Highly Efficient Ternary Solar Cells with Efficient Förster Resonance Energy Transfer for Simultaneously Enhanced Photovoltaic Parameters

Introducing a third component into organic bulk heterojunction solar cells has become an effective strategy to improve photovoltaic performance. Meanwhile, the rapid development of non-fullerene acceptors (NFAs) has pushed the power conversion efficiency (PCE) of organic solar cells (OSCs) to a higher standard. Herein, a series of fullerene-free ternary solar cells are fabricated based on a wide bandgap acceptor, IDTT-M, together with a wide bandgap donor polymer PM6 and a narrow bandgap NFA Y6. Insights from the morphological and electronic characterizations reveal that IDTT-M has been incorporated into Y6 domains without disrupting its molecular packing and sacrificing its electron mobility and work synergistically with Y6 to regulate the packing pattern of PM6, leading to enhanced hole mobility and suppressed recombination. IDTT-M further functions as an energy-level mediator that increases open-circuit voltage (V_OC) in ternary devices. In addition, efficient Förster resonance energy transfer (FRET) between IDTT-M and Y6 provides a non-radiative pathway for facilitating exciton dissociation and charge collection. As a result, the optimized ternary device features a significantly improved PCE up to 16.63% with simultaneously enhanced short-circuit current (J_SC), V_OC, and fill factor (FF).     

Ternary organic solar cells with improved efficiency and stability enabled by compatible dual-acceptor strategy

To further elevate the power conversion efficiency (PCE) of organic solar cells (OSCs), ternary strategy is one of the most efficient methods via simply incorporating a suitable third component. Here, a nonfullerene small molecule acceptor MOITIC was incorporated into the state-of-art PM6:Y6 binary system to further enhance the photovoltaic performance. Detailed investigation revealed that MOITIC exhibited a good miscibility and compatibility with Y6, forming alloy-like acceptors in the ternary blends. The alloy-like phase promoted the phase separation and optimized the morphology of ternary blend, which afforded higher and more balanced carrier mobility and reduced charge recombination in devices. Moreover, the larger energy offset between PM6 and MOITIC:Y6 acceptor alloy is beneficial to enhance open-circuit voltage (V_oc) of corresponding devices. As a consequence, the optimized ternary OSC (PM6:Y6:MOITIC = 1:1:0.1) showed a significantly increased PCE of 17.1% with simultaneously enhanced V_oc of 0.882 V, short-circuit current density (J_sc) of 25.6 mA cm⁻², and fill factor (FF) of 75.7%, which has about 9% enhancement compared to the control binary PM6:Y6 (15.7%). In addition, the optimized ternary device exhibited better stability. This work indicates that ternary strategy via combining two compatible small molecule acceptors is effective to simultaneously improve the efficiency and stability of OSCs.     

High-performance alloy-like ternary organic solar cells with two compatible non-fullerene acceptors

Ternary blending is one of the effective strategies to modulate the blend film morphology for achieving high efficiency organic solar cells (OSCs). In this work, high-performance ternary OSCs are fabricated by introducing a non-fullerene acceptor, namely IDTP-4F into the PM6:Y6 binary system to enhance the device performance. Detailed investigations indicate that IDTP-4F can form an alloy phase with Y6, resulting in the optimized morphology, which can facilitate the charge transport and reduce recombination, leading to enhanced open-circuit voltage (V_oc) and fill factor (FF) simultaneously. Consequently, the optimized ternary OSCs exhibit an excellent power conversion efficiency (PCE) of 17.1%, which is much higher than that of PM6:Y6 binary OSCs (15.9%). These results indicate that combining two compatible non-fullerene acceptors is an effective strategy to fabricate high efficiency ternary OSCs.     

Smartly Optimizing Crystallinity,Compatibility, and Morphology for Polymer Solar Cells by Small Molecule Acceptor with Unique 2D-EDOT Side Chain

A desired morphology is essential for achieving efficient polymer solar cells. Donors and acceptors with appropriate crystallization can lead to a suitable phase-separated morphology for effective photocurrent generation process. Inspired by the success of Y6 acceptors and the 2D side chain engineering on popular polymer donors and small molecule acceptors, the usage of unique 2D 3,4-ethylene dioxythiophene (EDOT) side chains on Y6 to regulate its crystallinity, compatibility, and thus the related blend morphology is explored. In this study, two molecules of BTP-EDOT-4F and BTP-EDOT-4Cl with such unique 2D EDOT side chains are designed and synthesized. Due to the advantage of EDOT side chain, when these molecules are blended with PM6, the decent power conversion efficiencies (PCEs) of 16.78% and 15.87% are obtained. Furthermore, BTP-EDOT-4F is selected as the third component and added into PM6:L8-BO binary system to form ternary blends. The optimized crystallinity, compatibility, and morphology of such ternary blend are discovered in the presence of BTP-EDOT-4F, which enables efficient exciton dissociation and charge transport as well as decreased recombination, resulting in higher short circuit current density (J_sc) and fill factor. Finally, the outstanding PCE of 18.56% is achieved in ternary blends containing PM6, L8-BO, and BTP-EDOT-4F.     

Ternary Polymer Solar Cells with High Efficiency of 14.24% by Integrating Two Well‐Complementary Nonfullerene Acceptors

Ternary polymer solar cells (PSCs) are one of the most promising device architectures that maintains the simplicity of single‐junction devices and provides an important platform to better tailor the multiple performance parameters of PSCs. Herein, a ternary PSC system is reported employing a wide bandgap polymeric donor (PBTA‐PS) and two small molecular nonfullerene acceptors (labeled as LA1 and 6TIC). LA1 and 6TIC keep not only well‐matched absorption profiles but also the rational crystallization properties. As a result, the optimal ternary PSC delivers a state of the art power conversion efficiency (PCE) of 14.24%, over 40% higher than the two binary devices, resulting from the prominently increased short‐circuit current density (J_sc) of 22.33 mA cm^?2, moderate open‐circuit voltage (V_oc) of 0.84 V, and a superior fill factor approaching 76%. Notably, the outstanding PCE of the ternary PSC ranks one of the best among the reported ternary solar cells. The greatly improved performance of ternary PSCs mainly derives from combining the complementary properties such as absorption and crystallinity. This work highlights the great importance of the rational design of matched acceptors toward highly efficient ternary PSCs.     

Optical and electronic property tailoring by MoS2-polymer hybrid solar cell

The ternary blend system such as binary donor and an acceptor or binary acceptor and a donor offers a way to improve the power conversion efficiency of the polymer solar cells (PSCs) by enhancing optical properties and electrical properties. In this work, PTB7, PC₇₁BM and Molybdenum disulfide nano-sheet (MoS₂NS) ternary blend system were investigated as an active material for OPV. The optimized ternary blend system showed increment of 17% power conversion efficiency (PCE) from 6.98% to 8.18%. The origin of improved PCE mainly arises from the significant increment in J_SC and marginal change in V_OC and FF. This improved PCE is due to increased light harvesting and improved charge carrier mobility in the active matrix. The marginal enhancement in V_OC and FF was correlated with the density of trap states (DOS) obtained from capacitance measurement of the device. The optical absorption and energy transfer mechanism of the ternary blend film is explained by absorption and photoluminescence measurement respectively. Further, the conversion efficiency due to improved charge carrier transport was described by modified SCLC mobility measurements for electron and hole only devices. The obtained result suggests that presence of MoS₂NS along with PTB7:PC₇₁BM binary system play dual role like an improved charge transport layer as well as light harvesting.     

High‐Performance Pseudoplanar Heterojunction Ternary Organic Solar Cells with Nonfullerene Alloyed Acceptor

The vast majority of ternary organic solar cells are obtained by simply fabricating bulk heterojunction (BHJ) active layers. Due to the inappropriate distribution of donors and acceptors in the vertical direction, a new method by fabricating pseudoplanar heterojunction (PPHJ) ternary organic solar cells is proposed to better modulate the morphology of active layer. The pseudoplanar heterojunction ternary organic solar cells (P‐ternary) are fabricated by a sequential solution treatment technique, in which the donor and acceptor mixture blends are sequentially spin‐coated. As a consequence, a higher power conversion efficiency (PCE) of 14.2% is achieved with a V_oc of 0.79 V, J_sc of 25.6 mA cm^?2, and fill factor (FF) of 69.8% compared with the ternary BHJ system of 13.8%. At the same time, the alloyed acceptor is likely formed between two the acceptors through a series of in‐depth explorations. This work suggests that nonfullerene alloyed acceptor may have great potential to realize effective P‐ternary organic solar cells.     

Fused-ring acceptors based on quinoxaline unit for highly efficient single-junction organic solar cells with low charge recombination

Two non-fullerene small molecule acceptors (TFQ-F and TFQ-Cl) based on quinoxaline unit were designed and synthesized for efficient organic solar cells (OSCs). These two acceptors showed intense absorption up to 900 nm and high thermal stabilities with decomposition temperatures over 360 °C due to their fused-ring skeletons. TFQ-F and TFQ-Cl are the A-D-A′-D-A type acceptors (A/A′ for acceptor unit and D for donor unit). TFQ-F and TFQ-Cl have the same D-A′-D fragment, which was flanked with different ending groups. The effect of different ending groups on their photophysical properties, electrochemical behaviors, micro-structures and charge recombination properties of active layers, and device performance were investigated systematically. PM6 with the complementary absorption to the two acceptors was used as the donor material. The pristine PM6:TFQ-F blend films displayed the optimal morphologies as revealed by AFM and TEM measurement. Organic solar cells based on PM6:TFQ-Cl blend film showed high J_SC of 25.19 mA/cm² and PCE of 13.2%. The Voc, J_SC and PCE for PM6:TFQ-F film based device were 0.857 V, 23.70 mA/cm² and 13.51%, respectively. The dependence of V_OC/J_SC on various light intensities indicated that PM6:TFQ-F/Cl based device had low charge recombination.     

New soluble porphyrin bearing a pyridinylethynyl group as donor for bulk heterojunction solar cells

Bulk heterojunction solar cells were fabricated using the blend films of a porphyrin bearing pyridinylethynyl group (POR) as electron donor and PC₆₀BM or PC₇₀BM as electron acceptor. Photoluminescence measurement of the blend films of POR with fullerene derivatives indicated that charge transfer was possible between POR and fullerene derivatives. The solution processed bulk heterojunction solar cells using the blend of POR with PC₆₀BM and PC₇₀BM exhibit overall power conversion efficiency (PCE) of 1.96% and 2.54%, respectively. The PCE of the BHJ solar cell has been further improved up to 3.27% when thermally annealed POR:PC₇₀BM was used as active layer, which is attributed mainly to the increase in short circuit current. The increase in J_sc is attributed to the enhanced crystallinity of the blend (particularly POR) and efficient π-electron conjugation of POR, resulting to an improvement in hole mobility, leading to more balance charge transport. The PCE of the device based on as cast POR:PC₇₀BM has been further improved up to 4.06% when DMF treated PEDOT:PSS buffer layer was used.     

A simple and effective method via PH1000 modified Ag-Nanowires electrode enable efficient flexible nonfullerene organic solar cells

Flexible transparent electrodes (FTEs) play an important role in determining the performance of flexible organic solar cells (OSCs), Ag-nanowires (AgNWs) with the unique merits of high conductivity, excellent flexibility, and good thermal stability has been taken into more consideration in fabricating highly efficient FTEs. However, the pristine AgNWs film usually suffers a huge surface roughness and incompatibility with the organic absorption layer, thus always leads to a poor power conversion efficiency (PCE). Herein, we demonstrated a simple and effective way through employing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PH1000) to modify the surface of AgNWs to prepare high-quality FTEs. Based on the PH1000 (100 nm)/AgNWs FTEs, the optimized flexible OSC with PM6:Y6 as active layer exhibits a highest PCE of 12.71%, with an open-circuit voltage (V_oc) of 0.814 V, a short-circuit current (J_sc) of 22.61 mA/cm², and a fill factor (FF) of 0.691, respectively. Which is much higher than the PCE (7.20%) of pristine AgNWs FTEs based device. The enhanced device performance was attributed to the improved morphologies both of the FTEs and the active layers, more effective charge transport and collection efficiency, as well as the decreased charge recombination properties. This work provides an efficient way to fabricate high-quality FTEs and realize efficient flexible OSCs.     

A Novel Wide‐Bandgap Polymer with Deep Ionization Potential Enables Exceeding 16% Efficiency in Ternary Nonfullerene Polymer Solar Cells

Ternary strategies have attracted extensive attention due to their potential in improving power conversion efficiencies (PCEs) of single‐junction polymer solar cells (PSCs). In this work, a novel wide bandgap polymer donor (E_g^opt ≈ 2.0 eV) named PBT(E)BTz with a deep highest occupied molecular orbital (HOMO) level (≈?5.73 eV) is designed and synthesized. PBT(E)BTz is first incorporated as the third component into the classic PBDB‐T‐SF:IT‐4F binary PSC system to fabricate efficient ternary PSCs. A higher PCE of 13.19% is achieved in the ternary PSCs with a 5% addition of PBT(E)BTz over binary PSCs (12.14%). Similarly, addition of PBT(E)BTz improves the PCE for PBDB‐T:IT‐M binary PSCs from 10.50% to 11.06%. The study shows that the improved PCE in ternary PSCs is mainly attributed to the suppressed charge carrier recombination and more balanced charge transport. The generality of PBT(E)BTz as a third component is further evidenced in another efficient binary PSC system—PBDB‐TF:BTP‐4Cl: an optimized PCE of 16.26% is realized in the ternary devices. This work shows that PBT(E)BTz possessing a deep HOMO level as an additional component is an effective ternary PSC construction strategy toward enhancing device performance. Furthermore, the ternary device with 5% PBT(E)BTz displays better thermal and light stability over binary devices.     

End-chain effects of non-fullerene acceptors on polymer solar cells

Four acceptor1-acceptor2-donor-acceptor2-acceptor1 (A1-A2-D-A2-A1) structural electron acceptors with different end-chains were designed and synthesized which all possessed indacenodithiophene (IDT) core, benzothiadiazole (BT) bridge as acceptor2, and rhodanine (R) end groups as acceptor1. The non-fullerene acceptor attached with ethyl group is called IDT-BT-R2 and used as control compound. And the other three of them are attached with methoxymethyl, trifluoroethyl and 1-piperidino groups generating IDT-BT-RO, IDT-BT-RF3 and IDT-BT-RN, respectively. The influence of end-chains on their optoelectronic properties were compared between four non-fullerene acceptors. Compared with IDT-BT-R2, the molecule IDT-BT-RF3 show red-shifted light absorption and lower LUMO level because of the electron withdrawing property of fluorine atoms. OSCs based on IDT-BT-RF3 display more efficient charge separation and lower degree of monomolecular recombination, allowing OSCs to show higher short-circuit current (J_sc) than the system of IDT-BT-R2. OSCs based on IDT-BT-RO also show more efficient charge separation and less monomolecular recombination. Due to the elevated LUMO level of the acceptor IDT-BT-RN, organic solar cells (OSCs) utilizing this material as acceptor display high open-circuit voltage (V_oc) of 1.10 eV and low energy loss of 0.49 eV when maintaining a relatively high power conversion efficiency (PCE) of 7.09%. We demonstrated that the end-chain engineering could finely tune the light absorption properties and energy levels of novel non-fullerene acceptors and eventually improved OSCs performance can be harvested.     

Rational Mutual Interactions in Ternary Systems Enable High-Performance Organic Solar Cells

Ternary organic solar cells (TOSCs) offer a facile and efficient approach to increase the power conversion efficiencies (PCEs). However, the critical roles that guest components play in complicated ternary systems remain poorly understood. Herein, two acceptors named LA1 and LA9 with differing crystallinity are investigated. The overly crystalline LA9 induces large self-aggregates in PM6:LA9 binary system, resulting in a lower PCE (13.12%) compared to PM6:LA1 device (13.89%). Encouragingly, both acceptors are verified as efficient guest candidates into the host binary PM6:NCBDT-4Cl (PCE = 13.48%) and afford markedly improved PCEs up to 15.39% and 15.75% in LA1 and LA9 ternary devices, respectively. Interestingly, the higher crystallinity LA9 reveals smaller interaction energies with both the host acceptor and donor PM6. Compared to LA1, the appropriate mutual interactions in the LA9 ternary system not only induces the orderly crystallinity of PM6 but also better compatibility with the host acceptor, generating further optimized molecular orientations and ternary morphology. Therefore, enhanced charge transport and minimized recombination loss are detected in LA9 ternary devices, affording the most competitive performance among Y6-sbsent TOSCs. This work suggests that complicated intermolecular interactions should be seriously considered when fabricating state-of-the-art multiple components OSCs.     

Donor–acceptor–acceptor–donor small molecules for solution processed bulk heterojunction solar cells

We report on the optical and electrochemical characterization (experimental and theoretical) of two donor substituted benzothiadiazole with different cyano based acceptor π-linkers, tetracyanobutadiene (TCBD) SM1 and dicyanoquinomethane (DCNQ) SM2, and explore them as the donor component for solution processed bulk heterojunction organic solar cells, along with PC₇₁BM as the electron acceptor. The solution bulk heterojunction (BHJ) solar cells based on dichloromethane (DCM) processed active layer with SM1 and SM2 as donor and PC₇₁BM as acceptor achieve power conversion efficiency (PCE) of 2.76% and 3.61%, respectively. The solar cells based on these two small molecules exhibit good Voc, which is attributed to their deep HOMO energy level. The higher PCE of the device based on SM2 compared to SM1 is attributed to the its small bandgap, broader absorption profile and enhanced hole mobility. Additionally, the PCE of the SM2:PC₇₁BM based solar cells processed with 1-chloronaphthalene CN (3 v%)/DCM is further improved reaching upto 4.86%. This increase in PCE has been attributed to the improved nanoscale morphology and more balanced charge transport in the device, due to the solvent additive.     

An A-D-D-A-type small-molecule electron acceptor with chlorine substitution for high-efficiency polymer solar cells

Chlorination is a very effective technique to adjust molecular energy levels, absorption spectra and intermolecular π–π stacking of small-molecule acceptors (SMAs). On this basis, a new acceptor-donor-donor-acceptor (A-D-D-A)-type SMA IDT2-IC-4Cl with chlorinated end units was developed. Compared with the unchlorinated counterpart (IDT2-IC), the IDT2-IC-4Cl exhibited an efficient absorption ability in the range of 550–900 nm region. Moreover, the blend films of PBDB-T:IDT2-IC-4Cl exhibited better charge generation properties and more balanced charge mobilities as compared to those of PBDB-T:IDT2-IC blend films. Polymer solar cells (PSCs) based on PBDB-T:IDT2-IC-4Cl exhibited a power conversion efficiency (PCE) of 12.53% with a short-circuit current (J_sc) of 22.22 mA cm⁻² and a fill factor (FF) of 69.81, while the PBDB-T:IDT2-IC device yielded a PCE of 8.18% with a J_sc of 13.23 mA cm⁻² and a FF of 65.71. The results show that chlorination is an effective way to obtain high-performance SMAs.     

Improving charge transport and suppressing charge recombination in small molecule ternary solar cells via incorporating Bis-PC71BM as a cascade material

The development of small molecule organic solar cells (SMOSCs) has attracted considerable attention and achieved comparable power conversion efficiency (PCE) with polymer solar cells. Here, we demonstrate a bulk heterojunction (BHJ) small molecular solar cell with PCE of 5.31% by incorporating Bisadduct of phenyl-C₇₁-butyric acid methyl ester (Bis-PC₇₁BM) as an additional acceptor material into the host binary blend of 2-[4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl]-4-[(4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl)-2,5-dien-1-ylidene]-3-oxocyclobut-1-en-1-olate (SQ-BP): [6,6]-phenyl C₇₁ butyric acid methyl ester (PC₇₁BM). The short circuit current (J_SC) and the fill factor (FF) of ternary SMOSCs are improved by decreasing the carrier recombination loss, increasing exciton dissociation and enhancing the carrier transport. The transient photovoltage (TPV) measurement indicates that the gradient HOMO energy alignment suppresses the charge recombination and leads to the increased charge carrier lifetime in ternary SMOSCs. As a result, the PCE of ternary devices with 5 wt% Bis-PC₇₁BM is about 20% greater than that of SQ-BP: PC₇₁BM based binary SMOSCs.     

Efficient co-sensitization of dye-sensitized solar cells by novel porphyrin/triazine dye and tertiary aryl-amine organic dye

A novel porphyrin dye ZnP-triazine-(gly)₂, consisting of a zinc-metallated porphyrin unit covalently linked through its peripheral aryl-amino group with a 1,3,5-triazine group which is functionalized by two carboxylic acid groups of glycine moieties, has been synthesized. Photophysical and electrochemical measurements, as well as theoretical DFT calculations, suggest that the compound exhibits appropriate light absorption characteristics and frontier molecular orbital levels for use as sensitizer in dye-sensitized solar cells (DSSCs). The ZnP-triazine-(gly)₂ based solar cell was found to exhibit a power conversion efficiency (PCE) value of 4.72%. A significant improvement of the overall photovoltaic efficiency of the solar cell was achieved up to 7.34% upon co-sensitization with a tertiary aryl-amine D with two ethynyl-pyridine substituents and cyano-acetic acid anchoring group, which exhibits complementary light absorption characteristics with the porphyrin dye. The higher PCE value of the co-sensitized solar cell is attributed to its enhanced short circuit current (J_sc), which is due to improved light harvesting efficiency, reduced porphyrin aggregation, and faster electron injection and charge collection, as well as its enhanced open circuit voltage (V_oc), which is due to increased electron density in the TiO₂ conduction band of the photoanode. These results are in accordance with electrochemical impedance spectra (EIS) of the solar cells, which revealed higher charge recombination resistance (R_rec), longer electron lifetime (τ_e), and shorter electron transport time (τ_d) for the co-sensitized solar cell.     

Highly Efficient Ternary All-Polymer Solar Cells with Enhanced Stability

Developing organic solar cells (OSCs) based on a ternary active layer is one of the most effective approaches to maximize light harvesting and improve their photovoltaic performance. However, this strategy meets very limited success in all-polymer solar cells (all-PSCs) due to the scarcity of narrow bandgap polymer acceptors and the challenge of morphology optimization. In fact, the power conversion efficiencies (PCEs) of ternary all-PSCs even lag behind binary all-PSCs. Herein, highly efficient ternary all-PSCs are realized based on an ultranarrow bandgap (ultra-NBG) polymer acceptor DCNBT-TPC, a medium bandgap polymer donor PTB7-Th, and a wide bandgap polymer donor PBDB-T. The optimized ternary all-PSCs yield an excellent PCE of 12.1% with a remarkable short-circuit current density of 21.9 mA cm⁻². In fact, this PCE is the highest value reported for ternary all-PSCs and is much higher than those of the corresponding binary all-PSCs. Moreover, the optimized ternary all-PSCs show a photostability with ≈ 68% of the initial PCE retained after 400 h illumination, which is more stable than the binary all-PSCs. This work demonstrates that the utilization of a ternary all-polymer system based on ultra-NBG polymer acceptor blended with compatible polymer donors is an effective strategy to advance the field of all-PSCs.     

Utilizing intermixing of conjugated polymer and fullerene from sequential solution processing for efficient polymer solar cells

Efficient polymer solar cells based on poly[2, 6-(4, 4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-fluorobenzothiadiazole)] (PCPDTFBT) and [6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) are successfully fabricated by a sequential processing (SqP). With appropriate orthogonal solvent and thermal treatment, the SqP film can form an inter-diffused layer, and the SqP devices show efficient photovoltaic performance in both conventional and inverted layouts. The SqP inverted device was firstly demonstrated and the highest power conversion efficiency (PCE) of 5.84% with the enhanced J_sc of 16.4 mA cm⁻² was able to be achieved with the high internal quantum efficiency (IQE). Photoluminescence quenching shows the SqP films can provide efficient exciton quenching. X-ray photoemission spectroscopy (XPS) and ellipsometry analysis shows a polymer-rich surface in SqP films after thermal annealing. The charge mobilities in the SqP films were significantly enhanced as measured by space-charge-limited-current (SCLC) method. All these contribute to the improved photovoltaic performance in the inverted SqP device. We believe that these results inspire a new way of forming the active layer with controllable morphology, efficient charge separation and collection in polymer solar cells.     

Releasing Acceptor from Donor Matrix to Accelerate Crystallization Kinetics with a Second Donor toward High-Efficiency Green-Printable Organic Photovoltaics

The state-of-the-art power conversion efficiency (PCE) of organic solar cells (OSCs) is typically achieved in the devices fabricated by toxic halogen solvents with complex post-treatment processes in strictly inert atmosphere. Developing suitable processing method for printing in ambient air using eco-friendly solvents with continuous solution supply and fabricating efficient devices without any post-treatment are intensively desired. Controlling the crystallization kinetics to fine-tune the acceptor's assembly behavior with a second donor for favorable morphological evolution is an effective approach to achieve above requirements. Herein, a kinetics-controlling strategy is implemented by introducing a strong crystalline small molecule, BTR-Cl, to enhance the crystallinity of acceptors. The combined in situ spectra characterizations revealed that the earlier aggregation of acceptor and modulation in conformation of PM6 can be achieved. This unique aggregation behavior facilitated enhanced film crystallization with reduced paracrystallinity of π–π stacking, resulting in improved charge transport and inhibited charge recombination. An outstanding PCE of 17.50% is obtained for the device processed with o-xylene via ambient air printing without any post-treatment. More significantly, efficient all-printed inverted devices and large-area modules are prepared. The generalization of this strategy has been confirmed in other efficient systems, suggesting a great potential for universally fabricating high-efficiency and eco-friendly OSCs.