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A Shockley-Type polymer
(2018)
Charge extraction rate in solar cells made of blends of electron donating/accepting organic semiconductors is typically slow due to their low charge carrier mobility. This sets a limit on the active layer thickness and has hindered the industrialization of organic solar cells (OSCs). Herein, charge transport and recombination properties of an efficient polymer (NT812):fullerene blend are investigated. This system delivers power conversion efficiency of >9% even when the junction thickness is as large as 800 nm. Experimental results indicate that this material system exhibits exceptionally low bimolecular recombination constant, 800 times smaller than the diffusion-controlled electron and hole encounter rate. Comparing theoretical results based on a recently introduced modified Shockley model for fill factor, and experiments, clarifies that charge collection is nearly ideal in these solar cells even when the thickness is several hundreds of nanometer. This is the first realization of high-efficiency Shockley-type organic solar cells with junction thicknesses suitable for scaling up.
Organic solar cells are currently experiencing a second golden age thanks to the development of novel non-fullerene acceptors (NFAs). Surprisingly, some of these blends exhibit high efficiencies despite a low energy offset at the heterojunction. Herein, free charge generation in the high-performance blend of the donor polymer PM6 with the NFA Y6 is thoroughly investigated as a function of internal field, temperature and excitation energy. Results show that photocurrent generation is essentially barrierless with near-unity efficiency, regardless of excitation energy. Efficient charge separation is maintained over a wide temperature range, down to 100 K, despite the small driving force for charge generation. Studies on a blend with a low concentration of the NFA, measurements of the energetic disorder, and theoretical modeling suggest that CT state dissociation is assisted by the electrostatic interfacial field which for Y6 is large enough to compensate the Coulomb dissociation barrier.
Tremendous progress in the development of thin film solar cell techniques has been made over the last decade. The field of organic solar cells is constantly developing, new material classes like Perowskite solar cells are emerging and different types of hybrid organic/inorganic material combinations are being investigated for their physical properties and their applicability in thin film electronics. Besides typical single-junction architectures for solar cells, multi-junction concepts are also being investigated as they enable the overcoming of theoretical limitations of a single-junction. In multi-junction devices each sub-cell operates in different wavelength regimes and should exhibit optimized band-gap energies. It is exactly this tunability of the band-gap energy that renders organic solar cell materials interesting candidates for multi-junction applications. Nevertheless, only few attempts have been made to combine inorganic and organic solar cells in series connected multi-junction architectures. Even though a great diversity of organic solar cells exists nowadays, their open circuit voltage is usually low compared to the band-gap of the active layer. Hence, organic low band-gap solar cells in particular show low open circuit voltages and the key factors that determine the voltage losses are not yet fully understood. Besides open circuit voltage losses the recombination of charges in organic solar cells is also a prevailing research topic, especially with respect to the influence of trap states.
The exploratory focus of this work is therefore set, on the one hand, on the development of hybrid organic/inorganic multi-junctions and, on the other hand, on gaining a deeper understanding of the open circuit voltage and the recombination processes of organic solar cells.
In the first part of this thesis, the development of a hybrid organic/inorganic triple-junction will be discussed which showed at that time (Jan. 2015) a record power conversion efficiency of 11.7%. The inorganic sub-cells of these devices consist of hydrogenated amorphous silicon and were delivered by the Competence Center Thin-Film and Nanotechnology for Photovoltaics in Berlin. Different recombination contacts and organic sub-cells were tested in conjunction with these inorganic sub-cells on the basis of optical modeling predictions for the optimal layer thicknesses to finally reach record efficiencies for this type of solar cells.
In the second part, organic model systems will be investigated to gain a better understanding of the fundamental loss mechanisms that limit the open circuit voltage of organic solar cells. First, bilayer systems with different orientation of the donor and acceptor molecules were investigated to study the influence of the donor/acceptor orientation on non-radiative voltage loss. Secondly, three different bulk heterojunction solar cells all comprising the same amount of fluorination and the same polymer backbone in the donor component were examined to study the influence of long range electrostatics on the open circuit voltage. Thirdly, the device performance of two bulk heterojunction solar cells was compared which consisted of the same donor polymer but used different fullerene acceptor molecules. By this means, the influence of changing the energetics of the acceptor component on the open circuit voltage was investigated and a full analysis of the charge carrier dynamics was presented to unravel the reasons for the worse performance of the solar cell with the higher open circuit voltage. In the third part, a new recombination model for organic solar cells will be introduced and its applicability shown for a typical low band-gap cell. This model sheds new light on the recombination process in organic solar cells in a broader context as it re-evaluates the recombination pathway of charge carriers in devices which show the presence of trap states. Thereby it addresses a current research topic and helps to resolve alleged discrepancies which can arise from the interpretation of data derived by different measurement techniques.
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.
Organic bulk heterojunction (BHJ) solar cells based on polymer:fullerene blends are a promising alternative for a low-cost solar energy conversion. Despite significant improvements of the power conversion efficiency in recent years, the fundamental working principles of these devices are yet not fully understood. In general, the current output of organic solar cells is determined by the generation of free charge carriers upon light absorption and their transport to the electrodes in competition to the loss of charge carriers due to recombination.
The object of this thesis is to provide a comprehensive understanding of the dynamic processes and physical parameters determining the performance. A new approach for analyzing the characteristic current-voltage output was developed comprising the experimental determination of the efficiencies of charge carrier generation, recombination and transport, combined with numerical device simulations.
Central issues at the beginning of this work were the influence of an electric field on the free carrier generation process and the contribution of generation, recombination and transport to the current-voltage characteristics. An elegant way to directly measure the field dependence of the free carrier generation is the Time Delayed Collection Field (TDCF) method. In TDCF charge carriers are generated by a short laser pulse and subsequently extracted by a defined rectangular voltage pulse. A new setup was established with an improved time resolution compared to former reports in literature. It was found that charge generation is in general independent of the electric field, in contrast to the current view in literature and opposed to the expectations of the Braun-Onsager model that was commonly used to describe the charge generation process. Even in cases where the charge generation was found to be field-dependend, numerical modelling showed that this field-dependence is in general not capable to account for the voltage dependence of the photocurrent. This highlights the importance of efficient charge extraction in competition to non-geminate recombination, which is the second objective of the thesis.
Therefore, two different techniques were combined to characterize the dynamics and efficiency of non-geminate recombination under device-relevant conditions. One new approach is to perform TDCF measurements with increasing delay between generation and extraction of charges. Thus, TDCF was used for the first time to measure charge carrier generation, recombination and transport with the same experimental setup. This excludes experimental errors due to different measurement and preparation conditions and demonstrates the strength of this technique. An analytic model for the description of TDCF transients was developed and revealed the experimental conditions for which reliable results can be obtained. In particular, it turned out that the $RC$ time of the setup which is mainly given by the sample geometry has a significant influence on the shape of the transients which has to be considered for correct data analysis.
Secondly, a complementary method was applied to characterize charge carrier recombination under steady state bias and illumination, i.e. under realistic operating conditions. This approach relies on the precise determination of the steady state carrier densities established in the active layer. It turned out that current techniques were not sufficient to measure carrier densities with the necessary accuracy. Therefore, a new technique {Bias Assisted Charge Extraction} (BACE) was developed. Here, the charge carriers photogenerated under steady state illumination are extracted by applying a high reverse bias. The accelerated extraction compared to conventional charge extraction minimizes losses through non-geminate recombination and trapping during extraction. By performing numerical device simulations under steady state, conditions were established under which quantitative information on the dynamics can be retrieved from BACE measurements.
The applied experimental techniques allowed to sensitively analyse and quantify geminate and non-geminate recombination losses along with charge transport in organic solar cells. A full analysis was exemplarily demonstrated for two prominent polymer-fullerene blends.
The model system P3HT:PCBM spincast from chloroform (as prepared) exhibits poor power conversion efficiencies (PCE) on the order of 0.5%, mainly caused by low fill factors (FF) and currents. It could be shown that the performance of these devices is limited by the hole transport and large bimolecular recombination (BMR) losses, while geminate recombination losses are insignificant. The low polymer crystallinity and poor interconnection between the polymer and fullerene domains leads to a hole mobility of the order of 10^-7 cm^2/Vs which is several orders of magnitude lower than the electron mobility in these devices. The concomitant build up of space charge hinders extraction of both electrons and holes and promotes bimolecular recombination losses.
Thermal annealing of P3HT:PCBM blends directly after spin coating improves crystallinity and interconnection of the polymer and the fullerene phase and results in comparatively high electron and hole mobilities in the order of 10^-3 cm^2/Vs and 10^-4 cm^2/Vs, respectively. In addition, a coarsening of the domain sizes leads to a reduction of the BMR by one order of magnitude. High charge carrier mobilities and low recombination losses result in comparatively high FF (>65%) and short circuit current (J_SC ≈ 10 mA/cm^2). The overall device performance (PCE ≈ 4%) is only limited by a rather low spectral overlap of absorption and solar emission and a small V_OC, given by the energetics of the P3HT.
From this point of view the combination of the low bandgap polymer PTB7 with PCBM is a promising approach. In BHJ solar cells, this polymer leads to a higher V_OC due to optimized energetics with PCBM. However, the J_SC in these (unoptimized) devices is similar to the J_SC in the optimized blend with P3HT and the FF is rather low (≈ 50%). It turned out that the unoptimized PTB7:PCBM blends suffer from high BMR, a low electron mobility of the order of 10^-5 cm^2/Vs and geminate recombination losses due to field dependent charge carrier generation.
The use of the solvent additive DIO optimizes the blend morphology, mainly by suppressing the formation of very large fullerene domains and by forming a more uniform structure of well interconnected donor and acceptor domains of the order of a few nanometers. Our analysis shows that this results in an increase of the electron mobility by about one order of magnitude (3 x 10^-4 cm^2/Vs), while BMR and geminate recombination losses are significantly reduced. In total these effects improve the J_SC (≈ 17 mA/cm^2) and the FF (> 70%). In 2012 this polymer/fullerene combination resulted in a record PCE for a single junction OSC of 9.2%.
Remarkably, the numerical device simulations revealed that the specific shape of the J-V characteristics depends very sensitively to the variation of not only one, but all dynamic parameters. On the one hand this proves that the experimentally determined parameters, if leading to a good match between simulated and measured J-V curves, are realistic and reliable. On the other hand it also emphasizes the importance to consider all involved dynamic quantities, namely charge carrier generation, geminate and non-geminate recombination as well as electron and hole mobilities. The measurement or investigation of only a subset of these parameters as frequently found in literature will lead to an incomplete picture and possibly to misleading conclusions.
Importantly, the comparison of the numerical device simulation employing the measured parameters and the experimental $J-V$ characteristics allows to identify loss channels and limitations of OSC. For example, it turned out that inefficient extraction of charge carriers is a criticical limitation factor that is often disobeyed. However, efficient and fast transport of charges becomes more and more important with the development of new low bandgap materials with very high internal quantum efficiencies. Likewise, due to moderate charge carrier mobilities, the active layer thicknesses of current high-performance devices are usually limited to around 100 nm. However, larger layer thicknesses would be more favourable with respect to higher current output and robustness of production. Newly designed donor materials should therefore at best show a high tendency to form crystalline structures, as observed in P3HT, combined with the optimized energetics and quantum efficiency of, for example, PTB7.
Non-geminate recombination, as one of the most relevant loss mechanisms in organic and perovskite solar cells, deserves special attention in research efforts to further increase device performance. It can be subdivided into first, second, and third order processes, which can be elucidated by the effects that they have on the time-dependent open-circuit voltage decay. In this study, analytical expressions for the open-circuit voltage decay exhibiting one of the aforementioned recombination mechanisms were derived. It was possible to support the analytical models with experimental examples of three different solar cells, each of them dominated either by first (PBDBT:CETIC-4F), second (PM6:Y6), or third (irradiated CH3NH3PbI3) order recombination. Furthermore, a simple approach to estimate the dominant recombination process was also introduced and tested on these examples. Moreover, limitations of the analytical models and the measurement technique itself were discussed.
Effects of solvent additive on "s-shaped" curves in solution-processed small molecule solar cells
(2016)
A novel molecular chromophore, p-SIDT(FBTThCA8)(2), is introduced as an electron-donor material for bulk heterojunction (BHJ) solar cells with broad absorption and near ideal energy levels for the use in combination with common acceptor materials. It is found that films cast from chlorobenzene yield devices with strongly s-shaped current-voltage curves, drastically limiting performance. We find that addition of the common solvent additive diiodooctane, in addition to facilitating crystallization, leads to improved vertical phase separation. This yields much better performing devices, with improved curve shape, demonstrating the importance of morphology control in BHJ devices and improving the understanding of the role of solvent additives.
While the performance of laboratory-scale organic solar cells (OSCs) continues to grow, development of high efficiency large area OSCs remains a big challenge. Although a few attempts to produce large area organic solar cells (OSCs) have been reported, there are still challenges on the way to realizing efficient module devices, such as the low compatibility of the thickness-sensitive active layer with large area coating techniques, the frequent need for toxic solvents and tedious optimization processes used during device fabrication. In this work, highly efficient thickness-insensitive OSCs based on PTB7-Th:PC71BM that processed with single-component green solvent 2-methylanisole are presented, in which both junction thickness limitation and solvent toxicity issues are simultaneously addressed. Careful investigation reveals that this green solvent prevents the evolution of PC71BM into large area clusters resulting in reduced charge carrier recombination, and largely eliminates trapping centers, and thus improves the thickness tolerance of the films. These findings enable us to address the scalability and solvent toxicity issues and to fabricate a 16 cm(2) OSC with doctor-blade coating with a state-of-the-art power conversion efficiency of 7.5% using green solvent.
Donor-acceptor (D-A) copolymers have revolutionized the field of organic electronics over the last decade. Comprised of a electron rich and an electron deficient molecular unit, these copolymers facilitate the systematic modification of the material's optoelectronic properties. The ability to tune the optical band gap and to optimize the molecular frontier orbitals as well as the manifold of structural sites that enable chemical modifications has created a tremendous variety of copolymer structures. Today, these materials reach or even exceed the performance of amorphous inorganic semiconductors. Most impressively, the charge carrier mobility of D-A copolymers has been pushed to the technologically important value of 10 cm^{2}V^{-1}s^{-1}. Furthermore, owed to their enormous variability they are the material of choice for the donor component in organic solar cells, which have recently surpassed the efficiency threshold of 10%. Because of the great number of available D-A copolymers and due to their fast chemical evolution, there is a significant lack of understanding of the fundamental physical properties of these materials. Furthermore, the complex chemical and electronic structure of D-A copolymers in combination with their semi-crystalline morphology impede a straightforward identification of the microscopic origin of their superior performance. In this thesis, two aspects of prototype D-A copolymers were analysed. These are the investigation of electron transport in several copolymers and the application of low band gap copolymers as acceptor component in organic solar cells. In the first part, the investigation of a series of chemically modified fluorene-based copolymers is presented. The charge carrier mobility varies strongly between the different derivatives, although only moderate structural changes on the copolymers structure were made. Furthermore, rather unusual photocurrent transients were observed for one of the copolymers. Numerical simulations of the experimental results reveal that this behavior arises from a severe trapping of electrons in an exponential distribution of trap states. Based on the comparison of simulation and experiment, the general impact of charge carrier trapping on the shape of photo-CELIV and time-of-flight transients is discussed. In addition, the high performance naphthalenediimide (NDI)-based copolymer P(NDI2OD-T2) was characterized. It is shown that the copolymer posses one of the highest electron mobilities reported so far, which makes it attractive to be used as the electron accepting component in organic photovoltaic cells.\par Solar cells were prepared from two NDI-containing copolymers, blended with the hole transporting polymer P3HT. I demonstrate that the use of appropriate, high boiling point solvents can significantly increase the power conversion efficiency of these devices. Spectroscopic studies reveal that the pre-aggregation of the copolymers is suppressed in these solvents, which has a strong impact on the blend morphology. Finally, a systematic study of P3HT:P(NDI2OD-T2) blends is presented, which quantifies the processes that limit the efficiency of devices. The major loss channel for excited states was determined by transient and steady state spectroscopic investigations: the majority of initially generated electron-hole pairs is annihilated by an ultrafast geminate recombination process. Furthermore, exciton self-trapping in P(NDI2OD-T2) domains account for an additional reduction of the efficiency. The correlation of the photocurrent to microscopic morphology parameters was used to disclose the factors that limit the charge generation efficiency. Our results suggest that the orientation of the donor and acceptor crystallites relative to each other represents the main factor that determines the free charge carrier yield in this material system. This provides an explanation for the overall low efficiencies that are generally observed in all-polymer solar cells.
Organic solar cells have the potential to become the cheapest form of electricity. Rapid increase in the power conversion efficiency of organic solar cells (OSCs) has been achieved with the development of non-fullerene small-molecule acceptors. Next generation photovoltaics based upon environmentally benign "green solvent" processing of organic semiconductors promise a step-change in the adaptability and versatility of solar technologies and promote sustainable development. However, high-performing OSCs are still processed by halogenated (non-environmentally friendly) solvents, so hindering their large-scale manufacture. In this perspective, we discuss the recent progress in developing highly efficient OSCs processed from eco-compatible solvents, and highlight research challenges that should be addressed for the future development of high power conversion efficiencies devices.