Bulk Heterojunction Organic Solar Cells Research Articles

Regulation of photoinduced charge transfer in all-small-molecule organic solar cells through the synergistic effect of external electric field and solvent

The donor (BTR-Cl) and acceptor (BTP-FCl-FCl) have well-defined small molecule properties and excellent repeatability, and they can form charge transfer complexes with a wide spectral absorption range. Using density functional theory (DFT), we simulate the photoinduced charge transfer of bulk-heterojunction (BHJ) organic solar cell (OSC) materials modulated by the external electric field (Fext) at the microscopic level. The excited-state properties, reorganization energy (λ), Gibbs free energy (ΔG), electron coupling matrix elements (VDA) and intermolecular charge transfer (ICT) rate dependent on Fext are systematically analyzed. The results manifest that Fext has apparent positive regulation on the charge separation rate (KCS), and VDA is the main factor affecting KCS. The synergistic effect of solvent and Fext on charge transfer process is further investigated. It is found that the charge transfer rate in solvent is lower than that in solvent-free conditions, and the charge transfer rate in chlorobenzene (CB) solvent does not change significantly under the control of Fext. At the same time, Fext has a positive effect on the charge transfer rate in tetrahydrofuran (THF) solvent. Considering the charge transfer rate under different solvents and Fext intensities, it is found that the solvent and Fext play an essential role in determining the KCS and charge recombination rate (KCR).

Hybrid Steroid‐[60]Fullerene as n‐Type Material for Organic Photovoltaics

AbstractFullerene derivatives have been used as electron acceptor and transport materials in organic photovoltaics as well as in perovskite solar cells. Among them, [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) has been one of the most widely used, in combination with poly‐3‐hexylthiophene (P3HT) as an electron donor semiconducting polymer, for the fabrication of organic bulk heterojunction solar cells (BHJ‐OSC). In this work, a steroid‐fullerene hybrid was synthesized through the Bingel–Hirsch reaction to compare its properties with PC61BM as the reference structure. Different spectroscopic techniques were employed to characterize the new fullerene derivative, namely 1D and 2D nuclear magnetic resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and high‐resolution mass spectrometry (HRMS). In addition, thermogravimetric analysis (TGA), and cyclic voltammetry were also performed. The characterization was completed by transmission electron microscopy (TEM), which explore the hybrid‘s morphology, where the presence of the steroid moiety increases the solubility of the fullerene material. DFT/PBE−D3(BJ)/6‐311G(d,p) calculations for both the steroid‐fullerene hybrid and PC61BM allowed to obtain geometry optimizations and electronic structure data. A comparative study to analyze the nature of the electronic properties of the synthesized steroid‐[60]fullerene hybrid and PC61BM with an oligomer of ten thiophene units, used in the active layer of organic solar cells, was carried out. Electron density maps using the [CIS|CNDOL/21] approach illustrate the photoexcitation of the donor followed by an electron‐charge transfer to the acceptor fullerene.

Selectively Modulating Componential Morphologies of Bulk Heterojunction Organic Solar Cells.

Achieving precise control over the nanoscale morphology of bulk heterojunction films presents a significant challenge for the conventional post-treatments employed in organic solar cells (OSCs). In this study, a near-infrared photon-assisted annealing (NPA) strategy is developed for fabricating high-performance OSCs under mild processing conditions. It is revealed a top NIR light illumination, together with the bottom heating, enables the selective tuning of the molecular arrangement and assembly of narrow bandgap acceptors in polymer networks to achieve optimal morphologies, as well as the acceptor-rich top surface of active layers. The derived OSCs exhibit a remarkable power conversion efficiency (PCE) of 19.25%, representing one of the highest PCEs for the reported binary OSCs so far. Moreover, via the NPA strategy, it has succeeded in accessing top-illuminated flexible OSCs using thermolabile polyethylene terephthalate from mineral water bottles, displaying excellent mechanical stabilities. Overall, this work will hold the potential to develop organic solar cells under mild processing with various substrates.

Fine-Tuned Active Layer Morphology for Bulk Heterojunction Organic Solar Cells with Indene-C60 Bisadduct as a Third Component.

Active layer morphology is of vital importance for the photovoltaic performance of organic solar cells (OSCs). As fullerene derivatives and nonfullerene acceptors are highly complementary in many aspects, fullerene derivatives as a third component in nonfullerene OSCs could tune the blend morphology and improve the power conversion efficiency (PCE). Relative to PCBM, the indene-C60 bisadduct (IC60BA) as the third component in nonfullerene binary OSCs has not been extensively studied. Here, the fullerene derivative IC60BA is introduced into the PTZ1:IDIC blend system to finely tune the active layer morphology. Although the addition of IC60BA reduced the film absorption in the visible region and weakened the crystallinity, the more symmetric charge transport property, smaller domain size, and higher domain purity led to improved photovoltaic performance. This study indicates that IC60BA is a promising candidate to finely tune the morphology for achieving highly efficient OSCs.

Enhancing the Efficiency of PM6:Y6 Bulk-Heterojunction Organic Solar Cells through SCAPS Simulation Optimization

Organic solar cell (OSC) is becoming a point of attraction in the solar cell industry due to their benefits, such as light weight, flexibility, low cost, semi-transparency, and easy fabricating methods. By replacing fullerene with non-fullerene acceptors like Y6, ITIC, PCBM, and ICBA, the power conversion efficiency (PCE) of OSCs has surpassed the 15% benchmark. Here, the proposed OSC structure includes an ITO front contact electrode, SnO2 electron transport layer (ETL), PM6:Y6 active layer, Cu2O hole transport layer (HTL), and Ag back contact electrode. Systematic numerical simulation of the above proposed OSC has been performed using a solar cell capacitance simulator (SCAPS)-1D (Version 3.3.09). The device improvement analysis has been carried out in steps by analyzing the ETL-HTL effect, selecting the optimum thickness of the active layer, and the optimum value of defect density. In the first step, a PCE of 24.60% was achieved, followed by an improvement to 27.55% with the optimized defect density value. The best PCE of 27.74% was achieved in the third step with an optimized active layer thickness, leading to high fill factor (80.56%), open-circuit voltage (0.9461 V), and short-circuit current density (36.188 mA/cm2). These simulated results promote an in-depth understanding of the optical and electronic properties of PM6:Y6 blend-based OSC and show the potential of NFA-BHJ OSCs as promising candidates for solar cells in the near future.

The critical role of temperature-dependent mobilities in determining the open-circuit voltage of bulk-heterojunction organic solar cells

While solution-processed bulk-heterojunction organic solar cells (OSCs) continue to attract attention as their efficiencies approach 20%, the physical origin of the non-radiative energy loss in OSCs remains under debate. Understanding the temperature dependence of open-circuit voltage (VOC) is thus important because it provides unique insights into the origin of energy loss. Herein, we simulate the VOC vs T relation of PTB7-Th:PC71BM bulk-heterojunction OSCs within the range of 160–295 K by incorporating experimentally measured temperature-dependent mobilities into the drift-diffusion model, assuming bimolecular recombination as the primary recombination mechanism. Significantly, we find that the temperature dependence of VOC can only be correctly reproduced by the model when the temperature dependence of the carrier mobilities is taken into account. The effect of the Langevin reduction coefficient on the temperature dependence of VOC is also investigated.

Isomeric Effect of a π Bridge in an IDT-Based Nonfused Electron Photovoltaic Acceptor.

A pair of isomers, IDT-BOF containing S⋅⋅⋅O/F⋅⋅⋅H noncovalently configurational locks and IDT-BFO containing F⋅⋅⋅H/O⋅⋅⋅H noncovalently configurational locks, with an acceptor-π-donor-π-acceptor (A-π-D-π-A) structure have been designed and synthesized by choosing 4,9-dihydro-s-indaceno[1,2-b : 5,6-b']dithiophene (IDT) as the D unit, an F/n-hexyloxy substituted phenyl ring as π bridge, and 3-(dicyanomethylidene)indan-1-one as the A unit. Owing to the S⋅⋅⋅O/F⋅⋅⋅H or F⋅⋅⋅H/O⋅⋅⋅H noncovalently configurational locks, both IDT-BOF and IDT-BFO have a completely planar structure. IDT-BOF exhibits a similar LUMO to IDT-BFO, but higher HOMO energy levels, leading to a smaller optical bandgap and red-shifted absorption. However, IDT-BOF-based bulk-heterojunction organic solar cells (BHJ-OSCs) coupled with PBDB-T, and PCE-10 as donor materials both exhibited a lower PCE than that of IDT-BFO (PBDB-T: 5.2 vs. 6.1 %; PCE-10: 1.7 vs. 3.2 %). Comprehensively comparing and investigating IDT-BOF : PBDB-T and IDT-BFO : PBDB-T OSCs suggested that the large phase separation and serious charge recombination of IDT-BOF-based OSCs contributed to its lower power conversion efficiency. Importantly, ternary solar cells based on PBDB-T : Y5 as control devices with an additional 10 % IDT-BFO exhibited a 5 % enhancement in the PCE compared to the control device (14.3 vs. 13.46 %).

PC71BM as Morphology Regulator for Highly Efficient Ternary Organic Solar Cells with Bulk Heterojunction or Layer-by-Layer Configuration.

The ternary strategy is one of the effective methods to regulate the morphology of the active layer in organic solar cells (OSCs). In this work, the ternary OSCs with bulk heterojunction (BHJ) or layer-by-layer (LbL) active layers are prepared by using the polymer donor PM6 and the non-fullerene acceptor L8-BO as the main system and the fullerene acceptor PC71BM as the third component. The power conversion efficiencies (PCEs) of BHJ OSCs and LbL OSCs are increased from 17.10% to 18.02% and from 17.20% to 18.20% by introducing PC71BM into the binary active layer, respectively. The in situ UV-vis absorption spectra indicate that the molecular aggregation and crystallization process can be prolonged by introducing PC71BM into the PM6:L8-BO or PM6/L8-BO active layer. The molecular orientation and molecular crystallinity in the active layer are optimized by introducing the PC71BM into the binary BHJ or LbL active layers, which can be confirmed by the experimental results of grazing incidence wide-angle X-ray scattering. This study demonstrates that the third component PC71BM can be used as a morphology regulator to regulate the morphology of BHJ or LbL active layers, thus effectively improving the performance of BHJ and LbL OSCs.

Thermally‐Induced Degradation in PM6:Y6‐Based Bulk Heterojunction Organic Solar Cells

AbstractThermally induced degradation of organic photovoltaic devices hinders the commercialization of this emerging PV technology. Thus, a precise understanding of the origin of thermal device instability, as well as identifying strategies to circumvent degradation is of utmost importance. Here, it investigates thermally‐induced degradation of state‐of‐the‐art PBDB‐T‐2F (PM6):BTP (Y6) bulk heterojunction solar cells at different temperatures and reveal changes of their optical properties, photophysics, and morphology. The open‐circuit voltage and fill factor of thermally degraded devices are limited by dissociation and charge collection efficiency differences, while the short‐circuit current density is only slightly affected. Energy‐resolved electrochemical impedance spectroscopy measurements reveal that thermally degraded samples exhibit a higher energy barrier for the charge‐transfer state to charge‐separated state conversion. Furthermore, the field dependence of charge generation, recombination, and extraction are studied by time‐delayed collection field and transient photocurrent and photovoltage experiments, indicating significant bimolecular recombination limits device performance. Finally, coupled optical‐electrical device simulations are conducted to fit the devices’ current‐voltage characteristics, enabling us to find useful correlations between optical and electrical properties of the active layers and device performance parameters.

Dependence of the characteristics of organic solar cells on cathode polymer interface

Increasing energy assumption and rising energy prices in the world forces to look for energy alternatives, one of the most promising is the photovoltaic energy. Solar cells made from organic materials are particularly attractive because they are relatively easy to produce, structurally flexible, and can be applied to large areas at low cost. Fill Factor is a more sensitive parameter compared to open-circuit voltage (Voc) and shortcircuits current density (Jsc). This FF depends also on the thickness of the active-polymer layer, on the morphology of the cathode-polymer interface and on temperature. In this article, we study the dependence of fill factor (FF) on different parameters in organic bulk heterojunction solar cells.

One-pot synthesis of PbS quantum dots decorated with graphene for assisting charge carriers transport in bulk heterojunction solar cells

The photocurrent of organic bulk heterojunction (BHJ) solar cells is improved by the introduction of PbS QDs decorated with graphene (G) in their photoactive layer. The insertion of PbS QDs:G is observed to improve the exciton dissociation and charge transfer paths. PbS QDs and PbS QDs:G are synthesized by the hot-injection method. The mechanism of PbS QDs formation and the role of their growth on G sheets are explained. Incorporation of PbS QDs and PbS QDs:G into the active layer of BHJ solar cells composed of poly (3-hexylthiophene-2,5-diyl) (El-Menyawy et al., 2019; El-Menyawy et al., 2019) [6,6]:-phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) is found to improve their performance. The solar cells composed of pristine P3HT:PC61BM active layer are found to deliver a photoelectrical conversion efficiency (PCE) of 2.02 %. By inserting PbS QDs in the active layer, the PCE value is increased up to 2.44 %. Further increase in PCE to 3.27 % is explored by the inclusion of PbS QDs:G in the organic active layer. The ternary composites (P3HT:PbS QDs:G:PC61BM) have supreme characteristics, and are recommended for optoelectronic applications.

Enhancing photovoltaic performance: Exploring quinoxaline donors in conjunction with Y6 and BTP-4Br small molecule acceptors via DFT calculations

Bulk heterojunction organic solar cells have helped increase power conversion efficiency and characterize and analyze possible factors influencing the improvement of solar-electrical energy conversion. Research in the last decades showed the link between the molecular electronic structure and the morphology of the photoactive layer with the photovoltaic process. Furthermore, both distinctive features are linked to halogenation in the acceptor and donor molecules that constitute the photoactive layer. It is worth mentioning that more attention has been paid to acceptor molecules compared to donors, particularly from the point of view of quantum mechanical calculations. Due to this, in the present work, a systematic study is carried out through density functional theory on the variation of halogenation in donors PBQ5 and PBQ6, which demonstrated outstanding efficiency when introduced into the photoactive layer of an organic solar cell complexed with the Y6 acceptor. Firstly, the correspondence of the electronic structure of both donors with higher efficiency of PBQ6, compared to PBQ5, stands out. An example is the lower position of the HOMO frontier molecular orbital of PBQ6, which predicts a higher open-circuit voltage, just as the experiment shows. Likewise, a smaller gap between the HOMO and LUMO orbitals in PBQ6 proposes an increase in the short-circuit current. The proposal of halogen exchange yields results of significant interest. Theoretical approximations of crucial parameters such as Voc, Jsc, and FF reveal promising avenues for enhancing power conversion efficiency through strategic adjustments in halogenation. In closing, despite the multitude of factors at play in the photoconversion of an organic solar cell—a complexity that poses challenges within the realm of computational theoretical studies—we consider that the uncovered findings can provide valuable insights into the determinants to be manipulated in terms of electronic structure, thereby paving the way for achieving heightened efficiency in photoconversion.

Photogeneration and excitons distribution function in organic bulk heterojunction solar cells

In this work, the excitons distribution function in organic bulk heterojunction solar cells, at a depth z has been determined from solving the charge continuity equation, by exploiting the Laplace transform with an appropriate boundary conditions. Next, the influence of the electron-hole pair separation distance on the excitons dissociation probability, the internal quantum efficiency and the binding energy, has been studied. The simulated results show that the probability density of the carriers photogenerated depend on the generation rate, excitons dissociation and the charge carriers in the cells. The potential improvement of the internal quantum efficiency of charge generation depends on electron-hole pair separation distance, the excitons dissociation probability into free charges and depends strongly on the optical absorption of the photons in the active layer.

Modeling of the photophysical and photovoltaic properties of an active layer based on the organic composite poly(2‐methoxy‐5‐(2‐ethyl‐hexyloxy)‐1,4‐phenylene‐vinylene) (MEH‐PPV)–poly(3‐hexylthiophene) (P3HT): (6,6)‐phenyl C61 butyric acid methyl ester (PCBM)

AbstractIn this work, two different composite architectures have been investigated. These materials are formed by the block and ramified MEHPPV‐P3HT copolymers mixing with the PCBM. Density Functional Theory (DFT) and Time‐Dependent Density Functional Theory (TD‐DFT) calculation methods have been used to simulate the properties of the photo‐physical and photovoltaic material. The results show that adding the PCBM decreases the HOMO–LUMO gap energy to approximately 1.4 eV compared to the basic copolymers. This reduction implies a higher charge transfer between the donor and acceptor materials. Therefore, these composites can be implemented as an active layer in bulk heterojunction organic solar cells. Furthermore, the coupling between the polymers MEH‐PPV and P3HT improves their performance order by 5.2%.

Optimization and Efficiency Enhancement of Modified Polymer Solar Cells.

In this study, an organic bulk heterojunction (BHJ) solar cell with a spiro OMeTAD as a hole transport layer (HTL) and a PDINO as an electron transport layer (ETL) was simulated through the one-dimensional solar capacitance simulator (SCAPS-1D) software to examine the performance of this type of organic polymer thin-film solar cell. As an active layer, a blend of polymer donor PBDB-T and non-fullerene acceptor ITIC-OE was used. Numerical simulation was performed by varying the thickness of the HTL and the active layer. Firstly, the HTL layer thickness was optimized to 50 nm; after that, the active-layer thickness was varied up to 80 nm. The results of these simulations demonstrated that the HTL thickness has rather little impact on efficiency while the active-layer thickness improves efficiency significantly. The temperature effect on the performance of the solar cells was considered by simulations performed for temperatures from 300 to 400 K; the efficiency of the solar cell decreased with increasing temperature. Generally, polymer films are usually full of traps and defects; the density of the defect (Nt) value was also introduced to the simulation, and it was confirmed that with the increase in defect density (Nt), the efficiency of the solar cell decreases. After thickness, temperature and defect density optimization, a reflective coating was also applied to the cell. It turned out that by introducing the reflective coating to the back side of the solar cell, the efficiency increased by 2.5%. Additionally, the positive effects of HTL and ETL doping on the efficiency of this type of solar cells were demonstrated.

Thiadiazole based π-conjugated small molecule as donor material for highly stable and efficient bulk heterojunction organic solar cells

Thiadiazole based π-conjugated small molecule as donor material for highly stable and efficient bulk heterojunction organic solar cells

Different Energetics at Donor:Acceptor Interfaces in Bilayer and Bulk‐Heterojunction Polymer:Non‐Fullerene Organic Solar Cells

To understand the limitations placed on the open‐circuit voltage of bulk heterojunction (BHJ) organic solar cells, the energy levels of neat donor and acceptor samples are often characterized and applied to study BHJ blends. However, energy levels derived from neat samples may not necessarily reflect those at the donor:acceptor interface in blends. The properties of organic semiconductors are sensitive to microstructural changes, with non‐fullerene acceptors (NFAs) in particular known to exhibit different thin‐film polymorphs. To investigate the influence of differences in molecular packing in neat and blend films, temperature‐dependent current–voltage characteristics are measured for bilayer (BL) and BHJ devices. Herein, the fullerene acceptor PC71BM is compared—whose energy levels are expected to be less sensitive to molecular packing—with the NFA ITIC, paired with the same donor polymer PTB7‐Th. It is found that the interfacial energy levels differ for BL and BHJ devices for the PTB7‐Th:ITIC system but remain the same for the PTB7‐Th:PC71BM system. Furthermore, X‐ray scattering measurements identify that ITIC exhibits a different packing mode in neat films and in BHJ blends. Such microstructure‐dependent differences between neat and blend samples need to be considered when studying energy losses in NFA BHJ solar cells.

Hybrid Solar Cells using Screen Printing Method

Abstract: Hybrid bulk heterojunction (BHJ) organic solar cells with a poly (3-hexylthiophene-2,5-diyl)(P3HT):(6,6)-phenyl C61- butyric acid methyl ester (PC61BM) active layer, a poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS) buffer layer, and an electrochemically deposited zinc oxide (ZnO) n-type inorganic layer were produced. The PET/ITO/ZnO/PEDOT:PSS/P3HT:PC61 BM/Al device was manufactured and tested under solar illumination (AM1.5G, 100 mW/cm2

Charge Carrier Dynamics in Non-Fullerene Acceptor-Based Organic Solar Cells: Investigating the Influence of Processing Additives Using Transient Absorption Spectroscopy.

In this study, we present a comprehensive investigation into the charge generation mechanism in bulk-heterojunction organic solar cells employing non-fullerene acceptors (NFAs) both with and without the presence of processing additives. While photovoltaic devices based on Y6 or BTP-eC9 have shown remarkable power conversion efficiencies, the underlying charge generation mechanism in polymer:NFA blends remains poorly understood. To shed light on this, we employ transient absorption (TA) spectroscopy to elucidate the charge transfer pathway within a blend of the donor polymer PM6 and NFAs. Interestingly, the charge carrier lifetimes of neat Y6 and BTP-eC9 are comparable, both reaching up to 20 ns. However, the PM6:BTP-eC9 blend exhibits substantially higher charge carrier generation and a longer carrier lifetime compared to PM6:Y6 blend films, leading to superior performance. By comparing TA data obtained from PM6:Y6 or PM6:BTP-eC9 blend films with and without processing additives, we observe significantly enhanced charge carrier generation and prolonged charge carrier lifetimes in the presence of these additives. These findings underscore the potential of manipulating excited species as a promising avenue for further enhancing the performance of organic solar cells. Moreover, this understanding contributes to the advancement of NFA-based systems and the optimization of charge transfer processes in polymer:NFA blends.

D-A-D type small molecule donors based on BODIPY skeleton for bulk heterojunction organic solar cells

In recent years, structural modification for boron-dipyrromethene (BODIPY) derivatives has been proven to be an effective way to improve their performance of organic solar cells (OSCs). Here, three D-A-D type small molecule donors BDP-1, BDP-2 and BDP-3 were synthesized based on 3,5,8-trimethyl BODIPY dye as the core by the introduction of 4-(diethylamino)phenyl, 4-diethylamino-2-methoxyphenyl and 4-(diphenylamino)phenyl at the 3, 5 and 8 positions, respectively, and used for the construction of organic solar cells. BDP-1, BDP-2, and BDP-3 are synthesized. Due to the strong electron-donating ability of the substituted groups at 3, 5, and 8 positions of BODIPY core, three donors exhibit extended π-conjugation and effective intramolecular charge transfer, resulting in the strong absorption in the range of 500–––900 nm with narrow band gaps below 1.52 eV. BDP-1, BDP-2 and BDP-3 display complementary absorption spectra and suitable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital levels (LUMO) with fullerene derivative PC71BM. These molecules (BDP-1, BDP-2 or BDP-3) as electron donor were applied into BHJ solar cells by using PC71BM as electron acceptor. The performance of BHJ organic solar cells is systematically investigated and compared. The optimized solar cells based on BDP-1, BDP-2 and BDP-3 show high power conversion efficiencies (PCEs) of 9.52%, 11.83% and 5.27%, respectively. The OSCs based on BDP-2: PC71BM exhibited excellent short-circuit current density (Jsc), high electron mobility and open-circuit voltage (Voc). This work demonstrates that BODIPY derivatives with simple-structured show great potential for high performance OSCs.