Delicate Morphology Control Triggers 14.7% Efficiency All‐Small‐Molecule Organic Solar Cells

Morphology is a critical factor to determine the photovoltaic performance of organic solar cells (OSCs). However, delicately fine‐tuning the morphology involving only small molecules is an extremely challenging task. Herein, a simple, generic, and effective concentration‐induced morphology manipulation approach is demonstrated to prompt both the state‐of‐the‐art thin‐film BTR‐Cl:Y6 and thick‐film BTR:PC₇₁BM all‐small‐molecule (ASM) OSCs to a record level. The morphology is delicately controlled by subtly altering the prepared solution concentration but maintaining the identical active layer thickness. The remarkable performance enhancement achieved by this approach mainly results from the enhanced absorption, reduced trap‐assistant recombination, increased crystallinity, and optimized phase‐separated network. These findings demonstrate that a concentration‐induced morphology manipulation strategy can further propel the reported best‐performing ASM OSCs to a brand‐new level, and provide a promising way to delicately control the morphology towards high‐performance ASM OSCs.     

Higher Mobility and Carrier Lifetimes in Solution‐Processable Small‐Molecule Ternary Solar Cells with 11% Efficiency

Solution‐processed small molecule (SM) solar cells have the prospect to outperform their polymer‐fullerene counterparts. Considering that both SM donors/acceptors absorb in visible spectral range, higher expected photocurrents should in principle translate into higher power conversion efficiencies (PCEs). However, limited bulk‐heterojunction (BHJ) charge carrier mobility (<10^‐4 cm² V^‐1 s^‐1) and carrier lifetimes (<1 µs) often impose active layer thickness constraints on BHJ devices (≈100 nm), limiting external quantum efficiencies (EQEs) and photocurrent, and making large‐scale processing techniques particularly challenging. In this report, it is shown that ternary BHJs composed of the SM donor DR3TBDTT (DR3), the SM acceptor ICC6 and the fullerene acceptor PC₇₁BM can be used to achieve SM‐based ternary BHJ solar cells with active layer thicknesses >200 nm and PCEs nearing 11%. The examinations show that these remarkable figures are the result of i) significantly improved electron mobility (8.2 × 10^‐4 cm² V^‐1 s^‐1), ii) longer carrier lifetimes (2.4 µs), and iii) reduced geminate recombination within BHJ active layers to which PC₇₁BM has been added as ternary component. Optically thick (up to ≈500 nm) devices are shown to maintain PCEs >8%, and optimized DR3:ICC6:PC₇₁BM solar cells demonstrate long‐term shelf stability (dark) for >1000 h, in 55% humidity air environment.     

All‐Polymer Solar Cells with over 12% Efficiency and a Small Voltage Loss Enabled by a Polymer Acceptor Based on an Extended Fused Ring Core

Although the field of all‐polymer solar cells (all‐PSCs) has seen rapid progress in device efficiencies during the past few years, there are limited choices of polymer acceptors that exhibit strong absorption in the near‐IR region and achieve high open‐circuit voltage (V_OC) at the same time. In this paper, an all‐PSC device is demonstrated with a 12.06% efficiency based on a new polymer acceptor (named PT‐IDTTIC) that exhibits strong absorption (maximum absorption coefficient: 2.41 × 10⁵ cm^?1) and a narrow optical bandgap (1.49 eV). Compared to previously reported polymer acceptors such as those based on the indacenodithiophene (IDT) core, the indacenodithienothiophene (IDTT) core has further extended fused ring, providing the polymer with extended absorption into the near‐IR region and also increases the electron mobility of the polymer. By blending PT‐IDTTIC with the donor polymer, PM6, a high‐efficiency all‐PSC is achieved with a small voltage loss of 0.52 V, without sacrificing J_SC and FF, which demonstrates the great potential of high‐performance all‐PSCs.     

Constructing High‐Performance All‐Small‐Molecule Ternary Solar Cells with the Same Third Component but Different Mechanisms for Fullerene and Non‐fullerene Systems

Two types of all‐small‐molecule ternary solar cells consisting of two small‐molecule donors and one acceptor (fullerene/non‐fullerene) are developed. Interestingly, both these devices have a common component: a carefully designed medium bandgap small molecule, which possesses appropriate energy levels and displays good compatibility with the host donor. In the fullerene system, the charge‐relaying role of the additive donor is confirmed by the improved charge transportation and suppressed charge recombination. While in the non‐fullerene system, the mixed face‐on and edge‐on orientation of the ternary film induced by the additive donor dominates the promotion of charge transportation. Accordingly, both ternary devices deliver higher short‐circuit current density, fill factor, and power conversion efficiencies of over 10% compared to binary ones. This work offers a promising guideline on the construction of high‐performance all‐small‐molecule ternary solar cells by incorporating a miscible small‐molecule donor.     

From Binary to Ternary: Improving the External Quantum Efficiency of Small‐Molecule Acceptor‐Based Polymer Solar Cells with a Minute Amount of Fullerene Sensitization

Ternary blend is proved to be a potential contender for achieving high efficiency in organic photovoltaics, which can apparently strengthen the absorption of active layer so as to better harvest light irradiation. Much of the previous work in ternary polymer solar cells focuses on broadening the absorption spectrum; however, a new insight is brought to study the third component, which in tiny amounts influents the small‐molecule acceptor‐based device performance. Without contributing to complementing the absorption, a minute amount of fullerene derivative, Bis‐PC₇₀BM, can effectively play an impressive role as sensitizer in enhancing the external quantum efficiency of the host binary blend, especially for polymeric donor. Detailed investigations reveal that the minute addition of Bis‐PC₇₀BM can realize morphology modification as well as facilitate electron transfer from polymeric donor to small molecule acceptor via cascade energy level modulation, and therefore lead to an improvement in device efficiency.     

Improve the Performance of the All‐Small‐Molecule Nonfullerene Organic Solar Cells through Enhancing the Crystallinity of Acceptors

Significant development has been achieved in nonfullerene organic solar cells. However, most of the high‐efficiency nonfullerene systems are composed of polymer donors and fused‐ring acceptors, and only a few small molecule donors can work well. Herein, a new A–D–A small molecule donor named NDTSR with naphtho[1,2‐b:5,6‐b′]dithiophene (NDT) as building blocks is synthesized. Two energy levels well‐matched fused‐ring acceptors ITIC and IDIC are chosen to construct all‐small‐molecule solar cells with NDTSR, respectively. When mixed with IDIC, a high power conversion efficiency (PCE) of 8.05% is achieved, which is the highest efficiency for NDT‐based small molecule donor. However, the NDTSR:ITIC system only exhibits a low PCE of 1.77%. The big difference in the performance of these two systems should be attributed to the different morphology and phase separation resulting from the crystallinity and aggregation ability of the acceptors. The results demonstrate that NDT‐based small molecule is a promising candidate donor for all‐small‐molecule systems, while the crystallinity of fused‐ring acceptors is a critical factor for optimizing the phase separation in the active layer.     

Ternary Blended Fullerene‐Free Polymer Solar Cells with 16.5% Efficiency Enabled with a Higher‐LUMO‐Level Acceptor to Improve Film Morphology

Ternary approaches to solar cell design utilizing a small bandgap nonfullerene acceptor as the near infrared absorber to increase the short‐circuit current density always decreases the open‐circuit voltage. Herein, a highly efficient polymer solar cell with an impressive efficiency of 16.28 ± 0.20% enabled by an effective voltage‐increased ternary blended fullerene‐free material approach is reported. In this approach, the structural similarity between the host and the higher‐LUMO‐level guest enables the two acceptors to be synergized, obtaining increased open‐circuit voltage and fill factor and a small increase of short‐circuit current density. The same beneficial effects are demonstrated by using two host binary systems. The homogeneous fine film morphologies and the π–π stacking patterns of the host blend are well maintained, while larger donor and acceptor phases and increased lamellar crystallinity, increased charge mobilities, and reduced monomolecular recombination can be achieved upon addition of the guest nonfullerene acceptor. The increased charge mobilities and reduced monomolecular recombination not only contribute to the improved fill factor but also enable the best devices to be fabricated with a relatively thicker ternary blended active layer (110 vs 100 nm). This, combined with the absorption from the added guest acceptor, contribute to the increased short‐circuit current.     

Green‐Solvent‐Processed All‐Polymer Solar Cells Containing a Perylene Diimide‐Based Acceptor with an Efficiency over 6.5%

To realize high power conversion efficiencies (PCEs) in green‐solvent‐processed all‐polymer solar cells (All‐PSCs), a long alkyl chain modified perylene diimide (PDI)‐based polymer acceptor PPDIODT with superior solubility in nonhalogenated solvents is synthesized. A properly matched PBDT‐TS1 is selected as the polymer donor due to the red‐shifted light absorption and low‐lying energy level in order to achieve the complementary absorption spectrum and matched energy level between polymer donor and polymer acceptor. By utilizing anisole as the processing solvent, an optimal efficiency of 5.43% is realized in PBDT‐TS1/PPDIODT‐based All‐PSC with conventional configuration, which is comparable with that of All‐PSCs processed by the widely used binary solvent. Due to the utilization of an inverted device configuration, the PCE is further increased to over 6.5% efficiency. Notably, the best‐performing PCE of 6.58% is the highest value for All‐PSCs employing PDI‐based polymer acceptors and green‐solvent‐processed All‐PSCs. The excellent photovoltaic performance is mainly attributed to a favorable vertical phase distribution, a higher exciton dissociation efficiency (P_diss) in the blend film, and a higher electrode carrier collection efficiency. Overall, the combination of rational molecular designing, material selection, and device engineering will motivate the efficiency breakthrough in green‐solvent‐processed All‐PSCs.     

8.0% Efficient All‐Polymer Solar Cells with High Photovoltage of 1.1 V and Internal Quantum Efficiency near Unity

In very recent years, growing efforts have been devoted to the development of all‐polymer solar cells (all‐PSCs). One of the advantages of all‐PSCs over the fullerene‐based PSCs is the versatile design of both donor and acceptor polymers which allows the optimization of energy levels to maximize the open‐circuit voltage (V_oc). However, there is no successful example of all‐PSCs with both high V_oc over 1 V and high power conversion efficiency (PCE) up to 8% reported so far. In this work, a combination of a donor polymer poly[4,8‐bis(5‐(2‐octylthio)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(5‐(2‐ethylhexyl)‐4H‐thieno[3,4‐c]pyrrole‐4,6(5H)‐dione)‐1,3‐diyl] (PBDTS‐TPD) with a low‐lying highest occupied molecular orbital level and an acceptor polymer poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐thiophene‐2,5‐diyl] (PNDI‐T) with a high‐lying lowest unoccupied molecular orbital level is used, realizing high‐performance all‐PSCs with simultaneously high V_oc of 1.1 V and high PCE of 8.0%, and surpassing the performance of the corresponding PC₇₁BM‐based PSCs. The PBDTS‐TPD:PNDI‐T all‐PSCs achieve a maximum internal quantum efficiency of 95% at 450 nm, which reveals that almost all the absorbed photons can be converted into free charges and collected by electrodes. This work demonstrates the advantages of all‐PSCs by incorporating proper donor and acceptor polymers to boost both V_oc and PCEs.     

Carrier Transport and Recombination in Efficient “All‐Small‐Molecule” Solar Cells with the Nonfullerene Acceptor IDTBR

Reaching device efficiencies that can rival those of polymer‐fullerene Bulk Heterojunction (BHJ) solar cells (>10%) remains challenging with the “All‐Small‐Molecule” (All‐SM) approach, in part because of (i) the morphological limitations that prevail in the absence of polymer and (ii) the difficulty to raise and balance out carrier mobilities across the active layer. In this report, the authors show that blends of the SM donor DR3TBDTT (DR3) and the nonfullerene SM acceptor O‐IDTBR are conducive to “All‐SM” BHJ solar cells with high open‐circuit voltages (V_OC) >1.1 V and PCEs as high as 6.4% (avg. 6.1%) when the active layers are subjected to a post‐processing solvent vapor‐annealing (SVA) step with dimethyl disulfide (DMDS). Combining electron energy loss spectroscopy (EELS) analyses and systematic carrier recombination examinations, the authors show that SVA treatments with DMDS play a determining role in improving charge transport and reducing non‐geminate recombination for the DR3:O‐IDTBR system. Correlating the experimental results and device simulations, it is found that substantially higher BHJ solar cell efficiencies of >12% can be achieved if the IQE and carrier mobilities of the active layer are increased to >85% and >10^?4 cm² V^?1 s^?1, respectively, while suppressing the recombination rate constant k to <10^?12 cm³ s^?1.     

Roll‐to‐Roll Printed Large‐Area All‐Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

The challenge of continuous printing in high‐efficiency large‐area organic solar cells is a key limiting factor for their widespread adoption. A materials design concept for achieving large‐area, solution‐coated all‐polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor is presented. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small‐scale solution shearing coater to a large‐scale continuous roll‐to‐roll (R2R) printer. Large‐area all‐polymer solar cells are continuously roll‐to‐roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm². This is among the highest efficiencies realized with R2R‐coated active layer organic materials on flexible substrate.     

Effects of Solvent Additives on Morphology,Charge Generation,Transport, and Recombination in Solution‐Processed Small‐Molecule Solar Cells

The effects of solvent additive (1,8‐diiodooctane (DIO)) on the morphology, charge generation, transport, and recombination in solution‐processed small‐molecule solar cells are studied and these parameters are correlated with device performance. In the optimum nanoscale morphology, which is processed with 0.4% DIO, the phase separation is large enough to create a percolating pathway for carrier transport, yet still small enough to form large interfacial area for efficient charge separation. Complete phase separation in this film reduces the interfacial defects, which occurs without DIO, and hence suppresses the monomolecular recombination. Moreover, balanced charge transport and weak bimolecular recombination lead to a high fill factor (72%). On the other hand, an excess amount of DIO (0.8%) in the solvent results in the over‐aggregation of the donor phase, which disturbs the percolating pathway of the acceptor phase and reduces the electron mobility. The over‐aggregation of the donor phase also shrinks the interfacial area for charge separation and consequently reduces the photocurrent generation.     

Benzo[1,2‐b:4,5‐b′]Dithiophene–6,7‐Difluoroquinoxaline Small Molecule Donors with >8% BHJ Solar Cell Efficiency

Solution‐processable small molecule (SM) donors are promising alternatives to their polymer counterparts in bulk‐heterojunction (BHJ) solar cells. While SM donors with favorable spectral absorption, self‐assembly patterns, optimum thin‐film morphologies, and high carrier mobilities in optimized donor–acceptor blends are required to further BHJ device efficiencies, material structure governs each one of those attributes. As a result, the rational design of SM donors with gradually improved BHJ solar cell efficiencies must concurrently address: (i) bandgap tuning and optimization of spectral absorption (inherent to the SM main chain) and (ii) pendant‐group substitution promoting structural order and mediating morphological effects. In this paper, the rational pendant‐group substitution in benzo[1,2‐b:4,5‐b′]dithiophene–6,7‐difluoroquinoxaline SMs is shown to be an effective approach to narrowing the optical gap (E_opt) of the SM donors ( SM1 and SM2 ), without altering their propensity to order and form favorable thin‐film BHJ morphologies with PC₇₁BM. Systematic device examinations show that power conversion efficiencies >8% and open‐circuit voltages (V_OC) nearing 1 V can be achieved with the narrow‐gap SM donor analog ( SM2 , E_opt = 1.6 eV) and that charge transport in optimized BHJ solar cells proceeds with minimal, nearly trap‐free recombination. Detailed device simulations, light intensity dependence, and transient photocurrent analyses emphasize how carrier recombination impacts BHJ device performance upon optimization of active layer thickness and morphology.