Refine
Has Fulltext
- no (247)
Year of publication
Document Type
- Article (247) (remove)
Language
- English (247)
Is part of the Bibliography
- yes (247)
Keywords
- organic solar cells (11)
- perovskite solar cells (10)
- morphology (5)
- charge transport (4)
- conjugated polymers (4)
- non-fullerene acceptors (4)
- solar cells (4)
- voltage losses (4)
- Solar cells (3)
- open-circuit voltage (3)
Institute
We have recently shown that efficient polymer solar cells can be fabricated by using a weakly soluble derivative of poly-p-vinylene (M3EH-PPV) as the electron donor. Here we present studies on bilayer devices using organic electron acceptors with varying LUMO levels and M3EH-PPV. It is found that the open-circuit voltage scales linearly with the LUMO level of the acceptor, reaching values as high as 1.5 V when cyano-substituted poly(p-phenyleneethynylene)-alt- poly(p-phenylenevinylene) copolymers are used. Further, we discovered that for an increasing number of triple bonds in the repeat unit of the acceptor polymer the device performance decreases with increasing thickness of the acceptor layer. Also, the quantum efficiency was smaller when using polymers with higher LUMO levels. Thus, further effort is needed to design optimum acceptor polymers for devices exhibiting large open-circuit voltage and high quantum efficiency
The performance of highly soluble regioregular poly[ (3-hexylthiophene)-co-(3-octylthiophetie)] (P3HTOT) as a semiconducting material in organic field-effect transistors (OFETs) is presented in comparison to that of the corresponding homopolymers. Transistors made from as-prepared layers of P3HTOT exhibit a mobility of ca. 7 x 10(-3) cm(2) V-1 s(-1), which is comparable to the performance of transistors made from as-prepared poly(3-hexylthiophene) (P3HT) and almost 6 times larger than the mobility of transistors prepared with poly(3-octylthiophene) (P3OT). On the other hand, the solubility parameter delta(p) of P3HTOT is close to that of the highly soluble P3OT. Moreover, compared to a physical blend of poly(3-hexylthiophene) and poly(3-octylthiophene), the mobility of P3HTOT devices is almost twice as large and the performance does not degrade upon annealing at elevated temperatures. Therefore, the copolymer approach outlined here may be one promising step toward an optimum balance between a Sufficient processability of the polymers from common organic solvents, a high solid state order, and applicable OFET performances
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.
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
Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.
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.
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.
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.
We report on the formation of wrinkle-patterned surface morphologies in cesium formamidinium-based Cs(x)FA(1-y)Pb(I1-yBry)(3) perovskite compositions with x = 0-0.3 and y = 0-0.3 under various spin-coating conditions. By varying the Cs and Br contents, the perovskite precursor solution concentration and the spin-coating procedure, the occurrence and characteristics of the wrinkle-shaped morphology can be tailored systematically. Cs(0.17)FA(0.83)Pb(I0.83Br0.17)(3) perovskite layers were analyzed regarding their surface roughness, microscopic structure, local and overall composition, and optoelectronic properties. Application of these films in p-i-n perovskite solar cells (PSCs) with indium-doped tin oxide/NiOx/perovskite/C-60/bathocuproine/Cu architecture resulted in up to 15.3 and 17.0% power conversion efficiency for the flat and wrinkled morphology, respectively. Interestingly, we find slightly red-shifted photoluminescence (PL) peaks for wrinkled areas and we are able to directly correlate surface topography with PL peak mapping. This is attributed to differences in the local grain size, whereas there is no indication for compositional demixing in the films. We show that the perovskite composition, crystallization kinetics, and layer thickness strongly influence the formation of wrinkles which is proposed to be related to the release of compressive strain during perovskite crystallization. Our work helps us to better understand film formation and to further improve the efficiency of PSCs with widely used mixed-perovskite compositions.
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.
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
The increase in the performance of organic solar cells observed over the past few years has reinvigorated the search for a deeper understanding of the loss and extraction processes in this class of device. A detailed knowledge of the density of free charge carriers under different operating conditions and illumination intensities is a prerequisite to quantify the recombination and extraction dynamics. Differential charging techniques are a promising approach to experimentally obtain the charge carrier density under the aforementioned conditions. In particular, the combination of transient photovoltage and photocurrent as well as impedance and capacitance spectroscopy have been successfully used in past studies to determine the charge carrier density of organic solar cells. In this Tutorial, these experimental techniques will be discussed in detail, highlighting fundamental principles, practical considerations, necessary corrections, advantages, drawbacks, and ultimately their limitations. Relevant references introducing more advanced concepts will be provided as well. Therefore, the present Tutorial might act as an introduction and guideline aimed at new prospective users of these techniques as well as a point of reference for more experienced researchers. Published under an exclusive license by AIP Publishing.
Photoinduced changes in the mechanical and dielectric properties of azobenzene polymer films were measured utilizing the method of electromechanical spectroscopy. The measurements revealed a strong correlation between the time- dependent behavior of the plate compliance and the dielectric constant under irradiation. Actinic light causes a light softening of the film that also manifests itself in the increase of the dielectric constant, whereas ultraviolet irradiation results in an initial plasticization of the film followed by its hardening. The latter is accompanied by decrease of the dielectric constant. A semiquantitative model based on the kinetics of the photoisomerization process in azobenzene polymers is proposed. We assume that both visible and ultraviolet irradiation increase the free volume in the layer due to photoisomerization. Additionally, ultraviolet light increases the modulus of the polymer matrix due to the presence of a high density of azobenzene moieties in the cis state. These assumptions allowed us to reproduce the time- dependent behavior of the bulk compliance as well as the dielectric constant at different irradiation intensities, for both visible and ultraviolet light, with only two adjustable parameters
If not oriented perfectly isotropically, the strong dipole moment of polar organic semiconductor materials such as tris-(8-hydroxyquinolate)aluminum (Alq3) will lead to the buildup of a giant surface potential (GSP) and thus to a macroscopic dielectric polarization of the organic film. Despite this having been a known fact for years, the implications of such high potentials within an organic layer stack have only been studied recently. In this work, the influence of the GSP on hole injection into organic layers is investigated. Therefore, we apply a concept called dipolar doping to devices consisting of the prototypical organic materials N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) as nonpolar host and Alq3 as dipolar dopant with different mixing ratios to tune the GSP. The mixtures are investigated in single-layer monopolar devices as well as bilayer metal/insulator/semiconductor structures. Characterization is done electrically using current-voltage (I-V) characteristics, impedance spectroscopy, and charge extraction by linearly increasing voltage and time of flight, as well as with ultraviolet photoelectron spectroscopy. We find a maximum in device performance for moderate to low doping concentrations of the polar species in the host. The observed behavior can be described on the basis of the Schottky effect for image-force barrier lowering, if the changes in the interface dipole, the carrier mobility, and the GSP induced by dipolar doping are taken into account.
Electroluminescence (EL) spectra of hybrid charge transfer states at metal oxide/organic type-II heterojunctions exhibit bias-induced spectral shifts. The reasons for this phenomenon have been discussed controversially and arguments for either electric field-induced effects or the filling of trap states at the oxide surface have been put forward. Here, we combine the results of EL and photovoltaic measurements to eliminate the unavoidable effect of the series resistance of inorganic and organic components on the total voltage drop across the hybrid device. For SnOx combined with the conjugated polymer [ladder type poly-(para-phenylene)], we find a one-to-one correspondence between the blue-shift of the EL peak and the increase of the quasi-Fermi level splitting at the hybrid heterojunction, which we unambiguously assign to state filling. Our data are resembled best by a model considering the combination of an exponential density of states with a doped semiconductor. Published under license by AIP Publishing.
Charge carrier recombination in organic disordered semiconductors is strongly influenced by the thermalization of charge carriers in the density of states (DOS). Measurements of recombination dynamics, conducted under transient or steady-state conditions, can easily be misinterpreted when a detailed understanding of the interplay of thermalization and recombination is missing. To enable adequate measurement analysis, we solve the multiple-trapping problem for recombining charge carriers and analyze it in the transient and steady excitation paradigm for different DOS distributions. We show that recombination rates measured after pulsed excitation are inherently time dependent since recombination gradually slows down as carriers relax in the DOS. When measuring the recombination order after pulsed excitation, this leads to an apparent high-order recombination at short times. As times goes on, the recombination order approaches an asymptotic value. For the Gaussian and the exponential DOS distributions, this asymptotic value equals the recombination order of the equilibrated system under steady excitation. For a more general DOS distribution, the recombination order can also depend on the carrier density, under both transient and steady-state conditions. We conclude that transient experiments can provide rich information about recombination in and out of equilibrium and the underlying DOS occupation provided that consistent modeling of the system is performed.
Charge carrier recombination in organic disordered semiconductors is strongly influenced by the thermalization of charge carriers in the density of states (DOS). Measurements of recombination dynamics, conducted under transient or steady-state conditions, can easily be misinterpreted when a detailed understanding of the interplay of thermalization and recombination is missing. To enable adequate measurement analysis, we solve the multiple-trapping problem for recombining charge carriers and analyze it in the transient and steady excitation paradigm for different DOS distributions. We show that recombination rates measured after pulsed excitation are inherently time dependent since recombination gradually slows down as carriers relax in the DOS. When measuring the recombination order after pulsed excitation, this leads to an apparent high-order recombination at short times. As times goes on, the recombination order approaches an asymptotic value. For the Gaussian and the exponential DOS distributions, this asymptotic value equals the recombination order of the equilibrated system under steady excitation. For a more general DOS distribution, the recombination order can also depend on the carrier density, under both transient and steady-state conditions. We conclude that transient experiments can provide rich information about recombination in and out of equilibrium and the underlying DOS occupation provided that consistent modeling of the system is performed.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer: fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
Diyne-containing poly(p-phenylene-vinylene)s, 4a-d, of general chemical structure-(Ph-C&3bond; C-C&3bond; C-Ph- CH&3bond; CH-Ph-CH&3bond; CH-)(n), obtained through polycondensation reactions of 1,4-bis(4-formyl-2,5-dioctyloxyphenyl)- buta-1,3-diyne (2) with various 2,5-dialkoxy-p-xylylenebis(diethylphosphonates), 3a-d, are the subject of this report. The polymers exhibit great disparity in their degree of polymerization, n, which might be ascribed to side-chain-related differences in reactivity of the reactive species during the polycondensation process and which led to n-dependent absorption (solution and solid state) and emission (solution) behaviors of the polymers. Polarizing optical microscopy and differential scanning calorimetry are employed to probe their thermal behavior. The structure is investigated by means of wide-angle X-ray diffraction for both isotropic and macroscopically oriented samples. Comparison of photophysical (experimental and theoretical) and electrochemical properties of the polymers with those of their yne- containing counterparts 6a-d [-(Ph-C&3bond; C-Ph-CH&3bond; CH-Ph-CH&3bond; CH-)(n)] has been carried out. Similar photophysical behavior was observed for both types of polymers despite the difference in backbone conjugation pattern. The introduction of a second yne unit in 4 lowers the HOMO and LUMO levels, thereby enhancing the electron affinity of polymers 4 compared to polymers 6. The "wider opening" introduced by the second yne unit facilitates moreover the movement of charges during the electrochemical processes leading to minimal discrepancy, Delta E-g between the optical and electrochemical band gap energies. Polymers 6, in contrast, show significant side-chain-dependent Delta E-g values. Low turn-on voltages between 2 and 3 V and maximal luminous efficiencies between 0.32 and 1.25 cd/A were obtained from LED devices of configuration ITO/PEDOT:PSS/polymer 4/Ca/Al
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.
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.
An understanding of the factors limiting the open-circuit voltage (V-oc) and related photon energy loss mechanisms is critical to increase the power conversion efficiency (PCE) of small-molecule organic solar cells (OSCs), especially those with near-infrared (NIR) absorbers. In this work, two NIR boron dipyrromethene (BODIPY) molecules are characterized for application in planar (PHJ) and bulk (BHJ) heterojunction OSCs. When two H atoms are substituted by F atoms on the peripheral phenyl rings of the molecules, the molecular aggregation type in the thin film changes from the H-type to J-type. For PHJ devices, the nonradiative voltage loss of 0.35 V in the J-aggregated BODIPY is lower than that of 0.49 V in the H-aggregated device. In BHJ devices with a nonradiative voltage loss of 0.35 V, a PCE of 5.5% is achieved with an external quantum efficiency (EQE) maximum of 68% at 700 nm.
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.
The optical, structural, and electrical properties of thin layers made from poly(3-hexylthiophene) (P3HT) samples of different molecular weights are presented. As reported in a previous paper by Kline et al., Adv. Mater 2003, 15, 1519, the mobilities of these layers are a strong function of the molecular weight, with the largest mobility found for the largest molecular weight. Atomic force microscopy studies reveal a complex polycrystalline morphology which changes considerably upon annealing. X-ray studies show the occurrence of a layered phase for all P3HT fractions, especially after annealing at 1.50 degreesC . However, there is no clear correlation between the differences in the transport properties and the data from structural investigations. In order to reveal the processes limiting the mobility in these layers, the transistor properties were investigated as a function of temperature. The mobility decreases continuously with increasing temperatures; with the same trend pronounced thermochromic effects of the P3HT films occur. Apparently, the polymer chains adopt a more twisted, disordered conformation at higher temperatures, leading to interchain transport barriers. We conclude that the backbone conformation of the majority of the bulk material rather than the crystallinity of the layer is the most crucial parameter controlling the charge transport in these P3HT layers. This interpretation is supported by the significant blue-shift of the solid-state absorption spectra with decreasing molecular weight, which is indicative of a larger distortion of the P3HT backbone in the low-molecular weight P3HT layers
Recently, two different groups have reported independently that the mobility of field-effect transistors made from regioregular poly(3-hexylthiophene) (P3HT) increases strongly with molecular weight. Two different models were presented: one proposing carrier trapping at grain boundaries and the second putting emphasis on the conformation and packing of the polymer chains in the thin layers for different molecular weights. Here, we present the results of detailed investigations of powders and thin films of deuterated P3HT fractions with different molecular weight. For powder samples, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to investigate the structure and crystallization behavior of the polymers. The GPC investigations show that all weight fractions possess a rather broad molecular weight distribution. DSC measurements reveal a strong decrease of the crystallization temperature and, most important, a significant decrease of the degree of crystallinity with decreasing molecular weight. To study the structure of thin layers in lateral and vertical directions, both transmission electron microscopy (TEM) and X-ray grazing incidence diffraction (GID) were utilized. These methods show that thin layers of the low molecular weight fraction consist of well-defined crystalline domains embedded in a disordered matrix. We propose that the transport properties of layers prepared from fractions of poly(3-hexylthiophene) with different molecular weight are largely determined by the crystallinity of the samples and not by the perfection of the packing of the chains in the individual crystallites
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.
Organic solar cells (OSCs) have progressed rapidly in recent years through the development of novel organic photoactive materials, especially non-fullerene acceptors (NFAs). Consequently, OSCs based on state-of-the-art NFAs have reached significant milestones, such as similar to 19% power conversion efficiencies (PCEs) and small energy losses (less than 0.5 eV). Despite these significant advances, understanding of the interplay between molecular structure and optoelectronic properties lags significantly behind. For example, despite the theoretical framework for describing the energetic disorder being well developed for the case of inorganic semiconductors, the question of the applicability of classical semiconductor theories in analyzing organic semiconductors is still under debate. A general observation in the inorganic field is that inorganic photovoltaic materials possessing a polycrystalline microstructure exhibit suppressed disorder properties and better charge carrier transport compared to their amorphous analogs. Accordingly, this principle extends to the organic semiconductor field as many organic photovoltaic materials are synthesized to pursue polycrystalline-like features. Yet, there appears to be sporadic examples that exhibit an opposite trend. However, full studies decoupling energetic disorder from aggregation effects have largely been left out. Hence, the potential role of the energetic disorder in OSCs has received little attention. Interestingly, recently reported state-of-the-art NFA-based devices could achieve a small energetic disorder and high PCE at the same time; and interest in this investigation related to the disorder properties in OSCs was revived. In this contribution, progress in terms of the correlation between molecular design and energetic disorder is reviewed together with their effects on the optoelectronic mechanism and photovoltaic performance. Finally, the specific challenges and possible solutions in reducing the energetic disorder of OSCs from the viewpoint of materials and devices are proposed.
Inorganic perovskite solar cells show excellent thermal stability, but the reported power conversion efficiencies are still lower than for organic-inorganic perovskites. This is mainly caused by lower open-circuit voltages (V(OC)s). Herein, the reasons for the low V-OC in inorganic CsPbI2Br perovskite solar cells are investigated. Intensity-dependent photoluminescence measurements for different layer stacks reveal that n-i-p and p-i-n CsPbI2Br solar cells exhibit a strong mismatch between quasi-Fermi level splitting (QFLS) and V-OC. Specifically, the CsPbI2Br p-i-n perovskite solar cell has a QFLS-e center dot V-OC mismatch of 179 meV, compared with 11 meV for a reference cell with an organic-inorganic perovskite of similar bandgap. On the other hand, this study shows that the CsPbI2Br films with a bandgap of 1.9 eV have a very low defect density, resulting in an efficiency potential of 20.3% with a MeO-2PACz hole-transporting layer and 20.8% on compact TiO2. Using ultraviolet photoelectron spectroscopy measurements, energy level misalignment is identified as a possible reason for the QFLS-e center dot V-OC mismatch and strategies for overcoming this V-OC limitation are discussed. This work highlights the need to control the interfacial energetics in inorganic perovskite solar cells, but also gives promise for high efficiencies once this issue is resolved.
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.
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.
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.
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.
Inorganic-organic perovskites like methylammonium-lead-iodide have proven to be an effective class of 17 materials for fabricating efficient solar cells. To improve their performance, light management techniques using textured surfaces, similar to those used in established solar cell technologies, should be considered. Here, we apply a light management foil created by UV nanoimprint lithography on the glass side of an inverted (p-i-n) perovskite solar cell with 16.3% efficiency. The obtained 1 mA cm(-2) increase in the short-circuit current density translates to a relative improvement in cell performance of 5%, which results in a power conversion efficiency of 17.1%. Optical 3D simulations based on experimentally obtained parameters were used to support the experimental findings. A good match between the simulated and experimental data was obtained, validating the model. Optical simulations reveal that the main improvement in device performance is due to a reduction in total reflection and that relative improvement in the short-circuit current density of up to 10% is possible for large-area devices. Therefore, our results present the potential of light management foils for improving the device performance of perovskite solar cells and pave the way for further use of optical simulations in the field of perovskite solar cells.
It is shown that several polymers can form insoluble interfacial layers on a poly (ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) layer after annealing of the double-layer structure. The thickness of the interlayer is dependent on the characteristics of the underlying PEDOT.PSS and the molecular weight of the polymers. It is further shown that the electronic structures of the interlayer polymers have a significant effect on the properties of red-light-emitting polymer-based electrophosphorescent devices. Upon increasing the highest occupied molecular orbital and lowest unoccupied molecular orbital positions, a significant increase in current density and device efficiency is observed. This is attributed to efficient blocking of electrons in combination with direct injection of holes from the interlayer to the phosphorescent dye. Upon proper choice of the interlayer polymer, efficient red, polymer-based electrophosphorescent devices with a peak luminance efficiency of 5.5 cd A(-1) (external quantum efficiency = 6 %) and a maximum power-conversion efficiency of 5 Im W-1 can be realized.
We report on polymer blend solar cells with an external quantum efficiency of more than 30% and a hi-h overall energy conversion efficiency (ECE) under white light illumination (100 mW/cm(2)) Of Lip to 1.7% using a blend of M3EH- PPV (poly [2,5-dimethoxy-1,4-phenylene-1,2-ethenylene-2-methoxy-5(2-ethylhexyloxy)-(1,4-pheiiylene-1,2-ethenylene)]) and CN-ether-PPV (poly[oxa-1,4-phenylene-1,2(1-cyano)ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)ethellyiene-1,4- phenylene]). We attribute these high efficiencies to the formation of a vertically composition graded structure during spin coating Photoluminescence measurements performed on the blend layers indicated the formation of exciplexes between both types of polymers, which we propose to be one factor preventing even higher efficiencies
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%.
Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11).
Energy transfer in a ladder-type methyl-poly(para-phenylene) doped by Pt(II)octaethylporphyrin
(2004)
The luminescence of a ladder-type methyl-poly(para-phenylene) (MeLPPP) doped by platinum-porphyrin dye PtOEP covering the concentration 10(-3) to 5% by weight has been measured employing cw and transient techniques. Upon excitating into the range of absorption of the host strong phosphorescence of the dopant is observed. Possible ways of populating of the dopant triplet state are considered. It is shown that the main channel is singlet-singlet energy transfer among chromophor groups of the polymer followed by Forster-type transfer to the guest and subsequent intersystem crossing. (C) 2003 Elsevier B.V. All rights reserved
The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C-60 and small amounts of organic donor molecules. We find a pronounced decline of all photovoltaic parameters with decreasing CT state energy. Using a combination of steady-state photocurrent measurements and time-delayed collection field experiments, we demonstrate that the power conversion efficiency, and more specifically, the fill factor of these devices, is mainly determined by the bias dependence of photocurrent generation. By combining these findings with the results from ultrafast transient absorption spectroscopy, we show that blends with small CT energies perform poorly because of an increased nonradiative CT state decay rate and that this decay obeys an energy-gap law. Our work challenges the common view that a large energy offset at the heterojunction and/or the presence of fullerene clusters guarantee efficient CT dissociation and rather indicates that charge generation benefits from high CT state energies through a slower decay to the ground state.
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.
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.
The luminescence of a ladder-type methyl-poly(para-phenylene) (MeLPPP) doped with platinum-porphyrin dye PtOEP covering the concentration 10(-3)-5% by weight has been measured employing cw and transient techniques. Upon excitation into the range of absorption of the host, strong phosphorescence of the dopant is observed. Possible ways of populating the dopant triplet state are considered. (c) 2004 Elsevier B.V. All rights reserved
Non-fullerene acceptors (NFAs) are far more emissive than their fullerene-based counterparts. Here, we study the spectral properties of photocurrent generation and recombination of the blend of the donor polymer PM6 with the NFA Y6. We find that the radiative recombination of free charges is almost entirely due to the re-occupation and decay of Y6 singlet excitons, but that this pathway contributes less than 1% to the total recombination. As such, the open-circuit voltage of the PM6:Y6 blend is determined by the energetics and kinetics of the charge-transfer (CT) state. Moreover, we find that no information on the energetics of the CT state manifold can be gained from the low-energy tail of the photovoltaic external quantum efficiency spectrum, which is dominated by the excitation spectrum of the Y6 exciton. We, finally, estimate the charge-separated state to lie only 120 meV below the Y6 singlet exciton energy, meaning that this blend indeed represents a high-efficiency system with a low energetic offset.
Organic solar cells (OSC) nowadays match their inorganic competitors in terms of current production but lag behind with regards to their open-circuit voltage loss and fill-factor, with state-of-the-art OSCs rarely displaying fill-factor of 80% and above. The fill-factor of transport-limited solar cells, including organic photovoltaic devices, is affected by material and device-specific parameters, whose combination is represented in terms of the established figures of merit, such as theta and alpha. Herein, it is demonstrated that these figures of merit are closely related to the long-range carrier drift and diffusion lengths. Further, a simple approach is presented to devise these characteristic lengths using steady-state photoconductance measurements. This yields a straightforward way of determining theta and alpha in complete cells and under operating conditions. This approach is applied to a variety of photovoltaic devices-including the high efficiency nonfullerene acceptor blends-and show that the diffusion length of the free carriers provides a good correlation with the fill-factor. It is, finally, concluded that most state-of-the-art organic solar cells exhibit a sufficiently large drift length to guarantee efficient charge extraction at short circuit, but that they still suffer from too small diffusion lengths of photogenerated carriers limiting their fill factor.