Fullerene Bulk Heterojunction Solar Cells Research Articles

Power losses in conventional and inverted non-polymeric donor:fullerene bulk heterojunction solar cells - The role of vertical phase separation in BQR:PC71BM blends

The performance of bulk heterojunction (BHJ) organic solar cells can be affected by a range of factors including the materials combination, processing solvent, post deposition annealing, and/or whether they are used in a conventional or inverted architecture. In this study we compared conventional and inverted BHJ solar cells composed of a non-polymeric donor (5 Z ,5′ Z )‐5,5'‐[(5‴,5‴''''‐{4,8‐bis[5‐(2‐ethylhexyl)‐4‐ n -hexylthiophen‐2‐yl]benzo[1,2‐b:4,5‐b']dithiophene‐2,6‐diyl}bis{3′,3'',3‴‐trihexyl‐[2,2':5′,2'':5'',2‴‐quaterthiophene]‐5‴,5‐diyl})bis(methanylylidene)]bis[3‐ n -hexyl‐2‐thioxothiazolidin‐4‐one] (BQR) and [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 71 BM) as the acceptor. It was found that the conventional device structure had power conversion efficiencies nearly two and a half times that of the inverted device, 9.0% versus 4.0%. Through a combination of Shockley equivalent circuit fitting, optical modelling, and light intensity dependent photocurrent measurements we identified that the origin of the power losses for the inverted architecture relative to the conventional device structure arose from a larger component of bimolecular recombination. Neutron reflectometry measurements showed that the origin of the larger bimolecular recombination losses for the inverted device was due to the PC 71 BM phase separating, with a PC 71 BM rich layer located near the anode reducing the hole extraction efficiency. • BQR and PC 71 BM conventional and inverted BHJ solar cells are compared. • The conventional device structure was two and a half times more efficient. • Increased bimolecular recombination identified as the origin of the power losses for the inverted architecture. • A PC 71 BM rich layer near the anode reduced the hole extraction efficiency in inverted device.

P3HT:PCBM polymer solar cells from a didactic perspective

Here, we studied the influence of pre- and post-thermal annealing on the performance of polymer:fullerene bulk heterojunction solar cells using the conventional architecture, comprising a conjugated polymer, namely, poly(3-hexylthiophene-2,5-diyl) (P3HT) and a fullerene derivative [6,6]-phenyl-C60-butyric acid methyl ester (PC60BM) as a photoactive layer. The non-annealed active layer device exhibited a power conversion efficiency of <1 % , which was significantly lower than the pre- and post-annealed devices. To investigate the impact of pre- and post thermal annealing on the natural morphological state of the polymer, regiorandom (P3HT-I) and regioregular (P3HT-II) type P3HT were compared in photoactive layers. In general, P3HT-I is amorphous, whereas P3HT-II is semi-crystalline. Changes in solar cell performance were associated with changes in carrier extraction efficiencies influenced by the annealing conditions. The charge photogeneration processes were investigated using spectroscopic techniques, including electroluminescence, steady-state, and time-resolved photoluminescence spectroscopy. Finally, to explore the morphological changes upon annealing, atomic force microscopy and electroluminescence imaging measurements were performed on films and solar cells, respectively.

Effect of fullerene substituent on low-light characteristics of polymer: fullerene bulk heterojunction solar cells

A halogen-free solvent 1,2,4-trimethylbenzene dissolves both unmodified fullerenes and conjugated polymers such as PTB7-Th. This unique feature enables the study on the effect of the substituent of fullerene in polymer:fullerene bulk heterojunction solar cells under low-light illumination. Although the power conversion efficiency (PCE) of the PTB7-Th:C70 solar cell was higher than that of the PTB7-Th:C70-PCBM solar cell under one sun illumination, the latter showed higher PCE than the former under 10−3 sun illumination. This result comes from the fact that C70-PCBM yields higher open-circuit voltage (VOC) at one sun and smaller dependence of VOC on illumination light intensity than C70.

Disentanglement of Degradation Mechanisms by Analyzing Aging Dynamics of Environmentally Friendly Processed Polymer Solar Cells

Lifecycle assessments suggest preventing halogenated solvents or solvent additives for environmentally friendly polymer solar cells. Thus, the active layers of polymer:fullerene bulk heterojunction solar cells based on poly{[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl]‐alt‐[2‐(20‐ethyl‐hexanoyl)‐thieno[3,4‐b]thiophen‐4,6‐diyl]} (PBDTTT‐CT) and the fullerene derivative [6,6]‐phenyl‐C70‐butyric acid methyl ester (PC70BM) are cast from m‐xylene solutions. Ortho‐vanilline is used as a nonhazardous and nontoxic solvent additive. Completed photovoltaic devices are subjected to accelerated laboratory weathering tests. Photovoltaic parameters are periodically obtained from current–voltage recordings of the solar cells twice an hour under well‐defined aging conditions following the International Summit on Organic Photovoltaic Stability (ISOS) protocols. An analysis of aging kinetics reveals the superposition of two individual degradation mechanisms, of which one is assigned to continued intermixing and the other one to the formation of a blocking layer by interfacial segregation.

Influence of binary additives into the solvent for preparation of polymer and fullerene bulk heterojunction solar cells by convective deposition method

Abstract Binary additives of 1,8-diiodooctane (DIO) and 1,3,5-trichlorobenzene (135-TCB) were utilized for preparation of poly[4,8-bis(5-(2-ethylhexyl) thiophen-2-yl)benzo[1,2-b; 4,5-b']dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl)] (PTB7-Th) and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) films for bulk heterojunction (BHJ) solar cells. The addition of binary additives of DIO 3.0 vol% + 135-TCB 2.1 vol% into PTB7-Th:PC71BM films exhibited nano-sized of PTB7-Th networks homogeneous distribution and smaller sizes than the film without additive and with DIO 3.0 vol%. The out-of-plane orientation of PTB7-Th:PC71BM films were improved by addition of binary additives and 135-TCB. A rectification ratio of the BHJ solar cells were improved by using binary additives of DIO 3.0 vol% + 135-TCB 2.1 vol%. As a consequence, fill factor (FF) and power conversion efficiency (PCE) of the device with binary additives increased up to 0.69 and 7.4% as compared with FF (0.66) and PCE (6.9%) of the device with DIO 3.0 vol%. The external quantum efficiency the device with binary additives was enhanced in the region from 550 nm to 750 nm as compared with that of the device with DIO 3.0 vol%. This result was probably caused by the improvement of PTB7-Th orientation, and phase separation between the PTB7-Th and PC71BM.

Balance Between Light Absorption and Recombination Losses in Solution‐Processed Small Molecule Solar Cells with Normal or Inverted Structures

AbstractComparison of the photovoltaic properties of F3:fullerene bulk heterojunction solar cells (where F3 is a donor molecule of intermediate dimensions) with normal and inverted structures as a function of photoactive layer thickness is carried out by using optical modeling and light‐dependent photoelectrical characterization. The larger short circuit current of inverted devices can be explained by higher light absorption in the active layer, relative to normal devices. However, worse charge extraction conditions and trap‐assisted recombination, in the bulk heterojunction blend in inverted devices, give rise to larger nongeminate recombination losses and an opposite thickness dependence of the short circuit current and fill factor than what is observed in counterparts with the conventional device architecture.

Roles of Interfacial Tension in Regulating Internal Organization of Low Bandgap Polymer Bulk Heterojunction Solar Cells by Polymer Additives

AbstractThe role of a tertiary polymer‐based additive is investigated in increasing the efficiency of inverted low bandgap polymer:fullerene bulk heterojunction (BHJ) solar cells. Charge separation in polymer BHJ solar cells relies on the phase separation between electron accepting fullerene derivatives and photoactive polymers. Proper distribution of individual phases of suitable crystallinities within the active layer is a key factor for efficient charge transport/extraction and high photovoltaic performance. Here, it is demonstrated that the minor addition of a tertiary amorphous polymer, polystyrene (PS), with optimized molecular weights can increase the overall photovoltaic efficiency of poly[N‐9′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)]:phenyl‐C61butyric acid methyl ester (PCDTBT:PCBM) inverted BHJ solar cells, through the interfacial‐tension‐driven increase in crystallinities of photoactive phases and redistribution of PCBM molecules away from the top hole‐collecting anode interface. Complementary studies correlating polymer interfacial tension, blend internal structure, charge transport, and photovoltaic characteristics show that tertiary, high molecular‐weight polymers can serve as effective additives for improving the performance of low bandgap polymer solar cells.

Importance of Solvent Removal Rate on the Morphology and Device Performance of Organic Photovoltaics with Solvent Annealing.

Solvent vapor annealing has been widely used in organic photovoltaics (OPV) to tune the morphology of bulk heterojunction active layer for the improvement of device performance. Unfortunately, the effect of solvent removal rate (SRR) after solvent annealing, which is one of the key factors that impact resultant morphology, on the morphology and device performance of OPV has never been reported. In this work, the nanoscale morphology of small molecule (SM):fullerene bulk heterojunction (BHJ) solar cell from different SRRs after solvent annealing was examined by small-angle neutron scattering and grazing incidence X-ray scattering. The results clearly demonstrate that the nanoscale morphology of SM:fullerene BHJ especially fullerene phase separation and concentration of fullerene in noncrystalline SM was significantly impacted by the SRR. The enhanced fullerene phase separation was found with a decrease of SRR, while the crystallinity and molecular packing of SM remained unchanged. Correlation to device performance shows that the balance between pure fullerene phase and mixing phase of SM and fullerene is crucial for the optimization of morphology and enhancement of device performance. Moreover, the specific interfacial area between pure fullerene phase and mixing phase is crucial for the electron transport and thus device performance. More importantly, this finding would provide a more careful and precise control of morphology of SM:fullerene BHJ and offers a guideline for further improvement of device performance with solvent annealing.

Boosting the photovoltaic thermal stability of fullerene bulk heterojunction solar cells through charge transfer interactions

Charge transfer interaction of a donor polymer with an appropriate 9-fluorenylidene malononitrile derivative in the active layer leads to profoundly enhanced thermal stability of fullerene-based bulk heterojunction organic solar cells.

Orthogonal solubility in fully conjugated donor-acceptor block copolymers: Compatibilizers for polymer/fullerene bulk-heterojunction solar cells

Donor-acceptor (D-A) type fully conjugated block copolymer systems have been rarely reported due to the challenges in synthetic approaches to prepare well-defined low-polydispersity products. In this work, fully conjugated block copolymers are synthesized in a one-pot reaction through Stille coupling polycondensation, by utilizing the end-functional polymer copolymerization method. End-functional P3HT are copolymerized with AA (2,7-dibromo-9-(heptadecan-9-yl)-9H-carbazole) and BB (4,7-bis(5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole, TBT) type monomers, respectively. The orthogonal solubility between the very soluble P3HT donor and the insoluble PCDTBT acceptor block improves the purity of block copolymers as well as distinct nano-scale phase-separation compared with other reports on miscibility of donor and acceptor polymer block. Further purification via preparative GPC is carried out to remove the excess of unreacted P3HT and free PCDTBT as well as to achieve low polydispersity of block copolymers. The chemical structure of the P3HT-b-PCDTBT block copolymers are verified via 1H-NMR, and further confirmed by FTIR spectra. The block copolymer shows broad absorption and moderate optical band gap of 1.8 eV. Furthermore, the fully conjugated block copolymer films exhibit significant fine structures, much smoother film morphology compared to P3HT/PCDTBT polymer blends. By adding a small amount of block copolymer P3HT-b-PCDTBT as a compatibilizer into the bulk-heterojunction of P3HT:PC61BM blends, polymer solar cells with an 8% increase of short circuit current (J sc and 10% increase of power conversion efficiency (PCE) are achieved owing to the improvement of the active-layer film morphology. To the best of our knowledge, this is the first report on donor-acceptor type fully conjugated block copolymer as an effective ternary additive in polymer: fullerene bulk heterojunction solar cells.

Molecular Engineering of Conjugated Polymers for Solar Cells: An Updated Report.

The device efficiency of polymer:fullerene bulk heterojunction solar cells has recently surpassed 11%, as a result of synergistic efforts among chemists, physicists, and engineers. Since polymers are unequivocally the "heart" of this emerging technology, their design and synthesis have consistently played the key role in the device efficiency enhancement. In this article, the first focus is a discussion on molecular engineering (e.g., backbone, side chains, and substituents), then the discussion moves on to polymer engineering (e.g., molecular weight). Examples are primarily selected from the authors contributions; yet other significant discoveries/developments are also included to put the discussion in a broader context. Given that the synthesis, morphology, and device physics are inherently related in explaining the measured device output parameters (Jsc , Voc and FF), we will attempt to apply an integrated and comprehensive approach (synthesis, morphology, and device physics) to elucidate the fundamental, underlying principles that govern the device characteristics, in particular, in the context of disclosing structure-property correlations. Such correlations are crucial to the design and synthesis of next generation materials to further improve the device efficiency.

Optimized phase separation in low-bandgap polymer:fullerene bulk heterojunction solar cells with criteria of solvent additives

We investigate a correlation between the type of solvent additives (SAs) with specific criteria such as aromatic additives (AAs) and non-aromatic additives (NAAs) and phase separation in the bulk heterojunction (BHJ) films comprising low-band gap polymer and fullerene derivatives. When AAs are used as SAs, the geometrical structures (π-π and lamellar stacking) of aggregated polymer chains do not significantly change. However, NAAs increase the lamellar stacking distance through a strong interaction with non-aromatic segments of polymers. Therefore, a well-phase separated BHJ morphology with the finer fibrils is developed, thereby leading to balanced charge mobilities and a reduced charge recombination in BHJ solar cells. Finally, the optimized solar cell exhibits a high power conversion efficiency of 7.9%.

Impact of Fullerene Structure on Nanoscale Morphology and Miscibility and Correlation of Performance on Small Molecules: Fullerene Solar Cell

This manuscript reports the impact of fullerene structure on the morphology and miscibility of small molecules via a fullerene bulk heterojunction solar cell. The small angle neutron scattering and neutron reflectometry measurements were analyzed to provide quantifiable measures of the morphology of the resultant mixtures, offering miscibility, domain sizes, interfacial area between the small molecule and fullerene, and depth profiles in the mixtures. These results indicate that the bis-adduct fullerenes exhibit lower miscibility in small molecules. Correlation of miscibility and morphology to photovoltaic properties indicates that small molecule/fullerene miscibility is crucial to rationally optimize the design of fullerenes for use in small molecule organic photovoltaics. A higher open circuit voltage was obtained for bis-adduct fullerene devices which, however, does not translate to an increased power conversion efficiency. This decrease in performance is associated with the lower miscibility of bis-fu...

Solution-processable MoOx nanocrystals enable highly efficient reflective and semitransparent polymer solar cells

Solution-manufacturing of organic solar cells with best-in-class power conversion efficiency (PCE) will require all layers to be solution-coated without compromising solar cell performance. To date, the hole transporting layer (HTL) deposited on top of the organic bulk heterojunction layer in the inverted architecture is most commonly an ultrathin (<10nm) metal oxide layer prepared by vacuum-deposition. Here, we show that an alcohol-based nanocrystalline MoOx suspension with carefully controlled nanocrystal (NC) size can yield state of the art reflective and semitransparent solar cells. Using NCs smaller than the target HTL thickness (∼10nm) can yield compact, pinhole-free films which result in highly efficient polymer:fullerene bulk heterojunction (BHJ) solar cells with PCE=9.5%. The solution processed HTL is shown to achieve performance parity with vacuum-evaporated HTLs for several polymer:fullerene combinations and is even shown to work as hole injection layer in polymer light emitting diodes (PLED). We also demonstrate that larger MoOx NCs (30–50nm) successfully composite MoOx with Ag nanowires (NW) to form a highly conducting, transparent top anode with exceptional contact properties. This yields state-of-the-art semitransparent polymer: fullerene solar cells with PCE of 6.5% and overall transmission >30%. The remarkable performance of reflective and semitransparent OPVs is due to the uncommonly high fill factors achieved using a carefully designed strategy for implementation of MoOx nanocrystals as HTL materials.

Open-Circuit Voltage in Inverted Polycarbazole:Fullerene Bulk Heterojunction Solar Cells

The correlation between cathode work function and open-circuit voltages ( V oc) in inverted polycarbazole:fullerene (PCDTBT:PC70BM) bulk-heterojunction solar cells has been investigated by postannealing of indium tin oxide (ITO) electrodes. The ITO function is seen to change from 4.2 to 4.5 eV without the need to insert additional interfacial layers with annealing temperature up to 400 °C. The best device performance was obtained at room temperature with the ITO work function of 4.2 eV with a V oc of 0.89 eV, a J sc of 8.06 mA·cm-2, a fill factor (FF) of 64.70%, and a power conversion efficiency of 4.62%. Together with previously published results, we are able to extract two regimes of V oc dependence on the cathode work function: first, a linear relationship when the cathode work function exceeds the lowest unoccupied molecular orbital (LUMO) of PCBM and, second, a constant V oc regime when the ITO work function reduces below the LUMO level. These results provide general guidelines for the cathode contact design in inverted polymer solar cells.

Structure-induced resonant tail-state regime absorption in polymer: fullerene bulk-heterojunction solar cells

In this work, we present resonant tail-state regime absorption enhanced organic photovoltaics. We combine periodically structured ${\mathrm{TiO}}_{2}$ bottom electrodes with P3HT-PCBM bulk-heterojunction solar cells in an inverted device configuration. The wavelength-scale patterns are transferred to the electron-selective bottom electrodes via direct laser interference patterning, a fast method compatible with roll-to-roll processing. Spectroscopic and optoelectronic device measurements suggest polarization-dependent absorption enhancement along with photocurrent generation unambiguously originating from the population of tail states. We discuss the effects underlying these absorption patterns with the help of electromagnetic simulations using the discontinuous Galerkin time domain method. For this, we focus on the total absorption spectra along with spatially resolved power loss densities. Our simulations stress the tunability of the absorption resonances towards arbitrary wavelength regions.

(Invited) The Effect of Increased Dielectric Screening on Bimolecular Recombination of Photogenerated Charges in Polymer:Fullerene Bulk Heterojunctions

Bimolecular recombination studies reveal a one order magnitude slower bimolecular recombination when normalized to charge mobility in a polymer:fullerene bulk heterojunction solar cell with a dielectric constant of seven. The techniques used were charge extraction using nanosecond switch combined with charge extraction by linearly increasing voltage and integral mode time of flight measurements. The measured high dielectric constant in the polymer:fullerene blend is due to the exceptionally high dielectric constant (16.7) of the conjugated polymer donor component employed. This value, indicative of increased dielectric screening of charges compared to most organic solar cell materials with a typical dielectric constant around 4,is one of the highest reported to date. The slower bimolecular recombination mentioned above is compared to well established poly(3-hexylthiophene) and low badngap polymer PCPDTBT:fullerene heterojunctions, and is explained by the smaller coulomb capture radius in a diffusion controlled recombination model. Longer charge carrier lifetimes together with a larger charge mobility in the high dielectric constant bulk heterojunctions leads to larger fill factors (0.6) and excellent photovoltaic performance in solar cells using large active layer thicknesses approaching 300 nm. Ultimately, increasing the dielectic constant of organic photoactive laterials to and beyond 10 is expected to bridge the performance gap between inorganic and organic solar cells.

Locally resolved large scale phase separation in polymer:fullerene blends

Large scale phase separation in polymer:fullerene bulk heterojunction solar cells investigated by electroluminescence imaging (ELI) and light-beam induced current (LBIC) measurements.

Real‐Time Investigation of Intercalation and Structure Evolution in Printed Polymer:Fullerene Bulk Heterojunction Thin Films

The complex intermixing morphology is critical for the performance of the nanostructured polymer:fullerene bulk heterojunction (BHJ) solar cells. Here, time resolved in situ grazing incidence X‐ray diffraction and grazing incidence small angle X‐ray scattering are used to track the structure formation of BHJ thin films formed from the donor polymer poly(2,5‐bis(3‐hexadecylthiophen‐2‐yl)thieno[3,2‐b]thiophene) with different fullerene derivative acceptors. The formation of stable bimolecular crystals through the intercalation of fullerene molecules between the side chains of polymer crystallites is investigated. Such systems exhibit more efficient exciton dissociation but lower photo‐conductance and faster decay of charges. On the basis of the experimental observations, intercalation obviously takes place before or with the formation of the crystalline polymer domains. It results in more stable structures whose volume remains constant upon further drying. Three distinct periods of drying are observed and the formation of unidimensional fullerene channels along the π‐stacking direction of polymer crystallites is confirmed.

Significant Stability Enhancement in High-Efficiency Polymer:Fullerene Bulk Heterojunction Solar Cells by Blocking Ultraviolet Photons from Solar Light.

Achievement of extremely high stability for inverted‐type polymer:fullerene solar cells is reported, which have bulk heterojunction (BHJ) layers consisting of poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3‐fluorothieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th) and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM), by employing UV‐cut filter (UCF) that is mounted on the front of glass substrates. The UCF can block most of UV photons below 403 nm at the expense of ≈20% reduction in the total intensity of solar light. Results show that the PTB7‐Th:PC71BM solar cell with UCF exhibits extremely slow decay in power conversion efficiency (PCE) but a rapidly decayed PCE is measured for the device without UCF. The poor device stability without UCF is ascribed to the oxidative degradation of constituent materials in the BHJ layers, which give rise to the formation of PC71BM aggregates, as measured with high resolution and scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The device stability cannot be improved by simply inserting poly(ethylene imine) (PEI) interfacial layer without UCF, whereas the lifetime of the PEI‐inserted PTB7‐Th:PC71BM solar cells is significantly enhanced when UCF is attached.