Polymer-fullerene Bulk Heterojunction Solar Cells Research Articles

Impact of Polymer Backbone Fluorination on the Charge Generation/Recombination Patterns and Vertical Phase Segregation in Bulk Heterojunction Organic Solar Cells.

Incorporating fluorine (–F) substituents along the main-chains of polymer donors and acceptors is an effective strategy toward efficient bulk-heterojunction (BHJ) solar cells. Specifically, F-substituted polymers often exhibit planar conformations, leading to favorable packing, and electronic coupling. However, the effects of fluorine substituents on the charge generation and recombination characteristics that determine the overall efficiency of BHJ active layers remain critically important issues to examine. In this report, two PBDT[2X]T polymer analogs –poly[4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4, 5-b′]dithiophene-thiophene] [PBDT[2H]T] and its F-substituted counterpart poly[4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-difluoro-thiophene] [PBDT[2F]T]—are studied to systematically examine how –F substituents impact the blend morphology, charge generation, carrier recombination and extraction in BHJ solar cells. Considering the large efficiency differences between PBDT[2H]T- and PBDT[2F]T-based BHJ devices, significant emphasis is given to characterizing the out-of-plane morphology of the blend films as vertical phase-separation characteristics are known to have dramatic effects on charge transport and carrier extraction in polymer-fullerene BHJ solar cells. Herein, we use electron energy loss spectroscopy (EELS) in tandem with charge transport characterization to examine PBDT[2X]T-fullerene blend films. Our analyses show that PBDT[2H]T and PBDT[2F]T possess very different charge generation, recombination and extraction characteristics, resulting from distinct aggregation, and phase-distribution within the BHJ blend films.

Mixed Domains Enhance Charge Generation and Extraction in Bulk‐Heterojunction Solar Cells with Small‐Molecule Donors

AbstractThe interplay between nanomorphology and efficiency of polymer‐fullerene bulk‐heterojunction (BHJ) solar cells has been the subject of intense research, but the generality of these concepts for small‐molecule (SM) BHJs remains unclear. Here, the relation between performance; charge generation, recombination, and extraction dynamics; and nanomorphology achievable with two SM donors benzo[1,2‐b:4,5‐b]dithiophene‐pyrido[3,4‐b]‐pyrazine BDT(PPTh2)2, namely SM1 and SM2, differing by their side‐chains, are examined as a function of solution additive composition. The results show that the additive 1,8‐diiodooctane acts as a plasticizer in the blends, increases domain size, and promotes ordering/crystallinity. Surprisingly, the system with high domain purity (SM1) exhibits both poor exciton harvesting and severe charge trapping, alleviated only slightly with increased crystallinity. In contrast, the system consisting of mixed domains and lower crystallinity (SM2) shows both excellent exciton harvesting and low charge recombination losses. Importantly, the onset of large, pure crystallites in the latter (SM2) system reduces efficiency, pointing to possible differences in the ideal morphologies for SM‐based BHJ solar cells compared with polymer‐fullerene devices. In polymer‐based systems, tie chains between pure polymer crystals establish a continuous charge transport network, whereas SM‐based active layers may in some cases require mixed domains that enable both aggregation and charge percolation to the electrodes.

All carbon non-covalent exohedral hybrids: C60 aggregates on nanotube networks

Exohedral van der Waals (vdW) hybrids comprising pristine carbon nanotubes (CNTs) and C60 fullerenes are expected to enable the engineering of carbonaceous materials with tunable physical and chemical properties due to the unperturbed sp2 hybridization of the comprising allotropes. In spite of theoretical predictions, experimental realization of exohedral non-covalent hybridization of unmodified C60 fullerenes and CNTs was not reported before, probably due to the relatively strong inter-fullerene and inter-tube interactions that drive the system toward phase separation and the formation of fullerene crystals and CNTs bundles. Here we describe a two-step process for preparation of C60–CNTs hybrids. The first step is based on solution-assembly of random, 3D-networks of individual, pristine CNTs followed by fast solvent-quenching. In the second step sublimated fullerenes are deposited onto the pre-assembled networks where structural defects serve as nucleation points for fullerite nanocrystals. Annealing at low temperature (80 °C) results in re-organization of the C60 nanocrystals into nanometric layers, forming a CNT-C60 core-shell like cylindrical hybrids. Raman characterization and the observed high mobility of the fullerenes at the CNT surface support the assumption that the exohedral hybrids are of vdW type. The approach presented here offers a pathway for preparation of exohedral hybrids with controlled nano-morphology: CNTs-networks decorated by nanometric C60 crystals and CNTs-3D-networks coated by a shell of non-covalently bonded mono- or multi-layers of C60 molecules that may serve to shape the nano-morphology of the active layer in polymer-fullerene bulk-heterojunction solar cells.

Improved efficiency of polymer-fullerene bulk heterojunction solar cells by the addition of Cu(II)-porphyrin-oligothiophene conjugates

Ternary organic photovoltaic devices were prepared through the addition of small amounts of metalloporphyin-terthiophenes to two established low bandgap polymer:fullerene blends. The methodology afforded a PCDTBT:PC71BM-based device that displayed an initial power conversion efficiency of 5.1%, an increase of 16% when compared to the binary blend. Among the range of metalloporphyrins considered in this study, the Cu(II)-porphyrin derivatives were found to result in the most significant efficiency improvements.

Criteria for validating polaron pair dissociation in polymer-fullerene bulk heterojunction solar cells

The dissociation of polaron pairs into free charge carriers in organic bulk heterojunction solar cells is a fundamental step in generating photocurrent and is still in debate. In this study, we propose two simple criteria that can be used to test the validity of any polaron pair dissociation model for polymer-fullerene bulk heterojunction solar cells. The first criterion states that the ratio of the bimolecular recombination current density to the maximum photocurrent density should increase as a function of applied voltage. The second criterion states that the ratio of the bimolecular recombination current density to the maximum photocurrent density at short circuit should not be larger than 1. We apply these criteria to test the validity of the widely used Onsager-Braun model by using the experimental current-voltage data of poly[2-methoxy-5-(3′-7′-dimethyloctyloxy)-p-phenylene vinylene] (OC1C10-PPV) and [6,6]-phenyl C61-butyric acid methylester (PCBM) based solar cells. We find that our numerical analysis is not suitable to employ these criteria. Our analytical analysis, on the other hand, clearly demonstrates that the Onsager-Braun model simply cannot fulfill the first criteria. The reason is because the polaron pair dissociation given by the Onsager-Braun model is too strongly influenced by the electric field (i.e., decreases too rapidly as the electric field decreases). The analysis provides a further evidence against the widely used Onsager-Braun model. The proposed criteria can help us to determine the correct model for polaron pair dissociation by serving as a guideline on how strongly the electric field is allowed to influence the polaron pair dissociation.

Naphthodithieno[3,2-b]thiophene-based donor-acceptor copolymers: Synthesis, characterization, and their photovoltaic and charge transport properties

Herein, we report the synthesis, characterization, and their photovoltaic and field–effect properties of two dialkoxyl-substituted naphthodithieno[3,2-b]thiophene (NDTT)-based copolymers, namely P1 and P2. The NDTT-based copolymers exhibit broad absorption profiles throughout the visible spectrum up to ca. 800 nm. The copolymers have HOMO/LUMO energy levels of ca. –5.14 eV/–3.52 eV. The dialkoxyl-substituted NDTT units endow the copolymers with enhanced solution processability, and crystalline stacking thin films with small π–π distances of down to 3.59 Å. Polymer-fullerene bulk heterojunction solar cells that fabricated from a blend of P2/PC71BM using diiodooctane as a solvent additive, afforded the highest power conversion efficiency of 3.54%. Solution-processed polymer field-effect transistors based on P1 with bottom-gate bottom-contact geometry exhibited promising hole mobilities of 0.070 cm2 V−1 s−1.

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

In the study of bulk heterojunction (BHJ) solar cells based on poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM), P3HT/PCBM device performance is strongly depending on the thickness of active region, materials in use and fabrication methods. In such devices, optoelectronic behaviors such as charge carrier generation and recombination, photocurrent generation and charge transport mechanism are different in devices of different fabrication methods. An electrical model accounting for study of the performance of P3HT:PCBM organic bulk heterojunction solar cells is developed to achieve the device parameter for high performance of the polymer-fullerene bulk heterojunction solar cells. In this model, by solving the drift–diffusion equations by considering the boundary condition and uniform potential energy, the effects of the active region thickness, potential energy and photocurrent generation on the performance of P3HT:PCBM bulk heterojunction solar cell have been studied. Simulated current–voltage characteristics as a function of active layer thickness reveal relatively good agreement between the model's predictions and published modeling and experimental reports.

Role of Oxygen Adsorption in Nanocrystalline ZnO Interfacial Layers for Polymer–Fullerene Bulk Heterojunction Solar Cells

Colloidal zinc oxide (ZnO) nanoparticles are frequently used in the field of organic photovoltaics for the realization of solution-producible, electron-selective interfacial layers. Despite of the widespread use, there is a lack of detailed investigations regarding the impact of structural properties of the particles on the device performance. In this work, ZnO nanoparticles with varying surface-area-to-volume ratio were synthesized and implemented into polymer-fullerene bulk heterojunction solar cells with a gas-permeable top electrode. By comparing the electrical characteristics before and after encapsulation, it was found that the internal surface area of the ZnO layer plays a crucial role under conditions where oxygen can penetrate the solar cells. The adsorption of oxygen species at the nanoparticle surface causes band bending and electron depletion next to the surface. Both effects result in the formation of a barrier for electron injection and extraction at the ZnO/bulk heterojunction interface and were more pronounced in case of small ZnO nanocrystals (high surface-area-to-volume ratio). Different transport-related phenomena in the presence of oxygen are discussed in detail, i.e., Ohmic losses, expressed in terms of series resistance, as well as the occurrence of space-charge-limited currents, related to charge accumulation in the polymer-fullerene blend. Since absorption of UV light can cause desorption of adsorbed oxygen species, the electrical properties depend also on the illumination conditions. With the help of systematic investigations of the current versus voltage characteristics of solar cells under different air exposure and illumination conditions as well as studies of the photoconductivity of pure ZnO nanoparticle layers, we gain detailed insight into the role of the ZnO nanoparticle surface for the functionality of the organic solar cells.

Influence of active region thickness on the performance of bulk heterojunction solar cells: electrical modeling and simulation

In the study of bulk heterojunction solar cells based on poly(3-hexylthiophene) (P3HT) and a methanofullerene derivative (PCBM), P3HT/PCBM device performance is strongly depends on the thickness of active region. In such devices, optoelectronic behaviors such as charge carrier generation and recombination, photocurrent generation and charge transport mechanism is different in devices of different thickness. An electrical model accounting for study the influences of active layer thickness on the device performance, is developed to achieve the device parameter for high performance of the polymer–fullerene bulk heterojunction solar cells. In this model, by solving the drift–diffusion equations by considering the boundary condition and uniform potential energy, the effects of the active region thickness on the performance of P3HT/PCBM bulk heterojunction solar cell has been studied. By using this model, we were able to show that the thickness dependence of electrical characteristics is responsible for a reduction of the overall performance of the solar cells. Simulated current–voltage characteristics as a function of active layer thickness reveals relatively good agreement between the model’s predictions and published modeling and experimental reports.

Substrate-oriented nanorod scaffolds in polymer-fullerene bulk heterojunction solar cells.

The use of a p-type inorganic semiconductor to form a nanorod scaffold within a polymer-fullerene bulk heterojunction solar cell is reported. The performance of this cell is compared to those made of the commonly used n-type scaffold of ZnO, which has been reported many times in the literature. The scaffold is designed to improve charge-carrier collection by increased mobility in thicker samples. Observations show that generally the device performance shows a negative correlation to nanorod length. By using CuSCN as a p-type inorganic scaffold, a very similar trend is observed.

Charge generation in polymer-fullerene bulk-heterojunction solar cells.

Charge generation in organic solar cells is a fundamental yet heavily debated issue. This article gives a balanced review of different mechanisms proposed to explain efficient charge generation in polymer-fullerene bulk-heterojunction solar cells. We discuss the effect of charge-transfer states, excess energy, external electric field, temperature, disorder of the materials, and delocalisation of the charge carriers on charge generation. Although a general consensus has not been reached yet, recent findings, based on both steady-state and transient measurements, have significantly advanced our understanding of this process.

Predicting Vertical Phase Segregation in Polymer-Fullerene Bulk Heterojunction Solar Cells by Free Energy Analysis

Blends of poly(3-hexylthiophene) (P3HT) and C61-butyric acid methyl ester (PCBM) are widely used as a model system for bulk heterojunction active layers developed for solution-processable, flexible solar cells. In this work, vertical concentration profiles within the P3HT:PCBM active layer are predicted based on a thermodynamic analysis of the constituent materials and typical solvents. Surface energies of the active layer components and a common transport interlayer blend, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), are first extracted using contact angle measurements coupled with the acid-base model. From this data, intra- and interspecies interaction free energies are calculated, which reveal that the thermodynamically favored arrangement consists of a uniformly blended "bulk" structure capped with a P3HT-rich air interface and a slightly PCBM-rich buried interface. Although the "bulk" composition is solely determined by P3HT:PCBM ratio, composition near the buried interface is dependent on both the blend ratio and interaction free energy difference between solvated P3HT and PCBM deposition onto PEDOT:PSS. In contrast, the P3HT-rich overlayer is independent of processing conditions, allowing kinetic formation of a PCBM-rich sublayer during film casting due to limitations in long-range species diffusion. These thermodynamic calculations are experimentally validated by angle-resolved X-ray photoelectron spectroscopy (XPS) and low energy XPS depth profiling, which show that the actual composition profiles of the cast and annealed films closely match the predicted behavior. These experimentally derived profiles provide clear evidence that typical bulk heterojunction active layers are predominantly characterized by thermodynamically stable composition profiles. Furthermore, the predictive capabilities of the comprehensive free energy approach are demonstrated, which will enable investigation of structurally integrated devices and novel active layer systems including low band gap polymers, ternary systems, and small molecule blends.

The Importance of Fullerene Percolation in the Mixed Regions of Polymer–Fullerene Bulk Heterojunction Solar Cells

AbstractMost 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.

Use of benzothiadiazole–triphenylamine amorphous polymer for reproducible performance of polymer–fullerene bulk-heterojunction solar cells

An amorphous polymer, poly(BTD-TPA), which consists of benzothiadiazole and triarylamine units, can be successfully utilized to fabricate bulk heterojunction (BHJ) organic photovoltaics (OPVs), and the OPV performance can be demonstrated to be independent of the casting solvent or thermal annealing temperature. The OPV based on poly(BTD-TPA):PC70BM (1:4) that was fabricated using chloroform (boiling point of 61°C) and annealed at 60°C for 10min exhibited a power conversion efficiency (PCE) of 2.81% under simulated solar irradiation through an air mass of 1.5 at 100mWcm−2. On the other hand, the OPV fabricated using o-dichlorobenzene (boiling point of 181°C) and annealed at 110°C for 10min exhibited a PCE of 2.65%. Almost the same PCEs and incident photon to current conversion efficiencies (IPCEs) were obtained in both OPVs. The use of an amorphous film of poly(BTD-TPA) in the fabrication of OPVs offers great advantages over the use of a polycrystalline film of regioregular poly(3-hexylthiophene) (P3HT) in terms of high reproducibility of the OPV performance.

Direct and charge transfer state mediated photogeneration in polymer–fullerene bulk heterojunction solar cells

We investigated photogeneration yield and recombination dynamics in blends of poly(3-hexyl thiophene) (P3HT) and poly[2-methoxy-5 -(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) with [6,6]-phenyl-C61butyric acid methyl ester (PC61BM) by means of temperature dependent time delayed collection field measurements. In MDMO-PPV:PC61BM, we find a strongly field dependent polaron pair dissociation which can be attributed to geminate recombination in the device. Our findings are in good agreement with field dependent photoluminescence measurements published before, supporting a scenario of polaron pair dissociation via an intermediate charge transfer state. In contrast, polaron pair dissociation in P3HT:PC61BM shows only a very weak field dependence, indicating an almost field independent polaron pair dissociation or a direct photogeneration. Furthermore, we found Langevin recombination for MDMO-PPV:PC61BM and strongly reduced Langevin recombination for P3HT:PC61BM.

Charge transfer state in highly efficient polymer–fullerene bulk heterojunction solar cells

In recent years, steady improvements in organic photovoltaic (OPV) performance have been reported with power conversion efficiency (PCE) reaching 9%. Despite this rapid improvement, the mechanisms limiting the existing performance are not completely known; therefore a better understanding of the loss processes is necessary. In this respect a crucial role may be played by the charge transfer (CT) state, which is the intermediate state between the excitons and the fully dissociated charges. In this review article we outline the dynamics of this intermediate state in light of their influence on the photovoltaic performance, with central emphasis on highly efficient polymer–fullerene bulk heterojunction solar cells.

Bulk heterojunction solar cells based on a new low-band-gap polymer: Morphology and performance

Polymer-fullerene bulk heterojunction (BHJ) solar cells have gained much attention in the past few years due to their potential as a low cost photovoltaic technology. The state-of-the-art power conversion efficiency (PCE) has been improved to 7% regime by the recent development of thieno[3,4- b]thiophene based low-band-gap polymers. This paper reports a new low-band-gap polymer with alternating thieno[3,4- b]thiophene and benzo[1,2- b:4,5- b′]dithiophene units for applications in BHJ solar cells. By optimizing the nano-scale morphology with DIO (1,8-diiodooctane) additive, the PCE of BHJ solar cells based on this new polymer has been improved dramatically from 1.4% to 4.8%. The correlation between photovoltaic performance and film morphology has been established for this new polymer/fullerene system.

Anthracene‐containing PPE‐PPV copolymers: Effect of side‐chain nature and length on photophysical and photovoltaic properties

AbstractHigh‐molecular weight anthracene containing poly(p‐phenylene‐ethynylene)‐alt‐poly(p‐phenylene‐vinylene) (PPE‐PPV) copolymers bearing linear and/or branched alkyl side chains have been synthesized and investigated for use in polymer–fullerene bulk heterojunction solar cells. By variation of the nature and length of alkyl side chains the ordering in thin films could be tuned. Besides the basic photophysical characterization, small‐angle X‐ray scattering on extruded fibers and cyclovoltammetry measurements are reported. The photovoltaic characterization indicates that improved ordering due to linear side chains on the arylene–ethynylene segment as well as lower side‐chain volume fraction yield higher photocurrents. Power conversion efficiencies of nearly 2.5% are reported for the best devices with a polymer:fullerene composition of 1:1 by weight.magnified imageIV‐characteristics of partly optimized photovoltaic devices based on [6,6]‐phenyl C61 butyric acid methyl ester (PCBM) blends with a blending ratio of 1:1 under solar simulator illumination.

Effect of ZnCdTe-Alloyed Nanocrystals on Polymer-Fullerene Bulk Heterojunction Solar Cells.

The photovoltaic properties of solar cell based on the blends of poly[2-methoxy-5-(2-ethylhexoxy-1,4-phenylenevinylene) (MEH-PPV), fullerene (C60), and ZnCdTe-alloyed nanocrystals were investigated. Comparing the spectral response of photocurrent of the MEH-PPV:C60(+ZnCdTe) nanocomposite device with that of the devices based on MEH-PPV:C60and pristine MEH-PPV, one can find that the nanocomposite device exhibits an enhanced photocurrent. In comparing the composite devices with different ZnCdTe:[MEH-PPV + C60] weight ratios of 10 wt% (D1–1), 20 wt% (D1–2), 40 wt% (D1–3), and 70 wt% (D1–4), it was found that the device D1–3exhibits the best performance. The power conversion efficiency (η) is improved doubly compared with that of the MEH-PPV:C60device.

Enhancement in open circuit voltage induced by deep interface hole traps in polymer-fullerene bulk heterojunction solar cells

A significant increase in open circuit voltage (VOC) is obtained in the polymer-fullerene bulk heterojunction solar cell by using the e-beam deposited Al cathode. Compared with the device with the thermal evaporated Al cathode, an obvious enhancement of VOC from 596 to 664 mV is obtained, which makes the overall device power conversion efficiency improved by 12.4% (from 3.79% to 4.26%). Electrical characterizations suggest that the energetic particles in the e-beam deposition induce deep interface hole traps in the poly(3-hexylthiophene-2,5-diyl) (P3HT), while leaving the fullerene unaffected. The deep trapped holes near the P3HT/cathode interface can induce the image negative charges in the cathode and thus form “dipoles.” These dipoles lead to the lowering of the Al effective work function and cause the enhancement of VOC.