The effect of PbS nanocrystal additives on the charge transfer state recombination in a bulk heterojunction blend

Polymer photovoltaic cells currently achieve power conversion efficiencies (PCE) above 10% on lab scale. To compete with the efficiencies above 20% of inorganic solar cells, understanding and elimination of all the loss channels is necessary. This thesis investigates charge generation and recombination processes in polymer-fullerene solar cells with the aim of elucidating the nature of such losses. Chapter 1 provides a general introduction to the subject of the thesis and an overview of the most relevant literature. In Chapter 2 the effect of the thermodynamic driving force on the efficiency of photoinduced charge transfer between semiconducting polymers and fullerene is investigated. A polyfluorene copolymer is mixed with a variety of fullerene mono- and bisadducts having different LUMO energy levels. The difference in LUMO energy of the acceptors results in different energies of the charge transfer (CT) states in the blends. By spectroscopic characterization of bulk heterojunction thin films and photovoltaic devices it is found that the CT state needs to be at least 0.1 eV lower in energy than the singlet excited state of the fullerene to be formed efficiently. The central finding of Chapters 3 to 5 is that the nanoscale morphology of the polymer-fullerene heterojunction strongly influences the CT state dissociation and recombination. Blends composed of a small optical bandgap semiconducting polymer (PCPDTBT) mixed with fullerene are studied with various techniques. The nanoscale phase separation of these blends is controlled by adding high-boiling point co-solvents to the solutions used to process the thin films. Without co-solvent the blends are very finely mixed and the addition of co-solvents increases the phase separation. In blends that are too finely mixed we observe recombination of the CT state to the triplet state of the polymer (Chapter 3). We monitor the formation of triplets and charges in the thin films by means of photo-induced absorption (PIA).The recombination to the triplet state is a loss mechanism, in competition with the dissociation of the CT state into free charges. This process is reduced in favor of free charge formation when the phase separation is increased, correlating with the increased device performance. Specifically, increased fill factor and short circuit current are observed in the devices with optimized morphology. These results show that photophysical processes are controlled by the nanoscale morphology. In Chapter 4 we perform charge extraction experiments on solar cells having different nanoscale phase separation and we support the results with PIA experiments on corresponding thin films. In the charge extraction and PIA experiments we study the same set of long lived charges. We confirm that CT recombination (to the triplet and to the ground state) is largely responsible for the poor device performances of not-optimized blends. Finally, in Chapter 5 we show a correlation between population of triplet excited states and decreased photo-stability of the blends. We suggest that triplet states can lead to the formation of singlet oxygen, which in turn can initiate destructive chemical reactions in the polymer chains. In Chapters 6 and 7 the influence of excess photon energy (i.e. the difference between the energy of the absorbed photon and that of the CT state) in the CT state dissociation is investigated by means of charge extraction and spectral response measurements in different polymer:fullerene blends. We find that excess energy is not necessary for CT dissociation in blends with coarse phase separation. A measurable influence of the excess photon energy on CT dissociation is observed only in PCPDTBT:PCBM finely dispersed blends, which were shown in the previous chapters to be strongly affected by CT state recombination. Chapter 8 investigates what is limiting the photo-current of solar cells close to the open-circuit voltage. It is found that under these conditions space-charge can build up, so that the photocurrent becomes space-charge limited. This condition is reached only in blends where CT dissociation is efficient at low electric fields. Impedance spectroscopy is the technique used here. The experimental results are supported by an analytical model and by drift diffusion simulations. Summarizing, in this thesis it is shown that the CT state is a critical intermediate state in the charge generation process in polymer solar cells. The energy of the CT state needs to be low enough to convert neutral excitations into charges. The blend morphology is a crucial factor determining the branching ratio between dissociation into free carriers and recombination to the ground state or to the triplet state of the polymer.

Charge carrier generation and drift dynamics have been investigated in two types of dye:fullerene heterojunctions: vacuum-deposited merocyanine:C60 and solution-processed merocyanine:PC61BM blends by combining electric-field-induced fluorescence quenching and ultrafast time-resolved carrier drift measurements. We demonstrate that interfacial charge transfer (CT) states are strongly heterogeneous with energies dependent on the acceptor material and its domain sizes. Interfacial CT states on large C60 domains have low energies, while CT states on PC61BM domains have larger energies, which are weakly dependent on the domain sizes. We distinguish two interfacial CT state dissociation pathways: (i) ultrafast, weakly dependent on the electric field and (ii) slow field-assisted dissociation during entire CT state lifetime. We attribute process i to low-energy, weakly bound CT states on large fullerene domains and process ii to strongly bound CT states on small domains or single fullerene molecules. The electron mobility in films with 50% of C60 is several times higher than in the films with PC61BM and orders of magnitude higher than the hole mobility. We conclude that efficient carrier generation at low electric fields typical for operating solar cells relies on unperturbed motion of highly mobile electrons; thus, fast motion and extraction of electrons are crucial for efficient solar cells.

Bulk heterojunction (BHJ) solar cells might one day play a vital role in realizing low-cost and environmentally benign photovoltaic devices. In this work, a BHJ solar cell was designed, based on a hexadeca-substituted phthalocyanine (FcPc) with ferrocenyl linked to the phthalocyanine ring. Next, we sought to obtain more quantitative information about the usability of this newly synthesized compound as a donor material in BHJ solar cells. Thus, BHJs with the structure of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/FcPc:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend/LiF/Al were fabricated and characterized. The effect of blend ratio (0.5-2.0) on the BHJ solar cell parameters was also investigated. Interesting results were obtained in FcPc and the PCBM blend-based BHJ solar cell under optimized conditions. Our results presented here demonstrate that BHJ devices employing FcPc as a donor has great potential for the development of highly efficient non-poly(3-hexylthiophen-2,5-diyl) photovoltaic devices.

Most optimized donor‐acceptor (D‐A) polymer bulk heterojunction (BHJ) solar cells have active layers too thin to absorb greater than ∼80% of incident photons with energies above the polymer's band gap. If the thickness of these devices could be increased without sacrificing internal quantum efficiency, the device power conversion efficiency (PCE) could be significantly enhanced. We examine the device characteristics of BHJ solar cells based on poly(di(2‐ethylhexyloxy)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐octylthieno[3,4‐c]pyrrole‐4,6‐dione) (PBDTTPD) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) with 7.3% PCE and find that bimolecular recombination limits the active layer thickness of these devices. Thermal annealing does not mitigate these bimolecular recombination losses and drastically decreases the PCE of PBDTTPD BHJ solar cells. We characterize the morphology of these BHJs before and after thermal annealing and determine that thermal annealing drastically reduces the concentration of PCBM in the mixed regions, which consist of PCBM dispersed in the amorphous portions of PBDTTPD. Decreasing the concentration of PCBM may reduce the number of percolating electron transport pathways within these mixed regions and create morphological electron traps that enhance charge‐carrier recombination and limit device quantum efficiency. These findings suggest that (i) the concentration of PCBM in the mixed regions of polymer BHJs must be above the PCBM percolation threshold in order to attain high solar cell internal quantum efficiency, and (ii) novel processing techniques, which improve polymer hole mobility while maintaining PCBM percolation within the mixed regions, should be developed in order to limit bimolecular recombination losses in optically thick devices and maximize the PCE of polymer BHJ solar cells.

Organic Solar Cells Based on Non-fullerene Small-Molecule Acceptors: Impact of Substituent Position

To determine the role of photon energy on charge generation in bulk heterojunction solar cells, the bias voltage dependence of photocurrent for excitation with photon energies below and above the optical band gap is investigated in two structurally related polymer solar cells. Charges generated in (poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothia­diazole)] (C‐PCPDTBT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) solar cells via excitation of the low‐energy charge transfer (CT) state, situated below the optical band gap, need more voltage to be extracted than charges generated with excitation above the optical band gap. This indicates a lower effective binding energy of the photogenerated electrons and holes when the excitation is above the optical band gap than when excitation is to the bottom of the CT state. In blends of PCBM with the silicon‐analogue, poly[(4,4‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐2,6‐diyl‐alt‐(2,1,3‐benzothiadiazole)‐4,7‐diyl] (Si‐PCPDTBT), there is no effect of the photon energy on the electric field dependence of the dissociation efficiency of the CT state. C‐PCPDTBT and Si‐PCPDTBT have very similar electronic properties, but their blends with PCBM differ in the nanoscale phase separation. The morphology is coarser and more crystalline in Si‐PCPDTBT:PCBM blends. The results demonstrate that the nanomorphological properties of the bulk heterojunction are important for determining the effective binding energy in the generation of free charges at the heterojunction.

Squaraine (SQ) dyes have been considered as efficient photoactive materials for organic solar cells. In this work, we purposely controlled the molecular aggregation of an SQ dye, 2,4-bis[4-(N,N-dibutylamino)-2-dihydroxyphenyl] SQ (DBSQ-(OH)2) in the DBSQ(OH)2:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend film by using the thermal annealing method, to study the influence of the molecular aggregation on film properties as well as the photovoltaic performance of DBSQ(OH)2:PCBM-based bulk heterojunction (BHJ) solar cells. Our results demonstrate that thermal annealing may change the aggregation behavior of DBSQ(OH)2 in the DBSQ(OH)2:PCBM film, and thus significantly influence the surface morphology, optical and electrical properties of the blend film, as well as the photovoltaic performance of DBSQ(OH)2:PCBM BHJ cells.

Harvesting near- and far-field plasmonic enhancements from large size gold nanoparticles for improved performance in organic bulk heterojunction solar cells

Knowledge of the critical factors that determine compatibility, blend morphology, and performance of bulk heterojunction (BHJ) solar cells composed of an electron-accepting polymer and an electron-donating polymer remains limited. To test the idea that bulk crystallinity is such a critical factor, we have designed a series of new semiconducting naphthalene diimide (NDI)-selenophene/perylene diimide (PDI)-selenophene random copolymers, xPDI (10PDI, 30PDI, 50PDI), whose crystallinity varies with composition, and investigated them as electron acceptors in BHJ solar cells. Pairing of the reference crystalline (crystalline domain size Lc = 10.22 nm) NDI-selenophene copolymer (PNDIS-HD) with crystalline (Lc = 9.15 nm) benzodithiophene-thieno[3,4-b]thiophene copolymer (PBDTTT-CT) donor yields incompatible blends, whose BHJ solar cells have a power conversion efficiency (PCE) of 1.4%. However, pairing of the new 30PDI with optimal crystallinity (Lc = 5.11 nm) as acceptor with the same PBDTTT-CT donor yields compatible blends and all-polymer solar cells with enhanced performance (PCE = 6.3%, Jsc = 18.6 mA/cm(2), external quantum efficiency = 91%). These photovoltaic parameters observed in 30PDI:PBDTTT-CT devices are the best so far for all-polymer solar cells, while the short-circuit current (Jsc) and external quantum efficiency are even higher than reported values for [70]-fullerene:PBDTTT-CT solar cells. The morphology and bulk carrier mobilities of the polymer/polymer blends varied substantially with crystallinity of the acceptor polymer component and thus with the NDI/PDI copolymer composition. These results demonstrate that the crystallinity of a polymer component and thus compatibility, blend morphology, and efficiency of polymer/polymer blend solar cells can be controlled by molecular design.

The precise mechanism and dynamics of charge generation and recombination in bulk heterojunction polymer:fullerene blend films typically used in organic photovoltaic devices have been intensively studied by many research groups, but nonetheless remain debated. In particular the role of interfacial charge-transfer (CT) states in the generation of free charge carriers, an important step for the understanding of device function, is still under active discussion. In this article we present direct optical probes of the exciton dynamics in pristine films of a prototypic polycarbazole-based photovoltaic donor polymer, namely poly[N-11''-henicosanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT), as well as the charge generation and recombination dynamics in as-cast and annealed photovoltaic blend films using methanofullerene (PC(61)BM) as electron acceptor. In contrast to earlier studies we use broadband (500-1100 nm) transient absorption spectroscopy including the previously unobserved but very important time range between 2 ns and 1 ms, which allows us not only to observe the entire charge carrier recombination dynamics but also to quantify the existing decay channels. We determine that ultrafast exciton dissociation occurs in blends and leads to two separate pools of products, namely Coulombically bound charge-transfer (CT) states and unbound (free) charge carriers. The recombination dynamics are analyzed within the framework of a previously reported model for poly(3-hexylthiophene):PCBM (Howard, I. A. J. Am. Chem. Soc. 2010, 132, 14866) based on concomitant geminate recombination of CT states and nongeminate recombination of free charge carriers. The results reveal that only ~11% of the initial photoexcitations generate interfacial CT states that recombine exclusively by fast nanosecond geminate recombination and thus do not contribute to the photocurrent, whereas ~89% of excitons create free charge carriers on an ultrafast time scale that then contribute to the extracted photocurrent. Despite the high yield of free charges the power conversion efficiency of devices remains moderate at about 3.0%. This is largely a consequence of the low fill factor of devices. We relate the low fill factor to significant energetic disorder present in the pristine polymer and in the polymer:fullerene blends. In the former we observed a significant spectral relaxation of exciton emission (fluorescence) and in the latter of the polaron-induced ground-state bleaching, implying that the density of states (DOS) for both excitons and charge carriers is significantly broadened by energetic disorder in pristine PCDTBT and in its blend with PCBM. This disorder leads to charge trapping in solar cells, which in turn causes higher carrier concentrations and more significant nongeminate recombination. The nongeminate recombination has a significant impact on the IV curves of devices, namely its competition with charge carrier extraction causes a stronger bias dependence of the photocurrent of devices, in turn leading to the poor device fill factor. In addition our results demonstrate the importance of ultrafast free carrier generation and suppression of interfacial CT-state formation and question the applicability of the often used Braun-Onsager model to describe the bias dependence of the photocurrent in polymer:fullerene organic photovoltaic devices.

Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short‐circuit currents (JSC) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open‐circuit voltages (VOC). 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 VOC (0.9 V) with very low energy losses (Eloss = 0.52 eV) from the energy of absorbed photons, a respectable JSC (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 JSC, VOC, and FF can all be improved, even with very low energetic offsets.

The performance of organic bulk heterojunction (BHJ) solar cells depends strongly on the nanoscale morphology formed by the donor and acceptor materials. However, the majority of device models for organic BHJ solar cells are based on an effective-medium formulation that does not capture details of the underlying morphology. In order to link more detailed models with effective-medium models, we derive a spatially smoothed formulation for organic BHJ solar cells based on volume-averaging of a mathematical model that considers charge carrier transport, generation, and recombination in both the acceptor and donor phases. The formulation captures two essential morphological characteristics of the organic BHJ layer that are not found in existing effective-medium models: the effective interfacial area and the volume fraction ratio between donor and acceptor materials. In addition, effective charge carrier mobilities and diffusion coefficients are identified, which are determined for an “ideal” interpenetrated BHJ solar cell.

Chapter 11 - Nanostructured Organic Bulk Heterojunction Solar Cells

A model for studying the performance of P3HT:PCBM organic bulk heterojunction solar cells

Bulk heterojunction (BHJ) solar cells based on blends comprising conjugated polymers and fullerene acceptors are the subject of considerable investigation because of their potential to enable the fabrication of low-cost devices that convert sunlight into electricity. Recently, poly(2,7-carbazole) derivatives have gained momentum as a class of promising alternative materials to poly(3-hexylthiophene) (P3HT) in organic solar cell applications. Among them, poly[N-900-hepta-decanyl-2,7-carbazole-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzo thiadiazole)] (PCDTBT) has a relatively deeper highest occupied molecular orbital (HOMO) of 5.45 eV compared to the HOMO of 5.1 eV of the P3HT. In this work we systematically study the effect of donor and acceptor ratio on the device performance of bulk heterojunction solar cells made with blends of PCDTBT and PC₇₁BM. We used PEDOT: PSS as a hole transport layer, and TiOX as a hole-blocking layer in order to improve the power conversion efficiency. The current density-voltage (JV) characteristics of photovoltaic cells were measured under the illumination of simulated solar light with 100 mW/cm² (AM 1.5G) by an Oriel 1000 W solar simulator. The power conversion efficiency of the solar cell is more than 5%.