Small Molecule Acceptors Research Articles

Progress in Non-Fullerene Acceptors: Evolution from Small to Giant Molecules.

With the rapid development of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) is increasing. According to their different chemical structures, NFAs can initially be divided into two categories: small molecule acceptors (SMAs) and polymerized small molecule acceptors (PSMAs). Due to the strong absorption capacity and controllable energy levels, the PCE of devices based on SMAs has approached 20%. Compared with SMAs, PSMAs have advantages in stability and flexibility, and the PCE of PSMA-based devices has exceeded 18%. However, the higher synthesis cost and lower batch repeatability hinder its further development. Recently, the concept of giant molecule acceptors (GMAs) has been proposed. These materials have a clear molecular structure and are considered novel acceptor materials that combine the advantages of SMAs and PSMAs. Currently, the PCE of devices based on GMAs has exceeded 19%. In this review, we will introduce the latest developments in SMAs, PSMAs, and GMAs. Then, the advantages of GMAs and the relationship between their structure and performance will be analyzed. In the end, perspectives on the opportunities and challenges of these materials are provided, which could inspire further development of NFAs for advanced OSCs.

Manipulating Alkyl Inner Side Chain of Acceptor for Efficient As-Cast Organic Solar Cells.

As-cast organic solar cells (OSCs) possess tremendous potential for low-cost commercial applications. Herein, five small-molecule acceptors (A1-A5) are designed and synthesized by selectively and elaborately extending the alkyl inner side chain flanking on the pyrrole motif to prepare efficient as-cast devices. As the extension of the alkyl chain, the absorption spectra of the films are gradually blue-shifted from A1 to A5 along with slightly uplifted lowest unoccupied molecular orbital energy levels, which is conducive for optimizing the trade-off between short-circuit current density and open-circuit voltage of the devices. Moreover, a longer alkyl chain improves compatibility between the acceptor and donor. The in situ technique clarifies that good compatibility will prolong molecular assembly time and assist in the preferential formation of the donor phase, where the acceptor precipitates in the framework formed by the donor. The corresponding film-formation dynamics facilitate the realization of favorable film morphology with a suitable fibrillar structure, molecular stacking, and vertical phase separation, resulting in an incremental fill factor from A1 to A5-based devices. Consequently, the A3-based as-cast OSCs achieve a top-ranked efficiency of 18.29%. This work proposes an ingenious strategy to manipulate intermolecular interactions and control the film-formation process for constructing high-performance as-cast devices.

Enhanced Fill Factor and Efficiency of Ternary Organic Solar Cells by a New Asymmetric Non-Fullerene Small Molecule Acceptor.

Asymmetric non-fullerene small molecules acceptor (as-NF-SMAs) exhibit greater vitality in photovoltaic materials compared to their symmetric counterparts due to their larger dipole moments and stronger intermolecular interactions, which facilitate exciton dissociation and charge transmission in organic solar cells (OSCs). Here, we introduced a new as-NF-SMAs, named IDT-TNIC, as the third component in ternary organic solar cells (TOSCs). The asymmetric IDT-TNIC used indacenodithiophene (IDT) as the central core, alkylthio-thiophene as a unilateral π-bridge and extended end groups as electron-withdrawing. Due to the non-covalent conformational lock (NCL) established between O⋅⋅⋅S and S⋅⋅⋅S, the IDT-TNIC molecule preserves its coplanar structure effectively. Furthermore, IDT-TNIC exhibits complementary absorption and excellent compatibility with donor and acceptor materials, as well as optimized ladder energy level arrangement, resulting in a higher and more balanced μh/μe value, more homogeneous and suitable phase separation morphology in TOSCs. Thus, the PCE of the TOSCs reached 17 % when the weight ratio of PM6 : Y6 : IDT-TNIC was 1 : 1.1 : 0.1, and it is noteworthy that when the device area was increased to 1 cm2, the PCE could still be maintained at over 14 %. Detailed studies and analysis indicate that IDT-TNIC has great potential as a third component in OSCs and for large-scale printing in the future.

High-Performance PM6:Y6-Based Ternary Solar Cells with Enhanced Open Circuit Voltage and Balanced Mobilities via Doping a Wide-Band-Gap Amorphous Acceptor.

Great progress has been made in organic solar cells (OSCs) in recent years, especially after the report of the highly efficient small-molecule electron acceptor Y6. However, the relatively low open circuit voltage (VOC) and unbalanced charge mobilities remain two issues that need to be resolved for further improvement in the performance of OSCs. Herein, a wide-band-gap amorphous acceptor IO-4Cl, which possessed a shallower lowest unoccupied molecular orbital (LUMO) energy level than Y6, was introduced into the PM6:Y6 binary system to construct a ternary device. The mechanism study revealed that the introduced IO-4Cl was alloyed with Y6 to prevent the overaggregation of Y6 and offer dual channels for effective hole transportation, resulting in balanced hole and electron mobilities. Taking these advantages, an enhanced VOC of 0.894 V and an improved fill factor of 75.58% were achieved in the optimized PM6:Y6:IO-4Cl-based ternary device, yielding a promising power conversion efficiency (PCE) of 17.49%, which surpassed the 16.72% efficiency of the PM6:Y6 binary device. This work provides an alternative solution to balance the charge mobilities of PM6:Y6-based devices by incorporating an amorphous high-performance LUMO A-D-A small molecule as the third compound.

Exploration of the synergistic effect of chrysene-based core and benzothiophene acceptors on photovoltaic properties of organic solar cells

To improve the efficacy of organic solar cells (OSCs), novel small acceptor molecules (CTD1–CTD7) were designed by modification at the terminal acceptors of reference compound CTR. The optoelectronic properties of the investigated compounds (CTD1–CTD7) were accomplished by employing density functional theory (DFT) in combination with time-dependent density functional theory (TD-DFT). The M06 functional along with a 6-311G(d,p) basis set was utilized for calculating various parameters such as: frontier molecular orbitals (FMO), absorption maxima (λmax), binding energy (Eb), transition density matrix (TDM), density of states (DOS), and open circuit voltage (Voc) of entitled chromophores. A red shift in the absorption spectra of all designed chromophores (CTD1–CTD7) was observed as compared to CTR, accompanied by low excitation energy. Particularly, CTD4 was characterized by the highest λmax value of 685.791 nm and the lowest transition energy value of 1.801 eV which might be ascribed to the robust electron-withdrawing end-capped acceptor group. The observed reduced binding energy (Eb) was linked to an elevated rate of exciton dissociation and substantial charge transfer from central core in HOMO towards terminal acceptors in LUMO. These results were further supported by the outcomes from TDM and DOS analyses. Among all entitled chromophores, CTD4 exhibited bathochromic shift (685.791 nm), minimum HOMO/LUMO band gap of 2.347 eV with greater CT. Thus, it can be concluded that by employing molecular engineering with efficient acceptor moieties, the efficiency of photovoltaic materials could be improved.

The Effect of Conjugated Nitrile Structures as Acceptor Moieties on the Photovoltaic Properties of Dye-Sensitized Solar Cells: DFT and TD-DFT Investigation.

A major challenge in improving the overall efficiency of dye-sensitized solar cells is improving the optoelectronic properties of small molecule acceptors. This work primarily investigated the effects of conjugation in nitriles incorporated as acceptor moieties into a newly designed series of D-A-A dyes. Density functional theory was employed to specifically study how single-double and single-triple conjugation in nitriles alters the optical and electronic properties of these dyes. The Cy-4c dye with a highly conjugated nitrile unit attained the smallest band gap (1.80 eV), even smaller than that of the strong cyanacrylic anchor group (2.07 eV). The dyes lacking conjugation in nitrile groups did not contribute to the LUMO, while LUMOs extended from donors to conjugated nitrile components, facilitating intramolecular charge transfer and causing a strong bind to the film surface. Density of state analysis revealed a considerable impact of conjugated nitrile on the electronic properties of dyes through an effective contribution in the LUMO, exceeding the role of the well-known strong 2,1,3-benzothiadiazole acceptor unit. The excited state properties and the absorption spectra were investigated using time-dependent density functional theory (TD-DFT). Conjugation in the nitrile unit caused the absorption band to broaden, strengthen, and shift toward the near-infrared region. The proposed dyes also showed optimum photovoltaic properties; all dyes possess high light-harvesting efficiency (LHE) values, specifically 96% for the dyes Cy-3b and Cy-4c, which had the most conjugated nitrile moieties. The dyes with higher degrees of conjugation had longer excitation lifetime values, which promote charge transfer by causing steady charge recombination at the interface. These findings may provide new insights into the structure of conjugated nitriles and their function as acceptor moieties in DSSCS, which may lead to the development of extremely effective photosensitizers for solar cells.

Efficient and Accurate Estimation of Electronic Polarization Energies for Organic Semiconductors: An Embedding Charge Quantum Mechanics/Continuum Dielectric Model.

Electronic polarization plays a pivotal role in determining the molecular energy levels of organic semiconductors (OSCs) in the condensed phase. However, accurate estimation of the electronic polarization energy is a challenging task due to the intricate imbalance between the precision and efficiency. In this work, we have developed an embedding charge quantum mechanics/continuum dielectric (EC-QM/CD) model, which enables quantitative evaluation of the ionization potential (IP), electron affinity (EA), and polarization energy in both crystalline and amorphous solids for OSCs. The benchmark calculations on both p-type OSCs of oligoacenes and n-type OSCs of A-D-A small-molecule acceptors show that the values of IP, EA, and polarization energy obtained by EC-QM/CD are in good accordance with the experimental measurements or the results by high-precision methods, while the computational costs are substantially reduced. Given its balance between the accuracy and efficiency, the EC-QM/CD model exhibits considerable potential to broaden the applications in the field of OSCs, for instance, high-throughput screening by using solid-state energy levels or polarization energies as critical descriptors.

Hybrid Organic-Si C-MOSFET Image Sensor Designed with Blue-, Green-, and Red-Sensitive Organic Photodiodes on Si C-MOSFET-Based Photo Signal Sensor Circuit.

The resolution of Si complementary metal-oxide-semiconductor field-effect transistor (C-MOSFET) image sensors (CISs) has been intensively enhanced to follow the technological revolution of smartphones, AI devices, autonomous cars, robots, and drones, approaching the physical and material limits of a resolution increase in conventional Si CISs because of the low quantum efficiency (i.e., ~40%) and aperture ratio (i.e., ~60%). As a novel solution, a hybrid organic-Si image sensor was developed by implementing B, G, and R organic photodiodes on four n-MOSFETs for photocurrent sensing. Photosensitive organic donor and acceptor materials were designed with cost-effective small molecules, i.e., the B, G, and R donor and acceptor small molecules were Coumarin6 and C_60, DMQA and MePTC, and ZnPc and TiOPc, respectively. The output voltage sensing margins (i.e., photocurrent signal difference) of the hybrid organic-Si B, G, and R image sensor pixels presented results 17, 11, and 37% higher than those of conventional Si CISs. In addition, the hybrid organic-Si B, G, and R image sensor pixels could achieve an ideal aperture ratio (i.e., ~100%) compared with a Si CIS pixel using the backside illumination process (i.e., ~60%). Moreover, they may display a lower fabrication cost than image sensors because of the simple image sensor structure (i.e., hybrid organic-Si photodiode with four n-MOSFETs).

Halogenated Dibenzo[f,h]quinoxaline Units Constructed 2D-Conjugated Guest Acceptors for 19% Efficiency Organic Solar Cells.

Halogenation of Y-series small-molecule acceptors (Y-SMAs) is identified as an effective strategy to optimize photoelectric properties for achieving improved power-conversion-efficiencies (PCEs) in binary organic solar cells (OSCs). However, the effect of different halogenation in the 2D-structured large π-fused core of guest Y-SMAs on ternary OSCs has not yet been systematically studied. Herein, four 2D-conjugated Y-SMAs (X-QTP-4F, including halogen-free H-QTP-4F, chlorinated Cl-QTP-4F, brominated Br-QTP-4F, and iodinated I-QTP-4F) by attaching different halogens into 2D-conjugation extended dibenzo[f,h]quinoxaline core are developed. Among these X-QTP-4F, Cl-QTP-4F has a higher absorption coefficient, optimized molecular crystallinity and packing, suitable cascade energy levels, and complementary absorption with PM6:L8-BO host. Moreover, among ternary PM6:L8-BO:X-QTP-4F blends, PM6:L8-BO:Cl-QTP-4F obtains a more uniform and size-suitable fibrillary network morphology, improved molecular crystallinity and packing, as well as optimized vertical phase distribution, thus boosting charge generation, transport, extraction, and suppressing energy loss of OSCs. Consequently, the PM6:L8-BO:Cl-QTP-4F-based OSCs achieve a 19.0% efficiency, which is among the state-of-the-art OSCs based on 2D-conjugated Y-SMAs and superior to these devices based on PM6:L8-BO host (17.70%) and with guests of H-QTP-4F (18.23%), Br-QTP-4F (18.39%), and I-QTP-4F (17.62%). The work indicates that halogenation in 2D-structured dibenzo[f,h]quinoxaline core of Y-SMAs guests is a promising strategy to gain efficient ternary OSCs.

Ultranarrow-bandgap small-molecule acceptor enables sensitive SWIR detection and dynamic upconversion imaging.

Short-wavelength infrared (SWIR) light detection plays a key role in modern technologies. Emerging solution-processed organic semiconductors are promising for cost-effective, flexible, and large-area SWIR organic photodiodes (OPDs). However, the spectral responsivity (R) and specific detectivity (D*) of SWIR OPDs are restricted by insufficient exciton dissociation and high noise current. In this work, we synthesized an SWIR small molecule with a spectral coverage of 0.3 to 1.3 micrometers peaking at 1100 nanometers. The photodiode, with optimized exciton dissociation, charge injection, and SWIR transmittance, achieves a record high R of 0.53 ampere per watt and D* of 1.71 × 1013 Jones at 1110 nanometers under zero bias. The D* at 1 to 1.2 micrometers surpasses that of the uncooled commercial InGaAs photodiode. Furthermore, large-area semitransparent all-organic upconversion devices integrating the SWIR photodiode realized static and dynamic SWIR-to-visible imaging, along with excellent upconversion efficiency and spatial resolution. This work provides alternative insights for developing sensitive organic SWIR detection.

A Difluoro-Methoxylated Ending-Group Asymmetric Small Molecule Acceptor Lead Efficient Binary Organic Photovoltaic Blend.

Developing a new end group for synthesizing asymmetric small molecule acceptors (SMAs) is crucial for achieving high-performance organic photovoltaics (OPVs). Herein, an asymmetric small molecule acceptor, BTP-BO-4FO, featuring a new difluoro-methoxylated end-group is reported. Compared to its symmetric counterpart L8-BO, BTP-BO-4FO exhibits an upshifted energy level, larger dipole moment, and more sequential crystallinity. By adopting two representative and widely available solvent additives (1-chloronaphthalene (CN) and 1,8-diiodooctane (DIO)), the device based on PM6:BTP-BO-4FO (CN) photovoltaic blend demonstrates a power conversion efficiency (PCE) of 18.62% with an excellent open-circuit voltage (VOC) of 0.933V, which surpasses the optimal result of L8-BO. The PCE of 18.62% realizes the best efficiencies for binary OPVs based on SMAs with asymmetric end groups. A series of investigations reveal that optimized PM6:BTP-BO-4FO film demonstrates similar molecular packing motif and fibrillar phase distribution as PM6:L8-BO (DIO) does, resulting in comparable recombination dynamics, thus, similar fill factor. Besides, it is found PM6:BTP-BO-4FO possesses more efficient charge generation, which yields better VOC-JSC balance. This study provides a new ending group that enables a cutting-edge efficiency in asymmetric SMA-based OPVs, enriching the material library and shed light on further design ideas.

Semitransparent organic photovoltaics enabled by transparent p-type inorganic semiconductor and near-infrared acceptor

Semitransparent organic photovoltaics (STOPVs) have gained wide attention owing to their promising applications in building-integrated photovoltaics, agrivoltaics, and floating photovoltaics. Organic semiconductors with high charge carrier mobility usually have planar and conjugated structures, thereby showing strong absorption in visible region. In this work, a new concept of incorporating transparent inorganic semiconductors is proposed for high-performance STOPVs. Copper(I) thiocyanate (CuSCN) is a visible-transparent inorganic semiconductor with an ionization potential of 5.45 eV and high hole mobility. The transparency of CuSCN benefits high average visible transmittance (AVT) of STOPVs. The energy levels of CuSCN as donor match those of near-infrared small molecule acceptor BTP-eC9, and the formed heterojunction exhibits an ability of exciton dissociation. High mobility of CuSCN contributes to a more favorable charge transport channel and suppresses charge recombination. The control STOPVs based on PM6/BTP-eC9 exhibit an AVT of 19.0% with a power conversion efficiency (PCE) of 12.7%. Partial replacement of PM6 with CuSCN leads to a 63% increase in transmittance, resulting in a higher AVT of 30.9% and a comparable PCE of 10.8%.

Side‐Chain Engineering of Non‐Fullerene Acceptors with Trialkylsilyloxy Groups for Enhanced Photovoltaic Performance†

Comprehensive SummarySide‐chain engineering has emerged as a highly effective strategy for tailoring the aggregation behavior and charge transport properties of non‐fullerene small molecule acceptors (SMAs). In this study, we designed and synthesized two SMAs, namely BTPSi‐Bu and BTPSi‐Pr, respectively incorporating tributylsilyloxy and triisopropylsilyloxy groups in their outer positions. Notably, BTPSi‐Bu exhibited better planarity, crystallization, and favorable phase separation when paired with PM6 donor polymer compared to its counterpart, BTPSi‐Pr. The resulting organic solar cells, utilizing the PM6:BTPSi‐Bu blend, demonstrated a remarkable power conversion efficiency of 17.41% and a high open‐circuit voltage of 0.859 V. These findings underscore the significance of integrating trialkylsilyloxy side chains into SMAs as a rational design approach for enhancing the performance of photovoltaic systems.

Tailoring Cyano Substitutions on Quinoxaline‐based Small‐Molecule Acceptors Enabling Enhanced Molecular Packing for High‐Performance Organic Solar Cells

AbstractCyanation is a common chemical modification strategy to fine‐tune the energy levels and molecular packing of organic semiconductors, especially materials used in organic solar cells (OSCs). Generally, cyanation is used to modify the end groups of high‐performance small‐molecule acceptors (SMAs). However, the cyanation strategy has not been investigated on the central backbone of SMAs, which could introduce stronger intermolecular interaction and enhance the π–π stacking for rapid charge transport. This paper, for the first time, reports a new cyanation strategy on the central benzo‐quinoxaline core and synthesizes two novel A‐DA'D‐A type SMAs, named BQx‐CN and BQx‐2CN, with mono‐ and di‐cyanide groups, respectively. Through tailoring the number of CN groups, the BQx‐CN‐based OSC exhibits the best device performance of 18.8%, which is significantly higher than the non‐cyano BQx‐based one. The reason for the superior performance of BQx‐CN‐based devices can be attributed to the fine‐tuned energy level, stronger packing, and ideal phase segregation, which lead to superior exciton dissociation, faster charge transport, and suppressed recombination, therefore the highest fill factor (FF) and power conversion efficiencies (PCE). The research demonstrates the effectiveness of the cyanation strategy on the central core of SMAs for enhanced molecular packing and better performance of OSCs.

Layer‐by‐Layer Organic Solar Cells Enabled by 1,3,4‐Selenadiazole‐Containing Crystalline Small Molecule with Double‐Fibril Network Morphology

AbstractA double‐fibril network of the photoactive layer morphology is recognized as an ideal structure facilitating exciton diffusion and charge carrier transport for high‐performance organic solar cells (OSCs). However, in the layer‐by‐layer processed OSCs (LbL‐OSCs), polymer donors and small molecule acceptors (SMAs) are separately deposited, and it is challenging to realize a fibril network of pure SMAs with the absence of tight interchain entanglement as polymers. In this work, crystalline small molecule donors (SMDs), named TDZ‐3TR and SeDZ‐3TR, were designed and introduced into the L8‐BO acceptor solution, forcing the phase separation and molecular fibrilization. SeDZ‐3TR showed higher crystallinity and lower miscibility with L8‐BO acceptor than TDZ‐3TR, enabling more driving force to favor the phase separation and better molecular fibrilization of L8‐BO. On the other hand, two donor polymers of PM6 and D18 with different fibril widths and lengths were put together to optimize the fibril network of the donor layer. The simultaneously optimization of the acceptor and donor layers resulted in a more ideal double‐fibril network of the photoactive layer and an impressive power conversion efficiency (PCE) of 19.38 % in LbL‐OSCs.

Layer-by-Layer Organic Solar Cells Enabled by 1,3,4-Selenadiazole-Containing Crystalline Small Molecule with Double-Fibril Network Morphology.

A double-fibril network of the photoactive layer morphology is recognized as an ideal structure facilitating exciton diffusion and charge carrier transport for high-performance organic solar cells (OSCs). However, in the layer-by-layer processed OSCs (LbL-OSCs), polymer donors and small molecule acceptors (SMAs) are separately deposited, and it is challenging to realize a fibril network of pure SMAs with the absence of tight interchain entanglement as polymers. In this work, crystalline small molecule donors (SMDs), named TDZ-3TR and SeDZ-3TR, were designed and introduced into the L8-BO acceptor solution, forcing the phase separation and molecular fibrilization. SeDZ-3TR showed higher crystallinity and lower miscibility with L8-BO acceptor than TDZ-3TR, enabling more driving force to favor the phase separation and better molecular fibrilization of L8-BO. On the other hand, two donor polymers of PM6 and D18 with different fibril widths and lengths were put together to optimize the fibril network of the donor layer. The simultaneously optimization of the acceptor and donor layers resulted in a more ideal double-fibril network of the photoactive layer and an impressive power conversion efficiency (PCE) of 19.38 % in LbL-OSCs.

Polymerized-Small-Molecule Acceptors Featuring Siloxane-Terminated Side Chains for Mechanically Robust All-Polymer Solar Cells.

Flexible and stretchable organic solar cells (OSCs) show great promise in wearable and stretchable electronic applications. However, current high-performance OSCs consisting of polymer donors (PDs) and small-molecule acceptors (SMAs) face significant challenges in achieving both high power conversion efficiency (PCE) and excellent stretch-ability. In this study, we synthesized a new polymerized-small-molecule acceptor (P-SMA) PY-SiO featuring siloxane-terminated side chains and compared its photovoltaic and mechanical performance to that of the reference PY-EH with ethylhexyl-terminated side chains. We found that the incorporation of siloxane-terminated side chains in PY-SiO enhanced the molecular aggregation and charge transport, leading to an optimized film morphology. The resultant of all-polymer solar cells (all-PSCs) based on PBDB-T/PY-SiO showed a higher PCE of 12.04% than the PY-EH-based one (10.85%). Furthermore, the siloxane-terminated side chains also increased the interchain distance and provided a larger free volume for chain rotation and reconfiguration, resulting in a higher film crack-onset strain (COS: 18.32% for PBDB-T/PY-SiO vs 11.15% for PBDB-T/PY-EH). Additionally, the PY-SiO-based stretchable all-PSCs exhibited an impressive PCE of 9.8% and retained >70% of its original PCE even under a substantial 20% strain, exceeding the performance of the PY-EH-based stretchable all-PSCs. Our result suggests the great potential of the siloxane-terminated side chain for achieving high-performance and stretchable OSCs.

Eliminating the Burn-in Loss of Efficiency in Organic Solar Cells by Applying Dimer Acceptors as Supramolecular Stabilizers.

The meta-stable active layer morphology of organic solar cells (OSCs) is identified as the main cause of the rapid burn-in loss of power conversion efficiency (PCE) during long-term device operation. However, effective strategies to eliminate the associated loss mechanisms from the initial stage of device operation are still lacking, especially for high-efficiency material systems. Herein, the introduction of molecularly engineered dimer acceptors with adjustable thermal transition properties into the active layer of OSCs to serve as supramolecular stabilizers for regulating the thermal transitions and optimizing the crystallization of the absorber composites is reported. By establishing intimate π-π interactions with small-molecule acceptors, these stabilizers can effectively reduce the trap-state density (Nt) in the devices to achieve excellent PCEs over 19%. More importantly, the low Nt associated with an initially optimized morphology can be maintained under external stresses to significantly reduce the PCE burn-in loss in devices. This research reveals a judicious approach to improving OPV stability by establishing a comprehensive correlation between material properties, active-layer morphology, and device performance, for developing burn-in-free OSCs.

Heterogeneous Nucleating Agent for High-Boiling-Point Nonhalogenated Solvent-Processed Organic Solar Cells and Modules.

High-boiling-point nonhalogenated solvents are superior solvents to produce large-area organic solar cells (OSCs) in industry because of their wide processing window and low toxicity; while, these solvents with slow evaporation kinetics will lead excessive aggregation of state-of-the-art small molecule acceptors (e.g. L8-BO), delivering serious efficiency losses. Here, a heterogeneous nucleating agent strategy is developed by grafting oligo (ethylene glycol) side-chains on L8-BO (BTO-BO). The formation energy of the obtained BTO-BO; while, changing from liquid in a solvent to a crystalline phase, is lower than that of L8-BO irrespective of the solvent type. When BTO-BO is added as the third component into the active layer (e.g. PM6:L8-BO), it easily assembles to form numerous seed crystals, which serve as nucleation sites to trigger heterogeneous nucleation and increase nucleation density of L8-BO through strong hydrogen bonding interactions even in high-boiling-point nonhalogenated solvents. Therefore, it can effectively suppress excessive aggregation during growth, achieving ideal phase-separation active layer with small domain sizes and high crystallinity. The resultant toluene-processed OSCs exhibit a record power conversion efficiency (PCE) of 19.42% (certificated 19.12%) with excellent operational stability. The strategy also has superior advantages in large-scale devices, showing a 15.03-cm2 module with a record PCE of 16.35% (certificated 15.97%).

Evaluating the impact of structural and rotational isomerization, as well as halogenation, on Y18 and Y18-ID small molecule acceptors: A DFT and TD-DFT study

In the present work, using a systematic approach with DFT and TD-DFT techniques, we investigate the isomerization impact on Y18 and Y18-ID, two electron acceptors belonging to the Y family. Furthermore, the effect of the halogen atom was assessed by changing the original fluorine atoms with chlorine, bromine, and iodine. Two structural isomers were proposed for each acceptor, and a configurational (rotamer) for each structural isomer. A benchmarking was performed for relative energies, molecular planarity, light-harvesting features, frontier molecular orbitals alignment, electron-accepting indexes, reorganization energies, and average electrostatic potential. Mainly, structural isomerization yields the most significant modification to the studied properties and, to a lower extent, rotamerization. Nonetheless, the impact of rotamers might not be ignored, mainly in electron-accepting character and intermolecular electric field. Indeed, the modification that rotamers induce in some properties is comparable to that induced by the modification of halogen atoms.