition ratios. The findings represent a conclusive understanding of bimolecular recombination for drift dominated photocurrents and allow one to minimize these losses for given device parameters.
Fluorine-containing low-energy-gap organic dyes with low voltage losses for organic solar cells
(2016)
Fluorine-containing donor molecules TFTF, CNTF and PRTF are designed and isomer selectively synthesized for application in vacuum-deposited organic solar cells. These molecules comprise a donor acceptor molecular architecture incorporating thiophene and benzothiadiazole derivatives as the electron-donating and electron-withdrawing moieties, respectively. As opposed to previously reported materials from this class, PRTF can be purified by vacuum sublimation at moderate to high yields because of its higher volatility and better stabilization due to a stronger intramolecular hydrogen bond, as compared to TFTF and CNTF. The UV-vis absorption spectra of the three donors show an intense broadband absorption between 500 nm and 800 nm with, similar positions of their frontier energy levels. The photophysical properties of the three donor molecules are thoroughly tested and optimized in bulk heterojunction solar cells with C-60 as acceptor. PRTF shows the best performance, yielding power conversion efficiencies of up to 3.8%. Moreover, the voltage loss for the PRTF device due to the non radiative recombination of free charge carriers is exceptionally low (0.26 V) as compared to typical values for organic solar cells (>0.34V). (C) 2016 Published by Elsevier B.V.
The electrical conductivity of organic semiconductors can be enhanced by orders of magnitude via doping with strong molecular electron acceptors or donors. Ground-state integer charge transfer and charge-transfer complex formation between organic semiconductors and molecular dopants have been suggested as the microscopic mechanisms causing these profound changes in electrical materials properties. Here, we study charge-transfer interactions between the common molecular p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and a systematic series of thiophene-based copolymers by a combination of spectroscopic techniques and electrical measurements. Subtle variations in chemical structure are seen to significantly impact the nature of the charge-transfer species and the efficiency of the doping process, underlining the need for a more detailed understanding of the microscopic doping mechanism in organic semiconductors to reliably guide targeted chemical design.
We investigate hybrid charge transfer states (HCTS) at the planar interface between a-NPD and ZnO by spectrally resolved electroluminescence (EL) and external quantum efficiency (EQE) measurements. Radiative decay of HCTSs is proven by distinct emission peaks in the EL spectra of such bilayer devices in the NIR at energies well below the bulk a-NPD or ZnO emission. The EQE spectra display low energy contributions clearly red-shifted with respect to the a-NPD photocurrent and partially overlapping with the EL emission. Tuning of the energy gap between the ZnO conduction band and a-NPD HOMO level (E-int) was achieved by modifying the ZnO surface with self-assembled monolayers based on phosphonic acids. We find a linear dependence of the peak position of the NIR EL on E-int, which unambiguously attributes the origin of this emission to radiative recombination between an electron on the ZnO and a hole on a-NPD. In accordance with this interpretation, we find a strictly linear relation between the open-circuit voltage and the energy of the charge state for such hybrid organicinorganic interfaces.
Hybrid multijunction solar cells comprising hydrogenated amorphous silicon and an organic bulk heterojunction are presented, reaching 11.7% power conversion efficiency. The benefits of merging inorganic and organic subcells are pointed out, the optimization of the cells, including optical modeling predictions and tuning of the recombination contact are described, and an outlook of this technique is given.
PCPDTBT, a marginally crystallizable polymer, is crystallized into a new crystal structure using solvent-vapor annealing. Highly ordered areas with three different polymer-chain orientations are identified using TEM/ED, GIWAXS, and polarized Raman spectroscopy. The optical and structural properties differ significantly from films prepared by standard device preparation protocols. Bilayer solar cells, however, show similar performance.
When arranged in a proper nanoaggregate architecture, gold nanoparticles can offer controllable plasmon-related absorption/scattering, yielding distinct color effects that depend critically on the relative orientation and distance between nanoparticle constituents. Herein, we report on the implementation of novel plasmonic nanoarchitectures based on complexes between gold nanoparticles and an azobenzene-modified cationic surfactant that can exhibit a light-tunable plasmonic response. The formation of such complexes becomes possible through the use of strongly negatively charged bare gold nanoparticles (similar to 10-nm diameter) prepared by the method of laser ablation in deionized water. Driven by electrostatic interactions, the cationic surfactant molecules attach and form a shell around the negatively charged nanoparticles, resulting in neutralization of the particle charge or even overcompensation beyond which the nanoparticles become positively charged. At low and high surfactant concentrations, Au nanoparticles are negatively and positively charged, respectively, and are represented by single species due to electric repulsion effects having absorption peaks around 523-527 nm, whereas at intermediate concentrations, the Au nanoparticles become neutral, forming nanoscale 100-nm clusterlike aggregates and exhibiting an additional absorption peak at gimel > 600 nm and a visible change in the color of the solution from red to blue. Because of the presence of the photosensitive azobenzene unit in the surfactant tail that undergoes trans-to-cis isomerization under irradiation with UV light, we then demonstrate a light-controlled nanoclustering of nanoparticles, yielding a switch in the plasmonic absorption band and a related change in the solution color. The formed hybrid architectures with a light-controlled plasmonic response could be important for a variety of tasks, including biomedical, surface-enhanced Raman spectroscopy (SERS), data transmission, and storage applications.
An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene): phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices. (C) 2015 AIP Publishing LLC.
This work elucidates the impact of charge transport on the photovoltaic properties of organic solar cells. Here we show that the analysis of current-voltage curves of organic solar cells under illumination with the Shockley equation results in values for ideality factor, photo-current and parallel resistance, which lack physical meaning. Drift-diffusion simulations for a wide range of charge-carrier mobilities and illumination intensities reveal significant carrier accumulation caused by poor transport properties, which is not included in the Shockley equation. As a consequence, the separation of the quasi Fermi levels in the organic photoactive layer (internal voltage) differs substantially from the external voltage for almost all conditions. We present a new analytical model, which considers carrier transport explicitly. The model shows excellent agreement with full drift-diffusion simulations over a wide range of mobilities and illumination intensities, making it suitable for realistic efficiency predictions for organic solar cells.
Time-delayed collection field (TDCF), bias-assisted charge extraction (BACE), and space charge-limited current (SCLC) measurements are combined with complete numerical device simulations to unveil the effect of the solvent additive 1,8-diiodooctane (DIO) on the performance of PTB7:PCBM bulk heterojunction solar cells. DIO is shown to increase the charge generation rate, reduce geminate and bimolecular recombination, and increase the electron mobility. In total, the reduction of loss currents by processing with the additive raises the power conversion efficiency of the PTB7:PCBM blend by a factor of almost three. The lower generation rates and higher geminate recombination losses in devices without DIO are consistent with a blend morphology comprising large fullerene clusters embedded within a PTB7-rich matrix, while the low electron mobility suggests that these fullerene clusters are themselves composed of smaller pure fullerene aggregates separated by disordered areas. Our device simulations show unambiguously that the effect of the additive on the shape of the currentvoltage curve (J-V) cannot be ascribed to the variation of only the mobility, the recombination, or the field dependence of generation. It is only when the changes of all three parameters are taken into account that the simulation matches the experimental J-V characteristics under all illumination conditions and for a wide range of voltages.
Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter theta, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor: acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor: acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination.
The IR-based method of infrared transition moment orientational analysis (IR-TMOA) is employed to unravel molecular order in thin layers of the semiconducting polymer poly[N,N'-bis(2-octyldodecyl),-1,4,5,8-naphthalene-diimide-2,6-diyl]-alt-5-5'-(2,2'-bithiophene) (P(NDI2OD-T2)). Structure-specific vibrational bands are analyzed in dependence On polarization and inclination of the sample-With respect to the optical axis. By that the molecular Order parameter tensor for the respective molecular moieties with regard to the sample: coordinate system is deduced. Making use of the specificity of the IR spectral range, we are able to determine separately the orientation of atomistic planes defined through the naphthalenediimide (NDI) and bithiophene (T2) units relative to the substrate, and hence, relative to each other. A pronounced solvent effect is observed While chlorobenzene causes the T2 planes to align preferentially parallel to the substrate at an angle of 29 degrees, using a 1:1 chloronaphthalene:xylene mixture results in a reorientation of the T2 units from a face on into an edge on arrangement. In contrast the NDI unit remains unaffected. Additionally, for both solvents evidence is observed for the aggregation of chains in accord With recently published results obtained by UV-vis absorption spectroscopy.
Blending the conjugated polymer poly(3-hexylthiophene) (P3HT) with the insulating electret polystyrene (PS), we show that the threshold voltage V-t of organic field-effect transistors (OFETs) can be easily and reversely tuned by applying a gate bias stress at 130 degrees C. It is proposed that this phenomenon is caused by thermally activated charge injection from P3HT into PS matrix, and that this charge is immobilized within the PS matrix after cooling down to room temperature. Therefore, room-temperature hysteresis-free FETs with desired V-t can be easily achieved. The approach is applied to reversely tune the OFET mode of operation from accumulation to depletion, and to build inverters. (C) 2015 AIP Publishing LLC.
carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold viaweakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer: fullerene, small-molecule:C-60 and polymer: polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.
Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to M-w approximate to 50 kg mol(-1) and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32-45%) in all-polymer solar cells compared to NDI-based materials (15-30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.
Each year we are bombarded with B.Sc. and Ph.D. applications from students that want to improve the world. They have learned that their future depends on changing the type of fuel we use and that solar energy is our future. The hope and energy of these young people will transform future energy technologies, but it will not happen quickly. Organic photovoltaic devices are easy to sketch, but the materials, processing steps, and ways of measuring the properties of the materials are very complicated. It is not trivial to make a systematic measurement that will change the way other research groups think or practice. In approaching this chapter, we thought about what a new researcher would need to know about organic photovoltaic devices and materials in order to have a good start in the subject. Then, we simplified that to focus on what a new researcher would need to know about poly-3-hexylthiophene: phenyl-C61-butyric acid methyl ester blends (P3HT: PCBM) to make research progress with these materials. This chapter is by no means authoritative or a compendium of all things on P3HT: PCBM. We have selected to explain how the sample fabrication techniques lead to control of morphology and structural features and how these morphological features have specific optical and electronic consequences for organic photovoltaic device applications.
We introduce a new and simple method to quantify the effective extraction mobility in organic solar cells at low electric fields and charge carrier densities comparable to operation conditions under one sun illumination. By comparing steady-state carrier densities at constant illumination intensity and under open-circuit conditions, the gradient of the quasi-Fermi potential driving the current is estimated as a function of external bias and charge density. These properties are then related to the respective steady-state current to determine the effective extraction mobility. The new technique is applied to different derivatives of the well-known low-band-gap polymer PCPDTBT blended with PC70BM. We show that the slower average extraction due to lower mobility accounts for the moderate fill factor when solar cells are fabricated with mono- or difluorinated PCPDTBT. This lower extraction competes with improved generation and reduced nongeminate recombination, rendering the monofluorinated derivative the most efficient donor polymer.
The effect of SiO2 nanoparticles on carbon nitride (C3N4) photoactivity performance is described. The composite SiO2-C3N4 materials exhibit a higher activity in the photo degradation of RhB dye. A detailed analysis of the chemical and optical properties of the composite C3N4 materials shows that the photo activity increases with higher SiO2 concentration. We found out that the presence of SiO2 nanoparticles strongly affects the fluorescence intensity of the matrix and life time by the creation of new energy states for charge transfer within the C3N4. Furthermore, the use of SiO2 in the synthesis of C3N4 leads to new morphology with higher surface area which results in another, secondary improvement of C3N4 photoactivity. The effect of different surfaces within C3N4 on its chemical and electronic properties is discussed and a tentative mechanism is proposed. The utilization of SiO2 nanoparticles improves both photophysical and chemical properties of C3N4 and opens new possibilities for further enhancement of C3N4 catalytic properties by the formation of composites with many other materials.
Inverted organic solar cells are fabricated using low-temperature-annealed ZnO film as an electron transport layer. Uniform ZnO films were prepared by spin coating a diethylzinc (DEZ) precursor solution in air, followed by annealing at 100 A degrees C. Organic solar cells prepared on these ZnO films with a 1:1 P3HT:PCBM blend as the active layer show a high power conversion efficiency of 4.03 %, which is more than 10 % higher than the PCE of solar cells comprising ZnO prepared via a high-temperature sol-gel route.
Time-delayed collection field (TDCF) and bias-amplified charge extraction (BACE) are applied to as-prepared and annealed poly(3-hexylthiophene):[6,6]-phenyl C-71 butyric acid methyl ester (P3HT:PCBM) blends coated from chloroform. Despite large differences in fill factor, short-circuit current, and power conversion efficiency, both blends exhibit a negligible dependence of photogeneration on the electric field and strictly bimolecular recombination (BMR) with a weak dependence of the BMR coefficient on charge density. Drift-diffusion simulations are performed using the measured coefficients and mobilities, taking into account bimolecular recombination and the possible effects of surface recombination. The excellent agreement between the simulation and the experimental data for an intensity range covering two orders of magnitude indicates that a field-independent generation rate and a density-independent recombination coefficient describe the current-voltage characteristics of the annealed P3HT: PCBM devices, while the performance of the as-prepared blend is shown to be limited by space charge effects due to a low hole mobility. Finally, even though the bimolecular recombination coefficient is small, surface recombination is found to be a negligible loss mechanism in these solar cells.
A model for the extraction of the charge density dependent mobility and variable contact resistance in thin film transistors is proposed by performing a full derivation of the current-voltage characteristics both in the linear and saturation regime of operation. The calculated values are validated against the ones obtained from direct experimental methods. This approach allows unambiguous determination of gate voltage dependent contact and channel resistance from the analysis of a single device. It solves the inconsistencies in the commonly accepted mobility extraction methods and provides additional possibilities for the analysis of the injection and transport processes in semiconducting materials. (C) 2014 AIP Publishing LLC.
New polymers with high electron mobilities have spurred research in organic solar cells using polymeric rather than fullerene acceptors due to their potential of increased diversity, stability, and scalability. However, all-polymer solar cells have struggled to keep up with the steadily increasing power conversion efficiency of polymer: fullerene cells. The lack of knowledge about the dominant recombination process as well as the missing concluding picture on the role of the semi-crystalline microstructure of conjugated polymers in the free charge carrier generation process impede a systematic optimization of all-polymer solar cells. These issues are examined by combining structural and photo-physical characterization on a series of poly(3-hexylthiophene) (donor) and P(NDI2OD-T2) (acceptor) blend devices. These experiments reveal that geminate recombination is the major loss channel for photo-excited charge carriers. Advanced X-ray and electron-based studies reveal the effect of chloronaphthalene co-solvent in reducing domain size, altering domain purity, and reorienting the acceptor polymer crystals to be coincident with those of the donor. This reorientation correlates well with the increased photocurrent from these devices. Thus, effi cient split-up of geminate pairs at polymer/polymer interfaces may necessitate correlated donor/acceptor crystal orientation, which represents an additional requirement compared to the isotropic fullerene acceptors.
Charge transport anisotropy in highly oriented thin films of the acceptor polymer P(NDI2OD-T2)
(2014)
The nanomorphology of the high mobility polymer poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} P(NDI2OD-T2) in thin films is explored as a function of different annealing conditions and correlated to optical and electrical properties. While nanofibrils with face-on orientation in form I are obtained directly after spin-coating and annealing below the melt transition temperature, clear evidence of lamellar structures is found after melt-annealing followed by slow cooling to room temperature. Interestingly these structural changes are accompanied by distinct changes in the absorption patterns. Electron diffraction measurements further show clear transitions towards predominant edge-on oriented chains in form II upon melt-annealing. Large-scale alignment with dichroic ratios up to 10 and improved order is achieved by high temperature rubbing and subsequent post-rubbing annealing. These highly oriented morphologies allow anisotropic in-plane charge transport to be probed with top-gate transistors parallel and perpendicular to the polymer chain direction. Mobilities up to 0.1 cm(2) V-1 s(-1) are observed parallel to the polymer chain, which is up to 10 times higher than those perpendicular to the polymer chain.
In this work, the authors present a 7.5% efficient hybrid tandem solar cell with the bottom cell made of amorphous silicon and a Si-PCPDTBT:PC70BM bulk heterojunction top cell. Loss-free recombination contacts were realized by combing Al-doped ZnO with either the conducting polymer composite PEDOT:PSS or with a bilayer of ultrathin Al and MoO3. Optimization of these contacts results in tandem cells with high fill factors of 70% and an open circuit voltage close to the sum of those of the sub-cells. This is the best efficiency reported for this type of hybrid tandem cell so far. Optical and electrical device modeling suggests that the efficiency can be increased to similar to 12% on combining a donor polymer with suitable absorption onset with PCBM. We also describe proof-of-principle studies employing light trapping in hybrid tandem solar cells, suggesting that this device architecture has the potential to achieve efficiencies well above 12%. (C) 2014 Elsevier B.V. All rights reserved.
Photogeneration, recombination, and transport of free charge carriers in all-polymer bulk heterojunction solar cells incorporating poly(3-hexylthiophene) (P3HT) as donor and poly([N,N'-bis(2-octyldodecyl)-naphthelene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)) (P(NDI2OD-T2)) as acceptor polymer have been investigated by the use of time delayed collection field (TDCF) and time-of-flight (TOF) measurements. Depending on the preparation procedure used to dry the active layers, these solar cells comprise high fill factors (FFs) of up to 67%. A strongly reduced bimolecular recombination (BMR), as well as a field-independent free charge carrier generation are observed, features that are common to high performance fullerene-based solar cells. Resonant soft X-ray measurements (R-SoXS) and photoluminescence quenching experiments (PQE) reveal that the BMR is related to domain purity. Our results elucidate the similarities of this polymeric acceptor with the superior recombination properties of fullerene acceptors.
The charge generation and recombination processes following photo-excitation of a low-bandgap polymer:perylene diimide photovoltaic blend are investigated by transient absorption pump-probe spectroscopy covering a dynamic range from femto-to microseconds to get insight into the efficiency-limiting photophysical processes. The several tens of picoseconds, and its efficiency is only half of that in a polymer:fullerene photoinduced electron transfer from the polymer to the perylene acceptor takes up to blend. This reduces the short-circuit current. Time-delayed collection field experiments reveal that the subsequent charge separation is strongly field-dependent, limiting the fill factor and lowering the short-circuit current in polymer:PDI devices. Upon excitation of the acceptor in the low-bandgap polymer blend, the PDI exciton undergoes charge transfer on a time scale of several tens of picoseconds. However, a significant fraction of the charges generated at the interface are quickly lost because of fast geminate recombination. This reduces the short-circuit current even further, leading to a scenario in which only around 2596 of the initial photoexcitations generate free charges that can potentially contribute to the photocurrent. In summary, the key photophysical limitations of perylene diimide as an acceptor in low-bandgap polymer blends appear at the interface between the materials, with the kinetics of both charge generation and separation inhibited as compared to that of fullerenes.
Herein we report a general liquid-mediated pathway for the growth of continuous polymeric carbon nitride (C3N4) thin films. The deposition method consists of the use of supramolecular complexes that transform to the liquid state before direct thermal condensation into C3N4 solid films. The resulting films exhibit continuous porous C3N4 networks on various substrates. Moreover, the optical absorption can be easily tuned to cover the solar spectrum by the insertion of an additional molecule into the starting complex. The strength of the deposition method is demonstrated by the use of the C3N4 layer as the electron acceptor in a polymer solar cell that exhibits a remarkable open-circuit voltage exceeding 1 V. The easy, safe, and direct synthesis of carbon nitride in a continuous layered architecture on different functional substrates opens new possibilities for the fabrication of many energy-related devices.
Herein, we report the use of upconversion agents to modify graphite carbon nitride (g-C3N4) by direct thermal condensation of a mixture of ErCl3 center dot 6H(2)O and the supramolecular precursor cyanuric acid-melamine. We show the enhancement of g-C3N4 photoactivity after Er3+ doping by monitoring the photodegradation of Rhodamine B dye under visible light. The contribution of the upconversion agent is demonstrated by measurements using only a red laser. The Er3+ doping alters both the electronic and the chemical properties of g-C3N4. The Er3+ doping reduces emission intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes.
Herein, we report the facile synthesis of an efficient roll-like carbon nitride (C3N4) photocatalyst for hydrogen production using a supramolecular complex composed of cyanuric acid, melamine, and barbituric acid as the starting monomers. Optical and photocatalytic investigations show, along with the known red shift of absorption into the visible region, that the insertion of barbituric acid results in the in situ formation of in-plane heterojuctions, which enhance the charge separation process under illumination. Moreover, platinum as the standard cocatalyst in photocatalysis could be successfully replaced with first row transition metal salts and complexes under retention of 50% of the catalytic activity. Their mode of deposition and interaction with the semiconductor was studied in detail. Utilization of the supramolecular approach opens new opportunities to manipulate the charge transfer process within carbon nitride with respect to the design of a more efficient carbon nitride photocatalyst with controlled morphology and optical properties.
Developing novel materials and device architectures to further enhance the efficiency of polymer solar cells requires a fundamental understanding of the impact of chemical structures on photovoltaic properties. Given that device characteristics depend on many parameters, deriving structureproperty relationships has been very challenging. Here we report that a single parameter, hole mobility, determines the fill factor of several hundred nanometer thick bulk heterojunction photovoltaic devices based on a series of copolymers with varying amount of fluorine substitution. We attribute the steady increase of hole mobility with fluorine content to changes in polymer molecular ordering. Importantly, all other parameters, including the efficiency of free charge generation and the coefficient of nongeminate recombination, are nearly identical. Our work emphasizes the need to achieve high mobility in combination with strongly suppressed charge recombination for the thick devices required by mass production technologies.
Zinc oxide (ZnO) is regarded as a promising alternative material for transparent conductive electrodes in optoelectronic devices. However, ZnO suffers from poor chemical stability. ZnO also has a moderate work function (WF), which results in substantial charge injection barriers into common (organic) semiconductors that constitute the active layer in a device. Controlling and tuning the ZnO WF is therefore necessary but challenging. Here, a variety of phosphonic acid based self-assembled monolayers (SAMs) deposited on ZnO surfaces are investigated. It is demonstrated that they allow the tuning the WF over a wide range of more than 1.5 eV, thus enabling the use of ZnO as both the hole-injecting and electron-injecting contact. The modified ZnO surfaces are characterized using a number of complementary techniques, demonstrating that the preparation protocol yields dense, well-defined molecular monolayers.
The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near-field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT-12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well-ordered dichroic areas at the ten-micrometer-scale, which are sub-divided into domains with different molecular in-plane orientation. These serve as a template for the formation of smaller needle-like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field-effect mobility of these layers of 10(-3) cm 2 V(-1) s(-1), whereas it is limited by the presence of domain boundaries at macroscopic distances.
Time-delayed collection field (TDCF) experiments are performed on bulk heterojunction solar cells comprised of a blend of poly(3-hexylthiophene) and [6,6]-phenyl C-71 butyric acid methyl ester. TDCF is analogous to a pump-probe experiment using optical excitation and an electrical probe with a resolution of < 100 ns. The number of free charge carriers extracted after a short delay is found to be independent of the electric field during illumination. Also, experiments performed with a variable delay between the optical excitation and the electrical probe do not reveal any evidence for the generation of charge via field-assisted dissociation of bound long-lived polaron pairs. Photocurrent transients are well fitted by computational drift diffusion simulations with only direct generation of free charge carriers. With increasing delay times between pump and probe, two loss mechanisms are identified; first, charge-carriers are swept out of the device by the internal electric field, and second, bimolecular recombination of the remaining carriers takes place with a reduced recombination coefficient.
We use the Kelvin probe method to study the energy-level alignment of four conjugated polymers deposited on various electrodes. Band bending is observed in all polymers when the substrate work function exceeds critical values. Through modeling, we show that the band bending is explained by charge transfer from the electrodes into a small density of states that extends several hundred meV into the band gap. The energetic spread of these states is correlated with charge-carrier mobilities, suggesting that the same states also govern charge transport in the bulk of these polymers.
Control of crystallographic texture from mostly face-on to edge-on is observed for the film morphology of the n-type semicrystalline polymer [N,N-9-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diy1]alt-5,59-(2,29-bithiophene)}, P(NDI2OD-T2), when annealing the film to the polymer melting point followed by slow cooling to ambient temperature. A variety of X-ray diffraction analyses, including pole figure construction and Fourier transform peak shape deconvolution, are employed to quantify the texture change, relative degree of crystallinity and lattice order. We find that annealing the polymer film to the melt leads to a shift from 77.5% face-on to 94.6% edge-on lamellar texture as well as to a 2-fold increase in crystallinity and a 40% decrease in intracrystallite cumulative disorder. The texture change results in a significant drop in the electron-only diode current density through the film thickness upon melt annealing while little change is observed in the in-plane transport of bottom gated thin film transistors. This suggests that the texture change is prevalent in the film interior and that either the (bottom) surface structure is different from the interior structure or the intracrystalline order and texture play a secondary role in transistor transport for this material.
Photo-induced deformations in azobenzene-containing polymers (azo-polymers) are central to a number of applications, such as optical storage and fabrication of diffractive elements. The microscopic nature of the underlying opto-mechanical coupling is yet not clear. In this study, we address the experimental finding that the scenario of the effects depends on molecular architecture of the used azo-polymer. Typically, opposite deformations in respect to the direction of light polarization are observed for liquid crystalline and amorphous azo-polymers. In this study, we undertake molecular dynamics simulations of two different models that mimic these two types of azo-polymers. We employ hybrid force field modeling and consider only trans-isomers of azobenzene, represented as Gay-Berne sites. The effect of illumination on the orientation of the chromophores is considered on the level of orientational hole burning and emphasis is given to the resulting deformation of the polymer matrix. We reproduce deformations of opposite sign for the two models being considered here and discuss the relevant microscopic mechanisms in both cases.
New materials for polymer organic light-emitting diodes based on a polymer matrix doped with phosphorescent dyes are presented. The matrix system is based on a polystyrene backbone bearing either electron or hole transporting units at the 4-position of each repeat unit. Random copolymers and polymer blend systems of the homopolymers are prepared, both with 62 wt.% electron transporting and 38 wt.% hole transporting moieties. Adding a green electrophosphorescent dye to the polymer matrix leads to efficient electroluminescence with a maximum current efficiency of 35 cd/A and a maximum external quantum efficiency of up to 10%. The mobilities of electrons and holes in the dye-doped copolymer, as measured by transient electroluminescence, are around 5 x 10(-5) and 5 x 10(-6) cm(2)/Vs, respectively, while the blend of the two homopolymers exhibits slightly lower mobilities of both types of carriers. Despite the pronounced imbalance of charge transport, the device performance is almost entirely limited by the phosphorescence efficiency of the dye, implying balanced flow of holes and electrons into the active region. Also, devices made with either the copolymer or the blend yielded very similar device efficiencies, despite the noticeable difference in electron and hole mobility. It is proposed that electrons are efficiently blocked at the interlayer and that the so-formed space charge assists the balanced injection of holes.
We simulate organic bulk heterojunction solar cells. The effects of energetic disorder are incorporated through a Gaussian or exponential model of density of states. Analytical models of open-circuit voltage (V(OC)) are derived from the splitting of quasi-Fermi potentials. Their predictions are backed up by more complex numerical device simulations including effects such as carrier-density-dependent charge-carrier mobilities. It is predicted that the V(OC) depends on: (1) the donor-acceptor energy gap; (2) charge-carrier recombination rates; (3) illumination intensity; (4) the contact work functions (if not in the pinning regime); and (5) the amount of energetic disorder. A large degree of energetic disorder, or a high density of traps, is found to cause significant reductions in V(OC). This can explain why V(OC) is often less than expected in real devices. Energetic disorder also explains the nonideal temperature and intensity dependence of V(OC) and the superbimolecular recombination rates observed in many real bulk heterojunction solar cells.
We investigate charge transport in a high-electron mobility polymer, poly(N, N-bis 2-octyldodecyl-naphthalene-1,4,5,8-bis dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene) [P(NDI2OD-T2), Polyera ActivInk (TM) N2200]. Time-of-flight measurements reveal electron mobilities approaching those measured in field-effect transistors, the highest ever recorded in a conjugated polymer using this technique. The modest temperature dependence and weak dispersion of the transients indicate low energetic disorder in this material. Steady-state electron-only current measurements reveal a barrier to injection of about 300 meV. We propose that this barrier is located within the P(NDI2OD-T2) film and arises from molecular orientation effects.
A fundamental understanding of the relationship between the bulk morphology and device performance is required for the further development of bulk heterojunction organic solar cells. Here, non-optimized (chloroform cast) and nearly optimized (solvent-annealed o-dichlorobenzene cast) P3HT:PCBM blend films treated over a range of annealing temperatures are studied via optical and photovoltaic device measurements. Parameters related to the P3HT aggregate morphology in the blend are obtained through a recently established analytical model developed by F. C. Spano for the absorption of weakly interacting H-aggregates. Thermally induced changes are related to the glass transition range of the blend. In the chloroform prepared devices, the improvement in device efficiency upon annealing within the glass transition range can be attributed to the growth of P3HT aggregates, an overall increase in the percentage of chain crystallinity, and a concurrent increase in the hole mobilities. Films treated above the glass transition range show an increase in efficiency and fill factor not only associated with the change in chain crystallinity, but also with a decrease in the energetic disorder. On the other hand, the properties of the P3HT phase in the solvent-annealed o-dichlorobenzene cast blends are almost indistinguishable from those of the corresponding pristine P3HT layer and are only weakly affected by thermal annealing. Apparently, slow drying of the blend allows the P3HT chains to crystallize into large domains with low degrees of intra- and interchain disorder. This morphology appears to be most favorable for the efficient generation and extraction of charges.
We correlate the morphology and energy level alignment of bilayer structures comprising the donor poly(3-hexylthiophene) (P3HT) and the acceptor polyfluorene copolymer poly(9,90dialklylfluorene-alt-4,7-bis(2,5-thiendiyl)-2,1,3-benzothiadiazole) (PFTBTT) with the performance of these bilayers in organic photovoltaic cells (OPVCs). The conducting polymer poly(ethylenedioxythiophene): poly (styrenesulfonate) (PEDT:PSS) was used as the bottom electrode and Ca as the top electrode. Ultraviolet photoelectron spectroscopy (UPS) revealed that notable interface dipoles occur at all interfaces across the OPVC structure, highlighting that vacuum level alignment cannot reliably be used to estimate the electronic properties for device design. Particularly the effective electrode work function values (after contact formation with the conjugated polymers) differ significantly from those of the pristine electrode materials. Chemical reactions between PEDT: PSS and P3HT on the one hand and Ca and PFTBTT on the other hand are identified as cause for the measured interface dipoles. The vacuum level shift between P3HT and PFTBTT is related to mutual energy level pinning at gap states. Annealing induced morphological changes at the P3HT/PFTBTT interface increased the efficiency of OPVCs, while the electronic structure was not affected by thermal treatment.
We performed molecular dynamics simulations of a liquid crystal elastomer of side-chain architecture. The network is formed from a melt of 28 molecules each having a backbone of 100 hydrocarbon monomers, to which 50 side chains are attached in a syndiotactic way. Crosslinking is performed in the smectic A phase. We observe an increase of the smectic-isotropic phase transition temperature of about 5 degrees as compared to the uncrosslinked melt. Memory effects in liquid crystalline order and in sample shape are well reproduced when the elastomer is driven through the smectic-isotropic transition. Above this transition, in the isotropic phase, the polydomain smectic phase is induced by a uniaxial load. Below the transition, in a monodomain smectic A phase, both experimentally observed effects of homogeneous director reorientation and stripe formation are reproduced when the sample is stretched along the director. When the load is applied perpendicularly to the director, the sample demonstrates reversible deformation with no change of liquid crystalline order, indicating elasticity of the two-dimensional network of polymer layers.
We have applied time-delayed collection field (TDCF) and charge extraction by linearly increasing voltage (CELIV) to investigate the photogeneration, transport, and recombination of charge carriers in blends composed of PCPDTBT/PC70BM processed with and without the solvent additive diiodooctane. The results suggest that the solvent additive has severe impacts on the elementary processes involved in the photon to collected electron conversion in these blends. First, a pronounced field dependence of the free carrier generation is found for both blends, where the field dependence is stronger without the additive. Second, the fate of charge carriers in both blends can be described with a rather high bimolecular recombination coefficients, which increase with decreasing internal field. Third, the mobility is three to four times higher with the additive. Both blends show a negative field dependence of mobility, which we suggest to cause bias-dependent recombination coefficients.
The authors present efficient all-polymer solar cells comprising two different low-bandgap naphthalenediimide (NDI)-based copolymers as acceptors and regioregular P3HT as the donor. It is shown that these naphthalene copolymers have a strong tendency to preaggregate in specific organic solvents, and that preaggregation can be completely suppressed when using suitable solvents with large and highly polarizable aromatic cores. Organic solar cells prepared from such nonaggregated polymer solutions show dramatically increased power conversion efficiencies of up to 1.4%, which is mainly due to a large increase of the short circuit current. In addition, optimized solar cells show remarkable high fill factors of up to 70%. The analysis of the blend absorbance spectra reveals a surprising anticorrelation between the degree of polymer aggregation in the solid P3HT:NDI copolymer blends and their photovoltaic performance. Scanning near-field optical microscopy (SNOM) and atomic force microscopy (AFM) measurements reveal important information on the blend morphology. It is shown that films with high degree of aggregation and low photocurrents exhibit large-scale phase-separation into rather pure donor and acceptor domains. It is proposed that, by suppressing the aggregation of NDI copolymers at the early stage of film formation, the intermixing of the donor and acceptor component is improved, thereby allowing efficient harvesting of photogenerated excitons at the donoracceptor heterojunction.
Aggregate formation in poly(3-hexylthiophene) depends on molecular weight, solvent, and synthetic method. The interplay of these parameters thus largely controls device performance. In order to obtain a quantitative understanding on how these factors control the resulting electronic properties of P3HT, we measured absorption in solution and in thin films as well as the resulting field effect mobility in transistors. By a detailed analysis of the absorption spectra, we deduce the fraction of aggregates formed, the excitonic coupling within the aggregates, and the conjugation length within the aggregates, all as a function of solvent quality for molecular weights from 5 to 19 kDa. From this, we infer in which structure the aggregated chains pack. Although the 5 kDa samples form straight chains, the 11 and 19 kDa chains are kinked or folded, with conjugation lengths that increase as the solvent quality reduces. There is a maximum fraction of aggregated chains (about 55 +/- 5%) that can be obtained, even for poor solvent quality. We show that inducing aggregation in solution leads to control of aggregate properties in thin films. As expected, the field-effect mobility correlates with the propensity to aggregation. Correspondingly, we find that a well-defined synthetic approach, tailored to give a narrow molecular weight distribution, is needed to obtain high field effect mobilities of up to 0.01 cm2/Vs for low molecular weight samples (=11 kDa), while the influence of synthetic method is negligible for samples of higher molecular weight, if low molecular weight fractions are removed by extraction.
We compare standard and inverted bulk heterojunction solar cells composed of PCPDTBT:PC70BM blends. Inverted devices comprising 100 nm thick active layers exhibited short circuit currents of 15 mA/cm(2), 10% larger than in corresponding standard devices. Modeling of the optical field distribution in the different device stacks proved that this enhancement originates from an increased absorption of incident light in the active layer. Internal quantum efficiencies (IQEs) were obtained from the direct comparison of experimentally derived and modeled currents for different layer thicknesses, yielding IQEs of similar to 70% for a layer thickness of 100 nm. Simulations predict a significant increase of the light harvesting efficiency upon increasing the layer thickness to 270 nm. However, a continuous deterioration of the photovoltaic properties with layer thickness was measured for both device architectures, attributed to incomplete charge extraction. On the other hand, our optical modeling suggests that inverted devices based on PCPDTBT should be able to deliver high power conversion efficiencies (PCEs) of more than 7% provided that recombination losses can be reduced.
Employing impedance spectroscopy, we have studied the hole density, conductivity, and mobility of poly(3-hexylthiophene), P3HT, doped with the strong molecular acceptor tetrafluorotetracyanoquinodimethane, F(4)TCNQ. We find that the hole density increases linearly with the F(4)TCNQ concentration. Furthermore, the hole mobility is decreased upon doping at low-to-medium doping level, which is rationalized by an analytic model of carrier mobility in doped organic semiconductors [V. I. Arkhipov, E. V. Emelianova, P. Heremans, and H. Bassler, Phys. Rev. B 72, 235202 (2005)]. We infer that the presence of ionized F(4)TCNQ molecules in the P3HT layer increases energetic disorder, which diminishes the carrier mobility.
A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC70BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC70BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm(2), an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells.
We explore the photophysics of P(NDI2OD-T2), a high-mobility and air-stable n-type donor/acceptor polymer. Detailed steady-state UV-vis and photoluminescence (PL) measurements on solutions of P(NDI2OD-T2) reveal distinct signatures of aggregation. By performing quantum chemical calculations, we can assign these spectral features to unaggregated and stacked polymer chains. NMR measurements independently confirm the aggregation phenomena of P(NDI2OD-T2) in solution. The detailed analysis of the optical spectra shows that aggregation is a two-step process with different types of aggregates, which we confirm by time-dependent PL measurements. Analytical ultracentrifugation measurements suggest that aggregation takes place within the single polymer chain upon coiling. By transferring these results to thin P(NDI2OD-T2) films, we can conclude that film formation is mainly governed by the chain collapse, leading in general to a high aggregate content of similar to 45%. This process also inhibits the formation of amorphous and disordered P(NDI2OD-T2) films.
A comprehensive numerical device simulation of the electrical and optical characteristics accompanied with experimental measurements of a new highly efficient system for polymer-based light-emitting diodes doped with phosphorescent dyes is presented. The system under investigation comprises an electron transporter attached to a polymer backbone blended with an electronically inert small molecule and an iridium-based green phosphorescent dye which serves as both emitter and hole transporter. The device simulation combines an electrical and an optical model. Based on the known highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of all components as well as the measured electrical and optical characteristics of the devices, we model the emissive layer as an effective medium using the dye's HOMO as hole transport level and the polymer LUMO as electron transport level. By fine-tuning the injection barriers at the electron and hole-injecting contact, respectively, in simulated devices, unipolar device characteristics were fitted to the experimental data. Simulations using the so-obtained set of parameters yielded very good agreement to the measured currentvoltage, luminancevoltage characteristics, and the emission profile of entire bipolar light-emitting diodes, without additional fitting parameters. The simulation was used to gain insight into the physical processes and the mechanisms governing the efficiency of the organic light-emitting diode, including the position and extent of the recombination zone, carrier concentration profiles, and field distribution inside the device. The simulations show that the device is severely limited by hole injection, and that a reduction of the hole-injection barrier would improve the device efficiency by almost 50%.
In this work, a nonaqueous method is used to fabricate thin TiO2 layers. In contrast to the common aqueous sol-gel approach, our method yields layers of anatase nanocrystallites already at low temperature. Raman spectroscopy, electron microscopy and charge extraction by linearly increasing voltage are employed to study the effect of sintering temperature on the structural and electronic properties of the nanocrystalline TiO2 layer. Raising the sintering temperature from 120 to 600 A degrees C is found to alter the chemical composition, the layer's porosity and its surface but not the crystal phase. The room temperature mobility increases from 2 x 10(-6) to 3 x 10(-5) cm(2)/Vs when the sinter temperature is increased from 400 to 600 A degrees C, which is explained by a better interparticle connectivity. Solar cells comprising such nanoporous TiO2 layers and a soluble derivative of cyclohexylamino-poly(p-phenylene vinylene) were fabricated and studied with regard to their structural and photovoltaic properties. We found only weak polymer infiltration into the oxide layer for sintering temperatures up to 550 A degrees C, while the polymer penetrated deeply into titania layers that were sintered at 600 A degrees C. Best photovoltaic performance was reached with a nanoporous TiO2 film sintered at 550 A degrees C, which yielded a power conversion efficiency of 0.5 %. Noticeably, samples with the TiO2 layer dried at 120 A degrees C displayed short-circuit currents and open circuit voltages only about 15-20 % lower than for the most efficient devices, meaning that our nonaqueous route yields titania layers with reasonable transport properties even at low sintering temperatures.
Derivatization of fullerene (C-60) with branched aliphatic chains softens C-60-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C-60 materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84 degrees C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6 + 0.1%) in comparison with another compound, 10 (PCE: 0.5 + 0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C-60 derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices.
We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.
A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein
(2013)
We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)-functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer-antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing.
To address the nature of charge transport and the origin of severe (intrinsic) trapping in electron-transporting polymers, transient and steady-state charge transport measurements have been conducted on the prototype donor/acceptor copolymer poly[2,7-(9,9-dialkyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PFTBTT). A charge-generation layer technique is used to selectively address transport of the desired charge carrier type, to perform time-of-flight measurements on samples with < 200 nm thickness, and to combine the time-of-flight and the photocharge extraction by linearly increasing voltage (photo-CELIV) techniques to investigate charge carrier dynamics over a wide time range. Significant trapping of free electrons is observed in the bulk of dioctyl-substituted PFTBTT (alt-PF8TBTT), introducing a strong relaxation of the charge carrier mobility with time. We used Monte-Carlo simulation to simulate the measured transient data and found that all measurements can be modeled with a single parameter set, with the charge transport behavior determined by multiple trapping and detrapping of electrons in an exponential trap distribution. The influence of the concomitant mobility relaxation on the transient photocurrent characteristics in photo-CELIV experiments is discussed and shown to explain subtle features that were seen in former publications but were not yet assigned to electron trapping. Comparable studies on PFTBTT copolymers with chemical modifications of the side chains and backbone suggest that the observed electron trapping is not caused by a distinct chemical species but rather is related to interchain interactions.
A new matrix system for phosphorescent organic light-emitting diodes (OLEDs) based on an electron transporting component attached to an inert polymer backbone, an electronically neutral co-host, and a phosphorescent dye that serves as both emitter and hole conductor are presented. The inert co-host is used either as small molecules or covalently connected to the same chain as the electron-transporting host. The use of a small molecular inert co-host in the active layer is shown to be highly advantageous in comparison to a purely polymeric matrix bearing the same functionalities. Analysis of the dye phosphorescence decay in pure polymer, small molecular co-host film, and their blend lets to conclude that dye molecules distribute mostly in the small molecular co-host phase, where the co-host prevents agglomeration and self-quenching of the phosphorescence as well as energy transfer to the electron transporting units. In addition, the co-host accumulates at the anode interface where it acts as electron blocking layer and improves hole injection. This favorable phase separation between polymeric and small molecular components results in devices with efficiencies of about 47 cd/A at a luminance of 1000 cd/m(2). Investigation of OLED degradation demonstrates the presence of two time regimes: one fast component that leads to a strong decrease at short times followed by a slower decrease at longer times. Unlike the long time degradation, the efficiency loss that occurs at short times is reversible and can be recovered by annealing of the device at 180 degrees C. We also show that the long-time degradation must be related to a change of the optical and electrical bulk properties.
Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors
(2013)
Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.
By means of optical spectroscopy, Kelvin probe, and conductivity measurements, we study the p-type doping of the donor polymer poly(3-hexylthiophene), P3HT, with the molecular acceptor tetrafluorotetracyanoquin-odimethane, F(4)TCNQ, covering a broad range of molar doping ratios from the ppm to the percent regime. Thorough quantitative analysis of the specific near-infrared absorption bands of ionized F(4)TCNQ reveals that almost every F(4)TCNQ dopant undergoes integer charge transfer with a P3HT site. However, only about 5% of these charge carrier pairs are found to dissociate and contribute a free hole for electrical conduction. The nonlinear behavior of the conductivity on doping ratio is rationalized by a numerical mobility model that accounts for the broadening of the energetic distribution of transport sites by the Coulomb potentials of ionized F(4)TCNQ dopants. DOI: 10.1103/PhysRevB.87.115209
Charge transport and nongeminate recombination are investigated in two solution-processed small molecule bulk heterojunction solar cells consisting of diketopyrrolopyrrole (DPP)-based donor molecules, mono-DPP and bis-DPP, blended with [6,6]-phenyl-C71-butyric acid methyl ester (PCBM). While the bis-DPP system exhibits a high fill factor (62%) the mono-DPP system suffers from pronounced voltage dependent losses, which limit both the fill factor (46%) and short circuit current. A method to determine the average charge carrier density, recombination current, and effective carrier lifetime in operating solar cells as a function of applied bias is demonstrated. These results and light intensity measurements of the current-voltage characteristics indicate that the mono-DPP system is severely limited by nongeminate recombination losses. Further analysis reveals that the most significant factor leading to the difference in fill factor is the comparatively poor hole transport properties in the mono-DPP system (2 x 10(-5) cm(2) V-1 s(-1) versus 34 x 10(-5) cm(2) V-1 s(-1)). These results suggest that future design of donor molecules for organic photovoltaics should aim to increase charge carrier mobility thereby enabling faster sweep out of charge carriers before they are lost to nongeminate recombination.
A detailed investigation of the open circuit voltage (V-OC) of organic bulk heterojunction solar cells comprising three different donor polymers and two different fullerene-based acceptors is presented. Bias amplified charge extraction (BACE) is combined with Kelvin Probe measurements to derive information on the relevant energetics in the blend. On the example of P3HT:PC70BM the influence of composition and preparation conditions on the relevant transport levels will be shown. Moderate upward shifts of the P3HT HOMO depending on crystallinity are observed, but contrarily to common believe, the dependence of V-OC on blend composition and thermal history is found to be largely determined by the change in the PCBM LUMO energy. Following this approach, we quantified the energetic contribution to the V-OC in blends with fluorinated polymers or higher adduct fullerenes.
Aqueous mixtures of a dye-labeled non-ionic thermoresponsive copolymer and a conjugated cationic polyelectrolyte are shown to exhibit characteristic changes in fluorescence properties in response to temperature and to the presence of salts, enabling a double-stimuli responsiveness. In such mixtures at room temperature, i.e., well below the lower critical solution temperature (LCST), the emission of the dye is strongly quenched due to energy transfer to the polycation, pointing to supramolecular interactions between the two macromolecules. Increasing the concentration of salts weakens the interpolymer interactions, the extent of which is simultaneously monitored from the change in the relative emission intensity of the components. When the mixture is heated above its LCST, the transfer efficiency is significantly reduced, signaling a structural reorganization process, however, surprisingly only if the mixture contains salt ions. To elucidate the reasons behind such thermo- and ion-sensitive fluorescence characteristics, we investigate the effect of salts of alkali chlorides, in particular of NaCl, on the association behavior of these macromolecules before and after the polymer phase transition by a combination of UV-vis, fluorescence, and H-1 NMR spectroscopy with light scattering and small-angle neutron scattering measurements.
The method of current extraction under linear increasing voltages (CELIV) allows for the simultaneous determination of charge mobilities and charge densities directly in thin-film geometries as used in organic photovoltaic (OPV) cells. It has been specifically applied to investigate the interrelation of microstructure and charge-transport properties in such systems. Numerical and analytical calculations presented in this work show that the evaluation of CELIV transients with the commonly used analysis scheme is error prone once charge recombination and, possibly, field- dependent charge mobilities are taken into account. The most important effects are an apparent time dependence of charge mobilities and errors in the determined field dependencies. Our results implicate that reports on time-dependent mobility relaxation in OPV materials obtained by the CELIV technique should be carefully revisited and confirmed by other measurement methods.
Carrier transport and recombination have been studied in single component layers and blends of the soluble PPV- derivative poly[2,5-dimethoxy-1,4-phenylenevinylene-2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylenevinylene] (M3EH-PPV) and the small molecule acceptor 4,7-bis(2-(1-hexyl-4,5-dicyanoimidazole-2-yl)vinyl) benzo[c][1,2,5]-thiadiazole (HV-BT). Measurements on single carrier devices show significantly smaller electron mobility in the blend compared to the pure HV- BT layer, which is suggestive of the formation of isolated clusters of the acceptor in a continuous polymer matrix. The significant change in fill factor (FF) with increasing illumination intensity is consistently explained by a model taking into account bimolecular recombination and space charge effects. The decay of the carrier density after photoexcitation has been studied by performing photo-CELIV measurements on pure and blend layers. It is found that the decay at long delay times follows a power-law dependence, which is, however, not consistent with a Langevin-type bimolecular recombination of free charges. A good description of the data is obtained by assuming trimolecular recombination to govern the charge carrier dynamics in these systems.
Current-voltage analysis of single-carrier transport is a popular method for the determination of charge carrier mobilities in organic semiconductors. Although in widespread use for the analysis of hole transport, only a few reports can be found where the method was applied to electron transport. Here, we summarize the experimental difficulties related to the metal electrode leakage currents and nonlinear differential resistance (NDR) effects and explain their origin. We present a modified preparation technique for the metal electrodes and show that it significantly increases the reliability of such measurements. It allows to produce test devices with low leakage currents and without NDR even for thin organic layers. Metal oxides were often discussed as a possible cause of NDR. Our measurements on forcibly oxidized metal electrodes demonstrate that oxide layers are not exclusively responsible for NDR effects. We present electron transport data for two electron-conducting polymers often applied in all-polymer solar cells for a large variety of layer thicknesses and temperatures. The results can be explained by established exponential trapping models.
The authors present organic photovoltaic (OPV) devices comprising a small molecule electron acceptor based on 2- vinyl-4,5-dicyanoimidazole (Vinazene (TM)) and a soluble poly(p-phenylenevinylene) derivative as the electron donor. A strong dependence of the fill factor (FF) and the external quantum efficiency [incident photons converted to electrons (IPCE)] on the heterojunction topology is observed. As-prepared blends provided relatively low FF and IPCE values of 26% and 4.5%, respectively, which are attributed to significant recombination of geminate pairs and free carriers in a highly intermixed blend morphology. Going to an all-solution processed bilayer device, the FF and IPCE dramatically increased to 43% and 27%, respectively. The FF increases further to 57% in devices comprising thermally deposited Vinazene layers where there is virtually no interpenetration at the donor/acceptor interface. This very high FF is comparable to values reported for OPV using fullerenes as the electron acceptor. Furthermore, the rather low electron affinity of Vinazene compound near 3.5 eV enabled a technologically important open circuit voltage (V-oc) of 1.0 V.
Layers made from soluble low molecular weight polythiophene PQT-12 with low polydispersity exhibit a highly ordered structure and charge-carrier mobilities of the order of 10(-3) cm(2)/(V s), which we attribute to its proximity to monodispersity. We propose that polydispersity is a decisive factor with regard to structure formation and transport properties of soluble low molecular weight polythiophenes.
Bimodal temperature behavior of structure and mobility in high molecular weight p3ht thin films
(2009)
We report a temperature dependent crystalline structure of spin-coated thin films of high molecular weight regioregular poly(3-hexylthiophene) (P3HT) (M-n similar to 30000 g/mol) and its correlation with charge carrier mobility. These investigations show a reversible change of the crystalline structure, where the interlayer lattice spacing (100)along the alkyl side chains continuously increases up to a temperature of about 220 degrees C; in contrast, the in-plane pi-pi distance reduces with increasing temperature. These changes in structure are reversible and can be repeated several times. The temperature-induced structural properties differ for thick and thin films, pointing to a surface/interface role in stabilization of the layer morphology. In contrast to the structural changes, the carrier mobility is rather constant in the temperature range from room temperature up to 100-120 degrees C, followed by a continuous decrease. For thick layers this drop is significant and the transistor performance almost vanishes at high temperature, however, it completely recovers upon cooling back to roorn temperature. The drop of the charge carrier mobility at higher temperatures is in contrast with expectations front the structural studies, considering the increase of crystalline fraction of the polycrystalline layer. our electrical measurements Underscore that the reduction of the macroscopic mobility is mostly caused by it pronounced decrease of the intergrain transport. The thermally induced crystallization along(100) direction and the creation of numerous small crystallites at the film-substrate interface reduce the number of long polymer chain, bridging crystalline domains, which ultimately limits the macroscopic charge transport.
We investigate solar cells comprised of a vinazene derivative (HV-BT) as the electron acceptor and the well- known polymer poly(3-hexylthiophene) as the electron donor. In the as-prepared blend, most of the excited state species, including the excimers on HV-BT, are quenched at the heterojunction. Although the photophysical properties of the blends change upon annealing, the blend solar cells largely remain uninfluenced by such treatments. A significant improvement is, however, observed when inducing phase separation at a longer length scale, for example, in solution-processed bilayer devices. Hereby, both the fill factor (FF) and the open circuit voltage are considerably increased, pointing to the importance of the heterojunction topology and the layer composition at the charge extracting contacts. An optimized device exhibits a power conversion efficiency of close to 1%.
Bulk electron transport and charge injection in a high mobility n-type semiconducting polymer
(2010)
Bulk electron transport in a high mobility n-type polymer is studied by time-of-flight photocurrent measurements and electron-only devices. Bulk electron mobilities of similar to 5 x 10(-3) cm(2)/Vs are obtained. The analysis of the electron currents suggests the presence of an injection barrier for all conventionally used low workfunction cathodes.