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Institute
Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1-sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non-radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open-circuit voltage and the internal quasi-Fermi level splitting (QFLS), the transport resistance-free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity-dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non-radiative fill factor and open-circuit voltage loss. It is found that potassium-passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit.
Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces.
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.
Optically induced mass transport studied by scanning near-field optical- and atomic force microscopy
(2004)
Some functionalised thin organic films show a very unusual property, namely the light induced material transport. This effect enables to generate three-dimensional structures on surfaces of azobenzene containing films only caused by special optical excitation. The physical mechanisms underlying this phenomenon have not yet been fully understood, and in addition, the dimensions of structures created in that way are macroscopic because of the optical techniques and the wavelength of the used light. In order to gain deeper insight into the physical fundamentals of this phenomenon and to open possibilities for applications it is necessary to create and study structures not only in a macroscopic but also in nanometer range. We first report about experiments to generate optically induced nano structures even down to 100 nm size. The optical stimulation was therefore made by a Scanning Near-field Optical Microscope (SNOM). Secondly, physical conditions inside optically generated surface relief gratings were studied by measuring mechanical properties with high lateral resolution via pulse force mode and force distance curves of an AFM
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.
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.
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.
Light-induced softening of azobenzene dye-doped polymer films probed with quartz crystal resonators
(2000)
Fullerene-based acceptors have dominated organic solar cells for almost two decades. It is only within the last few years that alternative acceptors rival their dominance, introducing much more flexibility in the optoelectronic properties of these material blends. However, a fundamental physical understanding of the processes that drive charge separation at organic heterojunctions is still missing, but urgently needed to direct further material improvements. Here a combined experimental and theoretical approach is used to understand the intimate mechanisms by which molecular structure contributes to exciton dissociation, charge separation, and charge recombination at the donor-acceptor (D-A) interface. Model systems comprised of polythiophene-based donor and rylene diimide-based acceptor polymers are used and a detailed density functional theory (DFT) investigation is performed. The results point to the roles that geometric deformations and direct-contact intermolecular polarization play in establishing a driving force ( energy gradient) for the optoelectronic processes taking place at the interface. A substantial impact for this driving force is found to stem from polymer deformations at the interface, a finding that can clearly lead to new design approaches in the development of the next generation of conjugated polymers and small molecules.
Photoaddressable alignment layers for fluorescent polymers in polarized electroluminescence devices
(2002)
Organic semiconductors are of great interest for a broad range of optoelectronic applications due to their solution processability, chemical tunability, highly scalable fabrication, and mechanical flexibility. In contrast to traditional inorganic semiconductors, organic semiconductors are intrinsically disordered systems and therefore exhibit much lower charge carrier mobilities-the Achilles heel of organic photovoltaic cells. In this progress review, the authors discuss recent important developments on the impact of charge carrier mobility on the charge transfer state dissociation, and the interplay of free charge extraction and recombination. By comparing the mobilities on different timescales obtained by different techniques, the authors highlight the dispersive nature of these materials and how this reflects on the key processes defining the efficiency of organic photovoltaics.
The in-depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter-related via the kinetics of charge transfer states-being singlet or triplet states. Although high-charge-photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low-mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta-analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field-dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a "spin-related factor" that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge-generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin-related factor.
Diketopyrrolopyrrole (DPP)-based donor acceptor copolymers have gained a significant amount of research interest in the organic electronics community because of their high charge carrier mobilities in organic field-effect transistors (OFETs) and their ability to harvest near-infrared (NIR) photons in solar cells. In this study, we have synthesized four DPP based donor-acceptor copolymers with variations in the donor unit and the branching point of the solubilizing alkyl chains (at the second or sixth carbon position). Grazing incidence wide-angle X-ray scattering (GIWAXS) results suggest that moving the branching point further away from the polymer backbone increases the tendency for aggregation and yields polymer phases with a higher degree of crystallinity (DoC). The polymers were blended with PC70BM and used as active layers in solar cells. A careful analysis of the energetics of the neat polymer and blend films reveals that the charge-transfer state energy (E-CT) of the blend films lies exceptionally close to the singlet energy of the donor (E-D*), indicating near zero electron transfer losses. The difference between the optical gap and open-circuit voltage (V-OC) is therefore determined to be due to rather high nonradiative 418 +/- 13 mV) and unavoidable radiative voltage losses (approximate to 255 +/- 8 mV). Even though the four materials have similar optical gaps, the short-circuit current density (J(SC)) covers a vast span from 7 to 18 mA cm(-2) for the best performing system. Using photoluminescence (PL) quenching and transient charge extraction techniques, we quantify geminate and nongeminate losses and find that fewer excitons reach the donor-acceptor interface in polymers with further away branching points due to larger aggregate sizes. In these material systems, the photogeneration is therefore mainly limited by exciton harvesting efficiency.
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.
Here we report a new and simple synthetic pathway to form ordered, hollow carbon nitride structures, using a cyanuric acid melamine (CM) complex in ethanol as a starting product. A detailed analysis of the optical and photocatalytic properties shows that optimum hollow carbon nitride structures are formed after 8 h of condensation. For this condensation time, we find a significantly reduced fluorescence intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes. Enhanced charge transfer is seen as well from a drastic increase of the photocatalytic activity in the degradation of rhodamine B dye, which is shown to proceed via photoinduced hole transfer. Moreover, we show that various CM morphologies can be obtained using different solvents, which leads to diverse ordered carbon nitride architectures. In all cases, the CM-C3N4 structures exhibited superior photocatalytic activity compared to the bulk material. The utilization of CM hydrogen-bonded complexes opens new opportunities for the significant improvement of carbon nitride synthesis, structure, and optical properties toward an efficient photoactive material for catalysis.
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.
The functionality of organic semiconductor devices crucially depends on molecular energies, namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity values of thin films are, however, sensitive to film morphology and composition, making their prediction challenging. In a combined experimental and simulation study on zinc-phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a function of molecular orientation in neat films or mixing ratio in blends are proportional to the molecular quadrupole component along the p-p-stacking direction. We apply these findings to organic solar cells and demonstrate how the electrostatic interactions can be tuned to optimise the energy of the charge-transfer state at the donor-acceptor interface and the dissociation barrier for free charge carrier generation. The confirmation of the correlation between interfacial energies and quadrupole moments for other materials indicates its relevance for small molecules and polymers.
Monolithic perovskite silicon tandem solar cells can overcome the theoretical efficiency limit of silicon solar cells. This requires an optimum bandgap, high quantum efficiency, and high stability of the perovskite. Herein, a silicon heterojunction bottom cell is combined with a perovskite top cell, with an optimum bandgap of 1.68 eV in planar p-i-n tandem configuration. A methylammonium-free FA(0.75)Cs(0.25)Pb(I0.8Br0.2)(3) perovskite with high Cs content is investigated for improved stability. A 10% molarity increase to 1.1 m of the perovskite precursor solution results in approximate to 75 nm thicker absorber layers and 0.7 mA cm(-2) higher short-circuit current density. With the optimized absorber, tandem devices reach a high fill factor of 80% and up to 25.1% certified efficiency. The unencapsulated tandem device shows an efficiency improvement of 2.3% (absolute) over 5 months, showing the robustness of the absorber against degradation. Moreover, a photoluminescence quantum yield analysis reveals that with adapted charge transport materials and surface passivation, along with improved antireflection measures, the high bandgap perovskite absorber has the potential for 30% tandem efficiency in the near future.
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.
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.
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.
The recent development of donor–acceptor copolymers has led to an enormous improvement in the performance of organic solar cells and organic field-effect transistors. Here we describe the synthesis, detailed characterisation, and application of a series of structurally modified copolymers to investigate fundamental structure–property relationships in this class of conjugated polymers. The interplay between chemical structure and optoelectronic properties is investigated. These are further correlated to the charge transport and solar cell performance, which allows us to link their chemical structure to the observed physical properties.
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.
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.
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.
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.
Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films
(2005)
It was discovered 10 years ago that the exposure of an initially flat layer of an azobenzene-containing polymer to an inhomogeneous light pattern leads to the formation of surface relief structures, accompanied by a mass transport over several micrometers. However, the driving force of this process is still unclear. We propose a new thermodynamic approach that explains a number of experimental findings including the light-induced deformation of free-standing films and the formation of surface relief gratings for main inscription geometries. Our basic assumption is that under homogeneous illumination, an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores. The magnitude of the elastic stress, estimated by taking the derivative of the free energy over the sample deformation, is shown to be sufficient to induce plastic deformation of the polymer film. Orientational distributions of chromophores predicted by our model are compared with those deduced from Raman intensity measurements
Perovskite semiconductors as the active materials in efficient solar cells exhibit free carrier diffusion lengths on the order of microns at low illumination fluxes and many hundreds of nanometers under 1 sun conditions. These lengthscales are significantly larger than typical junction thicknesses, and thus the carrier transport and charge collection should be expected to be diffusion controlled. A consensus along these lines is emerging in the field. However, the question as to whether the built-in potential plays any role is still of matter of some conjecture. This important question using phase-sensitive photocurrent measurements and theoretical device simulations based upon the drift-diffusion framework is addressed. In particular, the role of the built-in electric field and charge-selective transport layers in state-of-the-art p-i-n perovskite solar cells comparing experimental findings and simulation predictions is probed. It is found that while charge collection in the junction does not require a drift field per se, a built-in potential is still needed to avoid the formation of reverse electric fields inside the active layer, and to ensure efficient extraction through the charge transport layers.
Organic solar cells with large insensitivity to donor polymer molar mass across all acceptor classes
(2020)
Donor polymer number-average molar mass (M-n) has long been known to influence organic photovoltaic (OPV) performance via changes in both the polymer properties and the resulting bulk heterojunction morphology. The exact nature of these M-n effects varies from system to system, although there is generally some intermediate M-n that results in optimal performance. Interestingly, our earlier work with the difluorobenzotriazole (FTAZ)-based donor polymer, paired with either N2200 (polymer acceptor) or PC61BM (fullerene acceptor), PcBm demonstrated <10% variation in power conversion efficiency and a consistent morphology over a large span of M-n (30 kg/mol to over 100 kg/mol). Would such insensitivity to polymer M-n still hold true when prevailing small molecular acceptors were used with FTAZ? To answer this question, we explored the impact of FTAZ on OPVs with ITIC, a high-performance small-molecule fused-ring electron acceptor (FREA). By probing the photovoltaic characteristics of the resulting OPVs, we show that a similar FTAZ mn insensitivity is also found in the FTAZ:ITIC system. This study highlights a single-donor polymer which, when paired with an archetypal fullerene, polymer, and FREA, results in systems that are largely insensitive to donor M. Our results may have implications in polymer batch-to-batch reproducibility, in particular, relaxing the need for tight M-n control during synthesis.
Perovskite solar cells (PSCs) are currently one of the most promising photovoltaic technologies for highly efficient and cost-effective solar energy production. In only a few years, an unprecedented progression of preparation procedures and material compositions delivered lab-scale devices that have now reached record power conversion efficiencies (PCEs) higher than 20%, competing with most established solar cell materials such as silicon, CIGS, and CdTe. However, despite a large number of researchers currently involved in this topic, only a few groups in the world can reproduce >20% efficiencies on a regular n-i-p architecture. In this work, we present detailed protocols for preparing PSCs in regular (n-i-p) and inverted (p-i-n) architectures with >= 20% PCE. We aim to provide a comprehensive, reproducible description of our device fabrication , protocols. We encourage the practice of reporting detailed and transparent protocols that can be more easily reproduced by other laboratories. A better reporting standard may, in turn, accelerate the development of perovskite solar cells and related research fields.
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.
Alternative electron acceptors are being actively explored in order to advance the development of bulk-heterojunction (BHJ) organic solar cells (OSCs). The indene-C-60 bisadduct (ICBA) has been regarded as a promising candidate, as it provides high open-circuit voltage in BHJ solar cells; however, the photovoltaic performance of such ICBA-based devices is often inferior when compared to cells with the omnipresent PCBM electron acceptor. Here, by pairing the high performance polymer (FTAZ) as the donor with either PCBM or ICBA as the acceptor, we explore the physical mechanism behind the reduced performance of the ICBA-based device. Time delayed collection field (TDCF) experiments reveal reduced, yet field-independent free charge generation in the FTAZ:ICBA system, explaining the overall lower photocurrent in its cells. Through the analysis of the photoluminescence, photogeneration, and electroluminescence, we find that the lower generation efficiency is neither caused by inefficient exciton splitting, nor do we find evidence for significant energy back-transfer from the CT state to singlet excitons. In fact, the increase in open circuit voltage when replacing PCBM by ICBA is entirely caused by the increase in the CT energy, related to the shift in the LUMO energy, while changes in the radiative and nonradiative recombination losses are nearly absent. On the other hand, space charge limited current (SCLC) and bias-assisted charge extraction (BACE) measurements consistently reveal a severely lower electron mobilitiy in the FTAZ:ICBA blend. Studies of the blends with resonant soft X-ray scattering (R-SoXS), grazing incident wide-angle X-ray scattering (GIWAXS), and scanning transmission X-ray microscopy (STXM) reveal very little differences in the mesoscopic morphology but significantly less nanoscale molecular ordering of the fullerene domains in the ICBA based blends, which we propose as the main cause for the lower generation efficiency and smaller electron mobility. Calculations of the JV curves with an analytical model, using measured values, show good agreement with the experimentally determined JV characteristics, proving that these devices suffer from slow carrier extraction, resulting in significant bimolecular recombination losses. Therefore, this study highlights the importance of high charge carrier mobility for newly synthesized acceptor materials, in addition to having suitable energy levels.
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.
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.
We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder.
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.
The combined effect of ultraviolet (UV) light soaking and self-assembled monolayer deposition on the work function (WF) of thin ZnO layers and on the efficiency of hole injection into the prototypical conjugated polymer poly(3-hexylthiophen-2,5-diyl) (P3HT) is systematically investigated. It is shown that the WF and injection efficiency depend strongly on the history of UV light exposure. Proper treatment of the ZnO layer enables ohmic hole injection into P3HT, demonstrating ZnO as a potential anode material for organic optoelectronic devices. The results also suggest that valid conclusions on the energy-level alignment at the ZnO/organic interfaces may only be drawn if the illumination history is precisely known and controlled. This is inherently problematic when comparing electronic data from ultraviolet photoelectron spectroscopy (UPS) measurements carried out under different or ill-defined illumination conditions.
A long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics-however, the results have important implications on the operation of all optoelectronic devices with donor/ acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting in larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.
Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short-circuit currents (J(SC)) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open-circuit voltages (V-OC). Recently, reports have highlighted BHJ blends that are pushing at the accepted limits of energetic offsets necessary for high efficiency. Unfortunately, most of these BHJs have modest FF values. How the energetic offset impacts the solar cell characteristics thus remains poorly understood. Here, a comprehensive characterization of the losses in a polymer:fullerene BHJ blend, PIPCP:phenyl-C61-butyric acid methyl ester (PC61BM), that achieves a high V-OC (0.9 V) with very low energy losses (E-loss = 0.52 eV) from the energy of absorbed photons, a respectable J(SC) (13 mA cm(-2)), but a limited FF (54%) is reported. Despite the low energetic offset, the system does not suffer from field-dependent generation and instead it is characterized by very fast nongeminate recombination and the presence of shallow traps. The charge-carrier losses are attributed to suboptimal morphology due to high miscibility between PIPCP and PC61BM. These results hold promise that given the appropriate morphology, the J(SC), V-OC, and FF can all be improved, even with very low energetic offsets.
Aggregation of chromophores in the solid state commonly causes undesirable red shifts in the emission spectra and/or emission quenching. To overcome this problem, we have prepared soluble perylenetetracarboxidiimide dyes in which the chromophores are effectively shielded by polyphenylene dendrimers attached in the bay positions. Models show that attachment of the shielding units in the bay position should provide more efficient shielding than attaching them via the imide moieties. The dendrimers possess excellent film-forming properties due to alkyl substituents on their peripheries. The lack of a red shift in emission upon going from solution to the solid state indicates the dendrons suppress interaction of the emissive cores, leading to pure red-orange emission. Single-layer LEDs produce red-orange emission with relatively low efficiency especially for the higher generation dendrons, which is attributed to poor charge conduction. LEDs using blends of the dendrimers and the undendronized dye as a model compound in PVK have been investigated, and a model to extract relative charge injection rates through the dendritic scaffold from the spectral contributions in the EL spectra is developed
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.
Enhanced charge selectivity via anodic-C60 layer reduces nonradiative losses in organic solar cells
(2021)
Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction.
This work uses a neat C-60 interlayer on the anode to experimentally reveal that surface recombination is a significant contributor to nonradiative recombination losses in organic solar cells.
These losses are shown to proportionally increase with the extent of contact between donor molecules in the photoactive layer and a molybdenum oxide (MoO3) hole extraction layer, proven by calculating voltage losses in low- and high-donor-content bulk heterojunction device architectures.
Using a novel in-device determination of the built-in voltage, the suppression of surface recombination, due to the insertion of a thin anodic-C-60 interlayer on MoO3, is attributed to an enhanced built-in potential.
The increased built-in voltage reduces the presence of minority charge carriers at the electrodes-a new perspective on the principle of selective charge extraction layers.
The benefit to device efficiency is limited by a critical interlayer thickness, which depends on the donor material in bilayer devices.
Given the high popularity of MoO3 as an efficient hole extraction and injection layer and the increasingly popular discussion on interfacial phenomena in organic optoelectronic devices, these findings are relevant to and address different branches of organic electronics, providing insights for future device design.