Bulk Heterojunction Solar Cells Research Articles

A Review on Self-Assembly Driven Optoelectronic Properties of Polythiophene-Peptide and Polythiophene-Polymer Conjugates.

Polythiophene (PT) is an important conducting polymer for its outstanding optoelectronic properties. Here, we delineate the self-assembly-driven optoelectronic properties of PT-peptide and PT-polymer conjugates, taking examples from recent literature reports. PT-peptide conjugates made by both covalent and noncovalent approaches are discussed. Poly(3-thiophene acetic acid) (P3TAA) covalently coupled with Gly-Gly-His tripeptide, C-protected and deprotected tripeptide H2N-F-F-V-OMe, etc. exhibits self-assembly-driven absorbance, fluorescence, photocurrent, and electronic properties. Noncovalent PT-peptide conjugates produced via ionic, H-bonding, and π-stacking interactions show tunable morphology and optoelectronic properties by varying the composition of a component. PT conjugated with Alzheimer's disease peptide (KLVFFAE, Aβ16-22) shows enhanced photocatalytic water splitting, cationic PT(CPT-I)-perylene bisimide-appended dipeptide (PBI-DY), and anionic PT-perylene diimide-appended cationic peptide (PBI-NH3+) conjugates and exhibits self-assembly-driven enhanced photoswitching and organic mixed electronic and ionic conductivity (OMEIC) properties. In the PT-polymer conjugates, self-assembly-driven optoelectronic properties of covalently produced PT-random copolymers, PT-block copolymers, PT-graft-random copolymers, and PT-graft-block copolymer conjugates are discussed. The HOMO-LUMO levels of hyperbranched polymers are optimized to obtain better power conversion efficiency (PCE) in the bulk heterojunction (BHJ) solar cell than in linear polymers, and P3TAA-ran-P3HT (43 mol % P3TAA) conjugated with MAPbI3 perovskite exhibits higher PCE (10%) than that with only P3TAA hole-transporting material. In the ampholytic polythiophene (APT), on increasing pH, the morphology changes from the vesicle to fibrillar network for the dethreading of the PT chain, resulting in a red shift of the absorbance peak, an enormous increase in PL intensity, lowering of the charge transfer resistance, and an induction of Warburg impedance for the release of quencher I- ions. The PT-g-(PDMAEMA-co-PGLU-HEM) graft copolymer self-assembles with Con-A lectin, causing fluorescence quenching, and acts as a sensor for Con-A with a LOD of 57 mg/L. Varying sequences of the block copolymer containing pH-responsive PDMAEMA and temperature-responsive PDEGMEM grafted to the PT backbone shows different self-assembly, optical, electronic, and photocurrent properties depending on the proximity and preponderance of the block sequence on the PT backbone.

Computational analysis of ligand design for Ru half-sandwich sensitizers in bulk heterojunction (BHJ) solar cells: Exploring the role of –NO2 group position and π-conjugation in optimizing efficiency

Bulk Heterojunction (BHJ) solar cells offer cost-effective photovoltaic solutions, flexible manufacturing, and improved efficiency with reduced environmental impact. Organometallic half-sandwich complexes, specifically a series of monometallic ruthenium complexes (Ru(1)–Ru(6)), have emerged as promising candidates for BHJ solar cells due to their outstanding charge transport properties. This study utilised Density Functional Theory (DFT) calculations with the B3LYP functional and SDD basis set augmented with 6-31 + G(d,p) to assess these Ru complexes with various N,O-chelating ligands, featuring distinct π-conjugated systems and positions of nitro groups, for BHJ solar cell applications. Our investigation focused on elucidating their electronic structures, identifying key electrophilic and nucleophilic sites, and exploring their optical properties. Our findings indicate that these complexes have maximum absorption wavelengths (λmax) ranging from 702 to 1083 nm, highlighting their strong photon absorption capabilities. Specifically, Ru(6), which includes the NO2 group, exhibits the narrowest energy gap but shows relatively lower values for oscillator strengths (f) and light harvesting efficiencies (LHE), indicating efficient light absorption but reduced energy conversion efficiency. In contrast, Ru(3), lacking the NO2 group but featuring enhanced π conjugation through cyclisation, demonstrates the widest energy gap yet boasts the highest values for f and LHE, suggesting superior efficiency in converting absorbed energy into electronic energy. These results emphasise the crucial role of ligand π-conjugation in enhancing energy conversion efficiency, while the strategic positioning of the NO2 group aids effective light absorption. Our study offers valuable insights into the design principles for optimizing organometallic ruthenium complexes in BHJ solar cell applications.

A simulation of the photoconversion efficiency of P3HT:PCBM bulk heterojunction: An insight on the charge collection efficiency

In organic bulk heterojunction solar cells, the internal quantum efficiency can be considered as the product of the absorption efficiency, the exciton diffusion efficiency, the charge transfer efficiency, and the charge collection efficiency. In previous studies, it has been reported that charge transfer and charge collection is very high in these solar cells, approaching 100 %. With a Monte Carlo simulation approach that considers the hopping of charges within the two materials of the heterojunctions, it is highlighted that an estimate of the charge collection efficiency can be evaluated considering that a certain number of charges do not reach the electrodes because of the random arrangement of the two materials in the heterojunction. The case of P3HT:PCBM (1:1 ratio) has been analyzed in this study.

Facile Synthesis of Dithienobenzothiadiazoles and D18-Cl Polymer via Na2S-Mediated Rapid Thiophene-Annulations for Organic Solar Cells.

We present a novel synthetic route for the rapid construction of dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-c][1,2,5]thiadiazoles via Na2S-promoted thiophene annulation. This method facilitated the synthesis of D18-Cl polymer, known for its efficacy as a polymer donor in bulk-heterojunction polymer solar cells. Starting from commercially available 4,7-dihalo-5,6-difluorobenzo[c][1,2,5]thiadiazole, various 4,7-dialkynylated compounds were obtained through Sonogashira reaction conditions. Subsequent Na2S-promoted thiophene annulations yielded DTBT and its derivatives in excellent yields within 10 minutes. DTBT was then utilized as a precursor for the concise synthesis of D18-Cl, benefiting from reduced synthetic steps, mild reaction conditions, decreased complexity, and high overall yields. In another route, a space group-bridged DTBT was directly constructed via Na2S-promoted thiophene annulations and converted into D18-Cl through a couple of steps. This developed protocol offers a straightforward and reliable synthetic tool, conducive to reducing complexities in the production of DTBT-based organic electronic materials, thereby advancing the potential commercialization of organic solar cells.

Porphyrins as key components for photoinduced charge separation, solar cells, and optogenetics

This review presents typical examples of porphyrins, which serve as highly effective building blocks, primarily drawn from our past achievements. They function as both an electron donor and an energy donor/acceptor in various applications. These applications include photosynthetic and solar cell models, dye-sensitized solar cells, bulk heterojunction solar cells, and optogenetics based on photoinduced charge separation. Consequently, porphyrins are essential components for evaluating energy and electron transfer properties, as well as for energy and biological applications.

Correlating the Photovoltaic Performance and Stability of the All-Small-Molecule Organic Solar Cells to Their Intermixed Phases Determined by Concentration-Dependent Ultraviolet-Visible Absorption Spectroscopy.

In addition to the donor-acceptor nano phases, the intermixed phase within the organic blends is crucial for the photovoltaic performance and stability of the bulk-heterojunction organic solar cells (OSCs). Here, the intermixed phase of a representative M-PhS:BTP-eC9 all-small-molecule organic solar cell was investigated by a concentration-dependent ultraviolet-visible (UV-vis) absorption spectroscopy method, where a shift of the absorption maximum wavelength was measured for the acceptor component with the increase of the acceptor concentration. The blend ratios of the acceptor to the donor in the intermixed phase, corresponding to the critical concentration for the formation of the acceptor nanophase (CAP), were determined to be 0.35, 0.20, and 0.15 for the as-cast, thermal annealing (TA), and the combined TA and solvent vapor annealing films. These results indicated that M-PhS and BTP-eC9 are kinetically well intermixed during spin coating, whereas TA and the following solvent annealing promote the crystallization of BTP-eC9 molecules out of the intermixed phase. The photovoltaic performance of the M-PhS:BTP-eC9 cells with different blend ratios was investigated. The formation of the BTP-eC9 nano phase in the blend film leads to stable VOC and fast increased JSC, which can be understood by the reduction of bimolecular charge recombination and the formation of electron transporting pathways within the photoactive layer. Similarly, the critical concentration for the formation of the donor phase was estimated to be 0.15 by measuring the stabilized VOC and increased JSC values of the cells with different donor blending ratios. More importantly, after a fast "burn-in" thermal degradation, the M-PhS:BTP-eC9 cell showed excellent thermal stability aging at 85 °C for over 1128 h, which is in good accordance with the unchanged intermixed phases measured by the UV-vis spectra of the annealed films. The current work demonstrates the feasibility of the spectroscopy method to investigate the intermixed phases for organic bulk-heterojunction solar cells and proves that all-small-molecule solar cells can be intrinsically very stable.

Exploring photoexcited spin states for fullerene-derivatives based organic bulk heterojunction solar cells using magneto-photocurrent

Fullerene-derivatives based bulk heterojunctions hold an exceptionally important role on the roadmap of highly efficient organic solar cells (OSCs). In recent years, the utilization of the non-fused ring acceptors based OSCs has further improved photovoltaic power conversion efficiencies. Among these, one of the fundamental issues is to explore and to understand the spin-related polaron dissociation at charge transfer states because they act as the central unit for the photovoltaic action. It is also eagerly important to quantify some internal fields, such as hyperfine fields and the spin–orbit coupling. The aim of the work is to develop a method for unraveling the photoexcited spin states, particularly for the fullerene-derivative based OSC. Furthermore, it helps to elucidate a long-standing issue regarding the relatively high production of photocurrent for the P3HT:PC71BM system, which is indeed contrary to its counterpart the P3HT:PC61BM system. Their corresponding Jablonski diagrams have been determined in order to understand interior spin dynamics. The method of the study offers an alternative route for an understanding of device performance from the spin-related aspect.

The role of interfacial donor–acceptor percolation in efficient and stable all-polymer solar cells

Polymerization of Y6-type acceptor molecules leads to bulk-heterojunction organic solar cells with both high power-conversion efficiency and device stability, but the underlying mechanism remains unclear. Here we show that the exciton recombination dynamics of polymerized Y6-type acceptors (Y6-PAs) strongly depends on the degree of aggregation. While the fast exciton recombination rate in aggregated Y6-PA competes with electron-hole separation at the donor–acceptor (D–A) interface, the much-suppressed exciton recombination rate in dispersed Y6-PA is sufficient to allow efficient free charge generation. Indeed, our experimental results and theoretical simulations reveal that Y6-PAs have larger miscibility with the donor polymer than Y6-type small molecular acceptors, leading to D–A percolation that effectively prevents the formation of Y6-PA aggregates at the interface. Besides enabling high charge generation efficiency, the interfacial D–A percolation also improves the thermodynamic stability of the blend morphology, as evident by the reduced device “burn-in” loss upon solar illumination.

Process Parameter Optimisation for Endohedral Metallofullerene Synthesis via the Arc-Discharge Method

Fullerenes have a unique structure, capable of both encapsulating other molecules and reacting with those on the exterior surface. Fullerene derivatives have also been found to have enormous potential to address the challenges of the renewable energy sector and current environmental issues, such as in the production of n-type materials in bulk heterojunction solar cells, as antimicrobial agents, in photocatalytic water treatment processes, and in sensor technologies. Endohedral metallofullerenes, in particular, can possess unpaired electron spins, driven by the enclosed metal atom or cluster, which yield valuable magnetic properties. These properties have significant potential for applications in molecular magnets, spin probes, quantum computing, and devices such as quantum information processing,, atomic clocks, and molecular magnets. However, the intrinsically low yield of endohedral fullerenes remains a huge obstacle, impeding not only their industrial utilization but also the synthesis and characterization essential for exploring novel applications. The low yield and difficulty in separation of different types of endohedral fullerenes results in the usage of a large amount of solvents and energy, which is detrimental to the environment. In this paper, we analyse the methodologies proposed by various researchers and identify the critical synthesis parameters that play a role in increasing the yields of fullerenes.

The effect of structural modification of novel D-π-A-π-D molecules on their performance as donors in bulk heterojunction solar cells: Theoretical investigation

We have used density functional theory (DFT) and time-dependent density functional theory (TD-DFT) to perform a theoretical study of seven novel small molecules SMi (i = 1–7) characterized by their D-π-A-π-D structures, these molecules have been designed based on a reference molecule composed mainly of Diketopyrrolopyrole as acceptor. In addition, to improve the optoelectronic and photovoltaic properties, the D electron donor (Carbazole) was replaced by another donor (Pyranylidene), and the π bridge (Thiophene) was also replaced by other bridges. Thus, replacing the Carbazole with Pyranylidene results in a significant reduction in the energy gap Egap and an accompanying red shift in the absorption spectra, in addition to the decrease in electron and hole reorganization energy. On the other hand, modification of the π-bridge increased the VOC and LHE values. Finally, a study was conducted on the SMi (i = R, 1–7)/ PC61BM blend to assess the effective charge transport at the D/A interface.

Understanding the correlation between energy‐state mismatching and open‐circuit voltage loss in bulk heterojunction solar cells

AbstractPhotoinduced intermolecular charge transfer (PICT) determines the voltage loss in bulk heterojunction (BHJ) organic photovoltaics (OPVs), and this voltage loss can be minimized by inducing efficient PICT, which requires energy‐state matching between the donor and acceptor at the BHJ interfaces. Thus, both geometrically and energetically accessible delocalized state matching at the hot energy level is crucial for achieving efficient PICT. In this study, an effective method for quantifying the hot state matching of OPVs was developed. The degree of energy‐state matching between the electron donor and acceptor at BHJ interfaces was quantified using a mismatching factor (MF) calculated from the modified optical density of the BHJ. Furthermore, the correlation between the open‐circuit voltage (Voc) of the OPV device and energy‐state matching at the BHJ interface was investigated using the calculated MF. The OPVs with small absolute MF values exhibited high Voc values. This result clearly indicates that the energy‐state matching between the donor and acceptor is crucial for achieving a high Voc in OPVs. Because the MF indicates the degree of energy‐state matching, which is a critical factor for suppressing energy loss, it can be used to estimate the Voc loss in OPVs.

Metal oxide-embedded carbon-based materials for polymer solar cells and X-ray detectors.

This study examines the effects of hybrid nanoparticles made of NiO@rGO (reduced graphene oxide) and NiO@CNT (carbon nanotubes) on PCDTBT and PCBM active layers in glass/ITO/HTL/active-layer/LiF/Al structured bulk heterojunction (BHJ) polymer solar cells (PSCs) and X-ray photodetectors. These hybrid nanoparticles were used to create BHJ solar cells and photodetectors, and microscopic research was conducted to determine how they affect the structure of the devices. The findings show that compared to conventional matrices, the active layers with NiO@rGO and NiO@CNT incorporation have increased the charge carrier capacities and exciton dissociation properties. In order to assess their impact on the characteristics of charge transport, various weight ratios of these hybrid nanoparticles dispersed in polymer junctions are being investigated. Notably, compared to the pure PCDTBT:PCBM active layer (power conversion efficiency (PCE) = 4.35%), the NiO@CNT device has the highest PCE = 6.42% which, among the tested configurations, demonstrates its superior performance in converting sunlight into electricity. Among the tested X-ray detector materials, "NiO@CNT" achieves the best performance with a sensitivity of 1.92 mA Gy-1 cm-2. Through improved interfacial behaviors and effective charge transport, this work highlights the potential of these cutting-edge hybrid nanoparticles to enhance the performance of organic electronic devices.

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.

Multifunctional Photoelectroactive Materials for Optoelectronic Applications Based on Thieno[3,4-b]pyrazines and Thieno[1,2,5]thiadiazoles.

In this study, we introduce a novel family of symmetrical thiophene-based small molecules with a Donor-Acceptor-Donor structure. These compounds feature three different acceptor units: benzo[c][1,2,5]thiadiazole (Bz), thieno[3,4-b]pyrazine (Pz), and thieno[1,2,5]thiadiazole (Tz), coupled with electron donor units based on a carbazole-thiophene derivative. Using Density Functional Theory (DFT), we investigate how the molecular geometry and strength of the central acceptor unit impact the redox and spectroscopic properties. Notably, the incorporation of Pz and Tz moieties induces a significant redshift in the absorption and emission spectra, which extend into the near-infrared (NIR) region, simultaneously reducing their energy gaps (~1.4-1.6 eV). This shift is attributed to the increased coplanarity of the oligomeric inner core, both in the ground (S0 ) and excited (S1 ) states, due to the enhanced quinoidal character as supported by bond-length alternation (BLA) analysis. These structural changes promote better π-electron delocalization and facilitate photoinduced charge transfer processes in optoelectronic devices. Notably, we show that Pz- and Tz-containing molecules exhibit NIR electrochromic behavior and present ambivalent character in bulk heterojunction (BHJ) solar cells. Finally, theoretical calculations suggest that these molecules could serve as effective two-photon absorption (2PA) probes, further expanding their potential in optoelectronic applications.

Theoretical and experimental investigations on 5,12-di(methyl)-quinacridin-ylidene)-7,14-di(rhodanineimine) for optoelectronic applications

In searching for novel organic semiconductors, 5,12-di(methyl)-quinacridin-ylidene)-7,14-di(rhodanineimine) (DQAR) is designed and chemically synthesized by using condensation reaction. The molecular structure of DQAR is supported with spectral measurements. Electronic and geometrical properties of DQAR are investigated be means of combined computational and experimental analyses. Density function theory (DFT/B3LYP) utilizing 6-311G(d,p) basis set are used to optimize DQAR molecular structure and its related geometrical parameters. The intermolecular interactions are calculated using reduced density gradient (RDG) planes. The highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of DQAR are experimentally estimated by using the optical absorbance and cyclic voltammetry techniques. DQAR is used as a third component in the active layer of bulk heterojunction (BHJ) solar cells. The BHJ solar cells based on P3HT:DQAR:PC61BM (P3HT = poly(3-hexylthiophene and PC61BM = [6,6]-phenyl-C61-butyric acid methyl ester) active layers are found to be to be better that those based on only P3HT:PC61BM mainly due to the contribution of DQAR to the photocurrent. The obtained results are analyzed in terms of the computational and experimental data. Our initial results indicate that DQAR can be used in BHJ solar cells fabrications.

One-Pot Synthesis of Semiconducting Quantum Dots–Organic Linker–Carbon Nanotubes for Potential Applications in Bulk Heterojunction Solar Cells

Materials and composites with the ability to convert light into electricity are essential for a variety of applications, including solar cells. The development of materials and processes needed to boost the conversion efficiency of solar cell materials will play a key role in providing pathways for dependable light to electric energy conversion. Here, we show a simple, single-step technique to synthesize photoactive nanocomposites by coupling carbon nanotubes with semiconducting quantum dots using a molecular linker. We also discuss and demonstrate the potential application of nanocomposite for the fabrication of bulk heterojunction solar cells. Cadmium selenide (CdSe) quantum dots (QDs) were attached to multiwall carbon nanotubes (MWCNTs) using perylene-3, 4, 9, 10-tetracarboxylic-3, 4, 9, 10-dianhydride (PTCDA) as a molecular linker through a one-step synthetic route. Our investigations revealed that PTCDA tremendously boosts the density of QDs on MWCNT surfaces and leads to several interesting optical and electrical properties. Furthermore, the QD–PTCDA–MWCNTs nanocomposites displayed a semiconducting behavior, in sharp contrast to the metallic behavior of the MWCNTs. These studies indicate that, PTCDA interfaced between QDs and MWCNTs, acted as a molecular bridge which may facilitate the charge transfer between QDs and MWCNTs. We believe that the investigations presented here are important to discover simple synthetic routes for obtaining photoactive nanocomposites with several potential applications in the field of opto-electronics as well as energy conversion devices.

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.

Direct correlation between the built-in potential and the power conversion efficiency of NFA organic solar cells

While it is known that too low built-in potential is detrimental to cells' performance, there is no consensus regarding the importance of maximizing the internal electric field or the built-in potential for achieving the highest power conversion efficiency of non-fullerene acceptor (NFA) organic solar cells. We use one of the prototypical NFA bulk heterojunction solar cells to show a direct correlation between the built-in potential, the open circuit voltage, the fill factor, and the device's efficiency. This is achieved using statistical analysis of devices made of two different cathodes (Ag, Mg) and a simple, intuitive model for the solar cell's current–voltage characteristics. Designing device structures with enhanced built-in potential (internal electric field) is crucial for surpassing the 20% efficiency limit.

Remarkable Electrical Connectivity in the Acceptor Phase of Y6- and Fullerene-Based Bulk Heterojunction Solar Cells

Remarkable Electrical Connectivity in the Acceptor Phase of Y6- and Fullerene-Based Bulk Heterojunction Solar Cells

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.