High-performance Organic Solar Cells Research Articles

High-Performance Annealing-Free Polythiophene-Based Organic Solar Cells Enabled by Volatile Solid Additive

High-Performance Annealing-Free Polythiophene-Based Organic Solar Cells Enabled by Volatile Solid Additive

Dimerized Small Molecule Donor Enables Efficient Ternary Organic Solar Cells

Ternary organic solar cells (OSCs) are the feasible and efficient strategy to achieve the high-performance OSCs. It is of great significance to develop a superior third component candidate for constructing efficient ternary OSCs. In this work, we intelligently designed and synthesized a dimerized small molecule donor by connecting two asymmetric small molecule donors with the vinyl group, which is named DSMD-βV. This innovative oligomeric molecule DSMD-βV not only exhibits the complementary absorption and the cascade energy level arrangement with PM6 and BTP-eC9, but also regulates the phase separation micromorphology based on PM6:BTP-eC9. Consequently, PM6:DSMD-βV:BTP-eC9 based ternary device exhibits the improved exciton dissociation, charge transport and decreased recombination, thus achieving a superior power conversion efficiency (PCE) of 18.26%, surpassing PM6:BTP-eC9 based binary (17.63%). This work indicates that the dimerized small molecule donor is able to become a promising third component candidate, which also opens up a unique idea for the construction of efficient ternary organic solar cells.

Isomerization Engineering of Solid Additives Enables Highly Efficient Organic Solar Cells via Manipulating Molecular Stacking and Aggregation of Active Layer.

Morphology control is crucial in achieving high-performance organic solar cells (OSCs) and remains a major challenge in the field of OSC. Solid additive is an effective strategy to fine-tune morphology, however, the mechanism underlying isomeric solid additives on blend morphology and OSC performance is still vague and urgently requires further investigation. Herein, two solid additives based on pyridazine or pyrimidine as core units, M1 and M2, are designed and synthesized to explore working mechanism of the isomeric solid additives in OSCs. The smaller steric hindrance and larger dipole moment facilitate better π-π stacking and aggregation in M1-based active layer. The M1-treated all-small-molecule OSCs (ASM OSCs) obtain an impressive efficiency of 17.57%, ranking among the highest values for binary ASM OSCs, with 16.70% for M2-treated counterparts. Moreover, it is imperative to investigate whether the isomerization engineering of solid additives works in state-of-the-art polymer OSCs. M1-treated D18-Cl:PM6:L8-BO-based devices achieve an exceptional efficiency of 19.70% (certified as 19.34%), among the highest values for OSCs. The work provides deep insights into the design of solid additives and clarifies the potential working mechanism for optimizing the morphology and device performance through isomerization engineering of solid additives.

Precisely Regulating Intermolecular Interactions and Molecular Packing of Nonfused-Ring Electron Acceptors via Halogen Transposition for High-Performance Organic Solar Cells.

The structure of molecular aggregates is crucial for charge transport and photovoltaic performance in organic solar cells (OSCs). Herein, the intermolecular interactions and aggregated structures of nonfused-ring electron acceptors (NFREAs) are precisely regulated through a halogen transposition strategy, resulting in a noteworthy transformation from a 2D-layered structure to a 3D-interconnected packing network. Based on the 3D electron transport pathway, the binary and ternary devices deliver outstanding power conversion efficiencies (PCEs) of 17.46% and 18.24%, respectively, marking the highest value for NFREA-based OSCs.

Processing the Interlayer and Optimizing the Active Layer by One-Step Dissolution Compensation in Organic Solar Cells.

Optimized morphology of the active layer and electrode interface is critical for obtaining high-performance organic solar cells. However, achieving this typically involves a multifaceted, sequential process that renders outcomes unpredictable. Here, by exploiting the dissolution compensation, we propose a one-step method that integrates interlayer fabrication and a controllable morphology optimization. Taking an "out of the box" approach, we incorporate the good solvent of the active layer into the interlayer solution to act as dissolution compensation, breaking the orthogonal solvent principles to allow the morphology of the active layer to evolve to an optimized state while the interface layer is being processed. Using two commercially available material systems, D18:Y6 and D18:L8-BO, as examples, it was found that the JSC and fill factor (FF) device can be improved by using an appropriate ratio of the compensation solvent chloroform in the interlayer solution. As a result, the power conversion efficiency of the device based on the two state-of-the-art systems can be increased by about 7.5% (D18:Y6, from 17.04 to 18.31%; D18:L8-BO, from 17.97 to 19.31%). This one-step strategy has been shown to be universally applicable to other diverse systems and provides a simple yet reliable method for accurately depositing high-quality interlayers with an optimized active layer morphology in high-performance organic solar cells and other solution-processable organic electronics.

Non-Fused π-Extension of Endcaps of Small Molecular Acceptors Enabling High-Performance Organic Solar Cells.

The modular structure of small molecular acceptors (SMAs) allows for versatile modifications of the materials and boosts the photovoltaic efficiencies of organic solar cells (OSCs) in recent years. As a critical component, the endcaps of SMAs have been intensively investigated and modified to control the molecular aggregation and photo-electronic conversion. However, most of the studies focus on halogenation or π-fusion extension of the endcap moieties, but overlook the non-fused π-extension approach, which could be a promising strategy to balance the self-aggregation and compatibility behaviors. Herein, we reported two new acceptors namely BTP-Th and BTP-FTh based on non-fused π-extension of the endcap by chlorinated-thiophene, of which the latter molecule has better co-planarity and crystallinity because of the intramolecular noncovalent interactions. Paired with donor PBDB-T, the optimal device of BTP-FTh reveals a greater efficiency of 14.81% that that of BTP-Th (13.91%). Nevertheless, the BTP-Th based device realizes a lower energy loss, enabling BTP-Th as a good candidate to serve as guest acceptor. As a result, the ternary solar cells of PM6:BTP-eC9:BTP-Th output a champion efficiency up to 18.71% with enhanced open-circuit voltage. This study highlights the significance of rational decoration of endcaps for the design of high-performance SMAs and photovoltaic cells.

High Performance As-Cast Organic Solar Cells Enabled by a Refined Double-Fibril Network Morphology and Improved Dielectric Constant of Active Layer.

High performance organic solar cells (OSCs) are usually realized by using post-treatment and/or additive, which can induce the formation of metastable morphology, leading to unfavorable device stability. In terms of the industrial production, the development of high efficiency as-cast OSCs is crucially important, but it remains a great challenge to obtain appropriate active layer morphology and high power conversion efficiency (PCE). Here, efficient as-cast OSCs are constructed via introducing a new polymer acceptor PY-TPT with a high dielectric constant into the D18:L8-BO blend to form a double-fibril network morphology. Besides, the incorporation of PY-TPT enables an enhanced dielectric constant and lower exciton binding energy of active layer. Therefore, efficient exciton dissociation and charge transport are realized in D18:L8-BO:PY-TPT-based device, affording a record-high PCE of 18.60% and excellent photostability in absence of post-treatment. Moreover, green solvent-processed devices, thick-film (300nm) devices, and module (16.60 cm2) are fabricated, which show PCEs of 17.45%, 17.54%, and 13.84%, respectively. This work brings new insight into the construction of efficient as-cast devices, pushing forward the practical application of OSCs.

Conjugated polymers with thiazolothiazole as the acceptor unit for high performance organic solar cells

In this study, we used a simple, cost-effective, and high-yield synthetic route to successfully synthesize two thiazolothiazole-based wide-bandgap donor polymers, namely TTZ and ANTTZ. We systematically investigated how the solubility, absorption and photoelectric properties of the materials were influenced by the position of ester group at the thiophene unit as π-bridge. Theoretical calculations, UV–vis spectroscopy and GIWAXS results revealed that TTZ possesses planar molecular backbone and higher crystallinity. Ultimately, with BTP-ec9-4F as the acceptor, the TTZ based devices can achieve an impressive power conversion efficiency (PCE) of 13.96%; whereas the ANTTZ based devices can give a PCE of only 3.07%. This research underscores the effectiveness of a cost-efficient donor material synthesis route and highlights the crucial influence of the side chain position on crystallinity of the polymer, offering a new direction for designing low-cost, high-efficiency photovoltaic materials.

Synergistically manipulating the shape of alkyl-chain and asymmetric side groups of non-fullerene acceptors enables organic solar cells to reach 18.5% efficiency

Side-chain modification and asymmetric design for non-fullerene acceptors (NFAs) have been proven to be effective methods for harvesting high-performance organic solar cells (OSCs). Combining the two molecular design strategies, we adopted phenyl chain and alkyl chains with different shapes to develop two novel asymmetric NFAs, named BTP-P2EHC11 and BTP-P2EHC2C4. Compared with BTP-P2EHC2C4 attached 2-ethylhexyl side chain, BTP-P2EHC11 with linear alkyl side chain have slightly red-shifted absorption and intensive absorption strength. Moreover, the PM6:BTP-P2EHC11 blend film presents higher and more balanced charge mobilities, reducing charge recombination, tighter intermolecular packing and more favorable fibrous network morphology with appropriate phase separation than PM6:BTP-P2EHC2C4, which lead to significantly enhanced short-circuit current density (JSC) of PM6:BTP-P2EHC11-based devices. Thus, the OSCs based on PM6:BTP-P2EHC11 achieve a superior power conversion efficiency (PCE) of 18.50% with a good trade-off among open-circuit voltage (VOC) of 0.876 V, JSC of 26.85 mA cm−2 and fill factor (FF) of 78.65%, while PM6:BTP-P2EHC2C4-based device exhibits a lower PCE of 17.49%. Our investigation elucidates that the combination of finely optimizing the shape of alkyl-chain and asymmetric side groups of NFAs could pave a promising avenue toward morphology optimization and performance promotion of OSCs.

Computational method on highly efficient D-π-A-π-D-based different molecular acceptors for organic solar cells applications and non-linear optical behaviour

Eight molecular structures (BT-A1 to BT-A8) with high-performance non-fullerene acceptor (NFA) were selected for organic solar cells (OSCs) and non-linear optical (NLO) applications. Their electronic, photovoltaic (PV) and optoelectronic properties were tuned by adding powerful electron-withdrawing groups to the acceptor (A) of the D-π-A-π-D structure. Using time-dependent density functional theory (TD-DFT) techniques, based on the laws of quantum chemical calculations, the absorption spectra, stability of the highest and lowest-energy molecular orbitals (HOMO/LUMOs), electron density, intramolecular charge transfer (ICT), transition density matrix (TDM), were examined. The binding energy (Eb) and density of states (DOS) were probed to realize the optoelectronic analysis of the structures BT-A1 to BT-A8. Noncovalent interactions (NCIs) based on a reduced density gradient (RDG) were used to describe the nature and strength of D-A interactions in the molecules BT-A1 to BT-A8. The new refined molecules BT-A1 to BT-A8 exhibited strong absorbance bands between 408–721 nm and high electron transfer contribution (ETC) ranges between 87–96 %, along with the smallest excitation energies (Ex) between 1.71–3.55 eV in the solvent dichloromethane. Dipolar moment strengths ranging from 0.38 to 4.72 Debye in both the excited and ground states have determined with good solubility properties of BT-A1 to BT-A8 in polar solvent. Highly effective charge mobilities and prevention of charge recombination have been demonstrated by the electron (0.18–0.41 eV) and hole RE values (0.13–0.89 eV) for the new compounds. Power conversion efficiencies (PCE) of BT-A1 to BT-A8 were nearly the same because of better outcomes compared to the molecules in the BT. Compared to 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)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2–6-diyl)] (PTB7-Th), the open circuit voltages (Voc) of compounds BT-A1 to BT-A8 were ranged from 1.52 to 2.13 eV. The polarizability (α) and hyperpolarizability (β) of the molecules BT-A1 to BT-A8 were used to determine the non-linear optical (NLO) properties. The results showed that BT-A2, BT-A6 and BT-A7 have good NLO activity. This computational analysis demonstrates the superiority of the molecules with NFA. Hence the compounds are advised for the use in production of high-performance OSCs and NLO activity.

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.

On the role of asymmetric molecular geometry in high-performance organic solar cells

Although asymmetric molecular design has been widely demonstrated effective for organic photovoltaics (OPVs), the correlation between asymmetric molecular geometry and their optoelectronic properties is still unclear. To access this issue, we have designed and synthesized several symmetric-asymmetric non-fullerene acceptors (NFAs) pairs with identical physical and optoelectronic properties. Interestingly, we found that the asymmetric NFAs universally exhibited increased open-circuit voltage compared to their symmetric counterparts, due to the reduced non-radiative charge recombination. From our molecular-dynamic simulations, the asymmetric NFA naturally exhibits more diverse molecular interaction patterns at the donor (D):acceptor (A) interface as compared to the symmetric ones, as well as higher D:A interfacial charge-transfer state energy. Moreover, it is observed that the asymmetric structure can effectively suppress triplet state formation. These advantages enable a best efficiency of 18.80%, which is one of the champion results among binary OPVs. Therefore, this work unambiguously demonstrates the unique advantage of asymmetric molecular geometry, unveils the underlying mechanism, and highlights the manipulation of D:A interface as an important consideration for future molecular design.

P-Toluenesulfonic Acid Modified Two-Dimensional ZrSe2 as a Hole Transport Layer for High-Performance Organic Solar Cells.

Two-dimensional (2D) materials have attracted attention due to their excellent optoelectronic properties, but their applications are limited by their defects and vacancies. Surface modification is an effective method to restore their performance. Here, ZrSe2 is modified with conductive polymer p-toluenesulfonic acid (PTSA). It is found that PTSA can obtain electrons of ZrSe2 through the combination of -SO3H and ZrSe2, thus forming interfacial dipoles, which improve the work function of ZrSe2. In addition, -OH in PTSA can effectively fill the Se vacancy in ZrSe2 to form P-type doping, thereby improving its conductivity. ZrSe2 modified by the PTSA material is first used as a hole transport layer (HTL) in organic solar cells (OSCs). The efficiency of OSCs based on the PBDB-T:ITIC and PM6:L8-BO binary active layer with ZrSe2:PTSA as the novel HTL reaches 10.66 and 18.14%, which are obviously higher than the efficiency of OSCs with pure ZrSe2 as the HTL (8.48 and 15.64%). More interestingly, the stability of the device with ZrSe2:PTSA as HTL is significantly better than that of PEDOT:PSS. This study shows that the modification of the organic material can effectively improve the photoelectric performance of ZrSe2 and explores the physical mechanism of the interaction between the organic modifier and 2D materials.

2,5-dichloro-3,4-diiodothiophene as a versatile solid additive for high-performance organic solar cells

Volatile solid additive (SA) with diverse chemical structures has been proved to be an alternative to prepare high-efficient organic solar cells (OSCs). While, various organic photovoltaic materials raise challenges in selecting suitable SAs during the device optimization. Herein, based on the simple and commonly used thiophene unit, we proposed a perhalogenated 2,5-dichloro-3,4-diiodothiophene (SA-T5) as the SA for the device optimizations. As results, the capacity of SA-T5 in optimizing molecular packings of small-molecular acceptor L8-BO, dimeric acceptor DL8, and polymeric acceptor PY-DT based blend films has been demonstated. Their optimized morphologies assisted by SA-T5 contribute to the suppressed charge recombination and enhanced charge transportation, resulting in their improved short-circuit current density and fill factor, simultaneously. In comparsion with as-cast devices, SA-T5-treated devices showed significantly improved power conversion efficiencies (PCEs) of 18.8 % for PM6:L8-BO, 17.8 % for PM6:DL8, and 17.6 % for PM6:PY-DT, respectively. Furthermore, the potential of SA-T5 in obtaining high-performance ternary OSCs was also confirmed, for example, a 18.1 % efficiency was realized in PM6:DL8:L8-BO based device. To our knowledge, the performance of these SA-T5-treated devices reaches the best results of different acceptor-based OSCs. Importantly, this work provides a rare and successful case to develop versatile SAs for high-performance OSCs.

Solution-Processed Bilayered ZnO Electron Transport Layer for Efficient Inverted Non-Fullerene Organic Solar Cells

Organic solar cells (OSCs) are becoming increasingly popular in the scientific community because of their many desirable properties. These features include solution processability, low weight, low cost, and the ability to process on a wide scale using roll-to-roll technology. Enhancing the efficiency of photovoltaic systems, particularly high-performance OSCs, requires study into not only material design but also interface engineering. This study demonstrated that two different types of OSCs based on the PTB7-Th:IEICO-4F and PM6:Y6 active layers use a ZnO bilayer electron transport layer (ETL). The ZnO bilayer ETL comprises a ZnO nanoparticle (ZnO NP) and a ZnO layer created from a sol-gel. The effect of incorporating ZnO NPs into the electron transport layer (ETL) was studied; in particular, the effects on the electrical, optical, and morphological properties of the initial ZnO ETL were analyzed. The ability of ZnO films to carry charges is improved by the addition of ZnO nanoparticles (NPs), which increase their conductivity. The bilayer structure had better crystallinity and a smoother film surface than the single-layer sol-gel ZnO ETL. This led to a consistent and strong interfacial connection between the photoactive layer and the electron transport layer (ETL). Therefore, inverted organic solar cells (OSCs) with PTB7-Th:IEICO-4F and PM6:Y6 as photoactive layers exhibit improved power conversion efficiency and other photovoltaic properties when using the bilayer technique.

Balancing Flexible Side Chains on 2D Conjugated Acceptors Enables High-Performance Organic Solar Cell.

Balancing the rigid backbones and flexible side chains of light-harvesting materials is crucially important to reach optimized intermolecular packing, micromorphology, and thus photovoltaic performance of organic solar cells (OSCs). Herein, based on a distinctive CH-series acceptor platform with 2D conjugation extended backbones, a series of nonfullerene acceptors (CH-6F-Cn) are synthesized by delicately tuning the lengths of flexible side chains from n-octyl to n-amyl. A systemic investigation has revealed that the variation of the side chain's length can not only modulate intermolecular packing modes and crystallinity but also dramatically improve the micromorphology of the active layer and eventual photovoltaic parameters of OSCs. Consequently, the highest PCE of 18.73% can be achieved by OSCs employing D18:PM6:CH-6F-C8 as light-harvesting materials.

Improved efficiency of polymer solar cells using alcohol-soluble self-doped N-type polymers as cathode interface layer

Extensive research has been conducted on polymeric cathode interface substances, known for their self-doping features, for their application in organic solar cells (OSCs) to improve the ohmic interaction at the electrode with the active layer. In this paper, two novel polymers, PIIDN-F and PIIDN-FN, with self-doping effect, were successfully synthesized by combining isoindigo (IID), which contains an amino side chain, as an electrons-deficient group with fluorene, which contains different side chains. A thorough examination was conducted on the self-doping properties, electrical conductivity, work efficiency, and the angle of water contact between the two substances. Following this, PIIDN-F and PIIDN-FN were effectively utilized as cathode interface layers (CILs) within PTB7-Th:PC71BM OSCs. The PIIDN-F and PIIDN-FN achieve power conversion efficiencies (PCEs) of 8.97% and 9.04%, respectively. Findings indicate that the quantity of polar groups significantly influences the polymer's conductivity, adjustable work function, and the interaction at interfaces. These results show that by simply adjusting the number of polar groups, it is possible to provide efficient CILs for high-performance OSCs.

High-performance intrinsically stretchable organic solar cells based on flexible spacer incorporated dimerized small-molecule acceptors

High power conversion efficiency (PCE), long-term stability, and mechanical robustness are important requirements for the practical applications of organic solar cells (OSCs). Herein, we develop a series of flexible spacer (FS)-incorporated dimerized small-molecule acceptors (DSMAs; DYBT-C0, DYBT-C4, and DYBT-C8) and demonstrate high-performance OSCs with a high PCE of 18.6%, excellent mechanical robustness (crack-onset strain (COS) = 32%) and photostability (t80% lifetime = 1735 h under 1-sun illumination). The incorporation of aliphatic FS units with optimal length effectively reduces the backbone rigidity of the DSMAs and increases the fraction of intermixed domains in the blend films, while maintaining excellent electron transport properties. The DYBT-C4-based OSCs demonstrate higher PCE (18.6%) and stretchability (COS = 32%) compared to the OSCs based on the monomer acceptor (MYT; PCE = 15.9% and COS = 10%) and DSMA without FS units (DYBT-C0; PCE =17.2% and COS = 17%). In addition, due to the reduced diffusion coefficient and higher glass transition temperature of DYBT-C4, the DYBT-C4-based OSCs exhibit photostability significantly higher than that of the OSCs fabricated using MYT (t80% lifetime= 36 h). Consequently, DYBT-C4-based intrinsically stretchable (IS)-OSCs exhibit high device stretchability (strain at PCE80% = 36%) and PCE of 14.3%, demonstrating potential for wearable applications.

Synergistic Regulation of Crystallization Kinetics of Donor/Acceptor by New Volatile Additives for High Performance Organic Solar Cells

AbstractIdeal nanoscale morphology of heterojunction active layer is important for the development of organic solar cells (OSCs). However, the mismatched crystalline kinetic between the polymer donor and small molecular acceptor often leads to the difficulties in controlling the morphology of the active layer. Herein, polar 1,2‐dibromo‐4,5‐difluorobenzene (DFB) and non‐polar 1,4‐dibromotetrafluorobenzene (TFB) are developed as the volatile additives for OSCs. More attractively, different from the reported volatile additives, both new volatile additives can simultaneously interact with donor and acceptor, synergistic regulating the crystallization kinetic and well‐balancing the crystallization behaviors between the polymer donor and small molecular acceptor during film formation process. Notably, due to the stronger dipole‐dipole interactions with active layer, polar DFB induces the more favorable film morphology than non‐polar TFB. As a result, the two additives‐treated PM6:Y6 devices both outperform the CN‐treated device (16.13%), and the polar DFB‐treated device deliver a higher efficiency of 17.15% than non‐polar TFB‐treated one (16.30%). With polar DFB additive, PM6:L8‐BO and PM6: BTP‐eC9 also achieve superior efficiency of 18.46% and 18.17%, respectively. This work deepens the insights of regulating crystallization kinetics and optimizing nanoscale morphology by developing simple volatile additives for further achieving high‐efficient OSCs.