Stability of organic solar cells: toward commercial applications.

Organic solar cells (OSCs) have attracted a great deal of attention in the field of clean solar energy due to their advantages of transparency, flexibility, low cost and light weight. Introducing them to the market enables seamless integration into buildings and windows, while also supporting wearable, portable electronics and internet-of-things (IoT) devices. With the development of photovoltaic materials and the optimization of fabrication technology, the power conversion efficiencies (PCEs) of OSCs have rapidly improved and now exceed 20%. However, there is a significant lack of focus on material stability and device lifetime, causing a severe hindrance to commercial applications. In this review, we carefully review important strategies employed to improve the stability of OSCs over the past three years from the perspectives of material design and device engineering. Furthermore, we analyze and discuss the current important progress in terms of air, light, thermal and mechanical stability. Finally, we propose the future research directions to overcome the challenges in achieving highly stable OSCs. We expect that this review will contribute to solving the stability problem of OSCs, eventually paving the way for commercial applications in the near future.

Non-Fullerene Acceptors Assisted Target Therapy for Interface Treatment Enable High Performance Inverted Perovskite Solar Cells.

Targeted treatment of the interface between electron transport layers (ETL) and perovskite layers is highly desirable for achieving passivating effects and suppressing carrier nonradiative recombination, leading to high performance and long-term stability in perovskite solar cells (PSCs). In this study, a series of non-fullerene acceptors (NFAs, Y-H, Y-F, and Y-Cl) are introduced to optimize the properties of the perovskite/ETL interface. This optimization involves passivating Pb2+ defects, releasing stress, and modulating carrier dynamics through interactions with the perovskite. Remarkably, after modifying with NFAs, the absorption range of perovskite films into the near-infrared region is extended. As expected, Y-F, with the largest electrostatic potential, facilitates the strongest interaction between the perovskite and its functional groups. Consequently, champion power conversion efficiencies of 21.17%, 22.21%, 23.25%, and 22.31% are achieved for control, Y-H-, Y-F-, and Y-Cl-based FA0.88Cs0.12PbI2.64Br0.36 (FACs) devices, respectively. This treatment also enhances the heat stability and air stability of the corresponding devices. Additionally, these modifier layers are applied to enhance the efficiency of Cs0.05(FA0.95MA0.05)0.95PbI2.64Br0.36 (FAMA) devices. Notably, a champion PCE exceeding 24% is achieved in the Y-F-based FAMA device. Therefore, this study provides a facile and effective approach to target the interface, thereby improving the efficiency and stability of PSCs.

Self-Assembled Molecules with Asymmetric Backbone for Highly Stable Binary Organic Solar Cells with 19.7 % Efficiency.

The hole-transporting material (HTM), poly (3,4-ethylene dioxythiophene) poly(styrene sulfonate) (PEDOT : PSS), is the most widely used material in the realization of high-efficiency organic solar cells (OSCs). However, the stability of PEDOT : PSS-based OSCs is quite poor, arising from its strong acidity and hygroscopicity. In addition, PEDOT : PSS has an absorption in the infrared region and high highest occupied molecular orbital (HOMO) energy level, thus limiting the enhancement of short-circuit current density (Jsc) and open-circuit voltage (Voc), respectively. Herein, two asymmetric self-assembled molecules (SAMs), namely BrCz and BrBACz, were designed and synthesized as HTM in binary OSCs based on the well-known system of PM6 : Y6, PM6 : eC9, PM6 : L8-BO, and D18 : eC9. Compared with BrCz, BrBACz shows larger dipole moment, deeper work function and lower surface energy. Moreover, BrBACz not only enhances photon harvesting in the active layer, but also minimizes voltage losses as well as improves interface charge extraction/ transport. Consequently, the PM6 : eC9-based binary OSC using BrBACz as HTM exhibits a champion efficiency of 19.70 % with a remarkable Jsc of 29.20 mA cm-2 and a Voc of 0.856 V, which is a record efficiency for binary OSCs so far. In addition, the unencapsulated device maintains 95.0 % of its original efficiency after 1,000 hours of storage at air ambient, indicating excellent long-term stability.

Ultra Robust and Highly Efficient Flexible Organic Solar Cells with Over 18 % Efficiency Realized by Incorporating a Linker Dimerized Acceptor.

The wearable application of flexible organic solar cells (f-OSCs) necessitates high power conversion efficiency (PCE) and mechanical robustness. However, photoactive films based on efficient non-fullerene small molecule acceptors (NF-SMAs) are typically brittle, leading to poor mechanical stability in devices. In this study, we achieved a remarkable PCE of 18.06 % in f-OSCs while maintaining ultrahigh mechanical robustness (with a crack-onset strain (COS) of higher than 11 %) by incorporating a linker dimerized acceptor (DOY-TVT). Compared to binary blends, ternary systems exhibit reduced non-radiative recombination, suppressed crystallization and diffusion of NF-SMAs, and improved load distribution across the chain networks, enabling the dissipation of the load energy. Thus, the ternary f-OSCs developed in this study achieved, high PCE and stability, surpassing binary OSCs. Moreover, the developed f-OSCs retained 97 % of the initial PCE even after 3000 bending cycles, indicating excellent mechanical stability (9.1 % higher than binary systems). Furthermore, the rigid device with inverted structure based on the optimal active layer exhibited a substantial increase in efficiency retention, with 89.6 % after 865 h at 85 °C and 93 % after more than 1300 h of shelf storage at 25 °C. These findings highlight the potential of the linker oligomer acceptor for realizing high-performing f-OSCs with ultrahigh mechanical robustness.

Synthesis of 3H-Benzo[e]indoline and Its Application to Small-Molecule Organic Solar Cells.

A squaraine-based small molecule (USQ-BI) bearing 3H-benzo[e]indoline was synthesized as an electron donor, and the corresponding organic solar cells show power conversion efficiency of 5.35 % with an excellent short circuit current of over 15 mA cm-2 . The hole mobility of USQ-BI was about 5 times (9.57×10-5 vs. 2.00×10-5  cm2 V-1 s-1 ) higher than that of indoline-based squaraine.

An Azulene-Containing Low Bandgap Small Molecule for Organic Photovoltaics with High Open-Circuit Voltage.

A simple azulene-containing squaraine dye (AzUSQ) showing bandgap of 1.38 eV and hole mobility up to 1.25×10(-4)  cm(2) V(-1) s(-1) was synthesized. With its low bandgap, an organic photovoltaic (OPV) device based on it has been made that exhibits an impressive open-circuit voltages (Voc ) of 0.80 V. Hence, azulene might be a promising structural unit to construct OPV materials with simultaneous low bandgap, high hole mobility and high Voc .

Bisphosphonate-Anchored Self-Assembled Molecules with Larger Dipole Moments for Efficient Inverted Perovskite Solar Cells with Excellent Stability.

In the fabrication of inverted perovskite solar cells (PSCs), the wettability, adsorbability, and compactness of self-assembled monolayers (SAMs) on conductive substrates have critical impacts on the quality of the perovskite films and the defects at the buried perovskite-substrate interface, which control the efficiency and stability of the devices. Herein, three bisphosphonate-anchored indolocarbazole (IDCz)-derived SAMs, IDCz-1, IDCz-2, and IDCz-3, are designed and synthesized by modulating the position of the two nitrogen atoms of the IDCz unit to improve the molecular dipole moments and strengthen the π-π interactions. Regulating the work functions (WF) of FTO electrodes through molecular dipole moments and energy levels, the perovskite band bends upwards with a small offset for ITO/IDCz-3/perovskite, thereby promoting hole extraction and blocking electrons. As a result, the inverted PSC employing IDCz-3 as hole-collecting layer exhibits a champion PCE of 25.15%, which is a record efficiency for the multipodal SAMs-based PSCs. Moreover, the unencapsulated device with IDCz-3 can be stored for at least 1800 h with little degradation in performance.

Guest Acceptors with Lower Electrostatic Potential in Ternary Organic Solar Cells for Minimizing Voltage Losses.

The ternary strategy, in which one guest component is introduced into one host binary system, is considered to be one of the most effective ways to realize high-efficiency organic solar cells (OSCs). To date, there is no efficient method to predict the effectiveness of guest components in ternary OSCs. Herein, three guest compositions (i.e., ANF-1, ANF-2 and ANF-3) with different electrostatic potential (ESP) are designed and synthesized by modulating the electron-withdrawing ability of the terminal groups through density functional theory simulations. The effects of the introduction of guest component into the host system (D18:N3) on the photovoltaic properties are investigated. The theoretical and experimental studies provide a key rule for guest acceptor in ternary OSCs to improve the open-circuit voltage, that is, the larger ESP difference between the guest and host acceptor, the stronger the intermolecular interactions and the higher the miscibility, which improves the luminescent efficiency of the blend film and the electroluminescence quantum yield (EQEEL) of the device by reducing the aggregation-caused-quenching, thereby effectively decreasing the non-radiative voltage loss of ternary OSCs. This work will greatly contribute to the development of highly efficient guest components, thereby promoting the rapid breakthrough of the 20% efficiency bottleneck for single-junction OSCs.

Ductile Oligomeric Acceptor-Modified Flexible Organic Solar Cells Show Excellent Mechanical Robustness and Near 18% Efficiency.

High power conversion efficiency (PCE) and mechanical robustness are key requirements for wearable applications of organic solar cells (OSCs). However, almost all highly efficient photoactive films comprising polymer donors (PD ) and small molecule acceptors (SMAs) are mechanically brittle. In this study, highly efficient (PCE = 17.91%) and mechanically robust (crack-onset strain [COS] = 11.7%) flexible OSCs are fabricated by incorporating a ductile oligomeric acceptor (DOA) into the PD :SMA system, representing the most flexible OSCs to date. The photophysical, mechanical, and photovoltaic properties of D18:N3 with different DOAs are characterized. By introducing DOA DOY-C4 with a longer flexible alkyl linker and lower polymerization, the D18:N3:DOY-C4-based flexible OSCs exhibit a significantly higher PCE (17.91%) and 50% higher COS (11.7%) than the D18:N3-based device (PCE = 17.06%, COS = 7.8%). The flexible OSCs based on D18:N3:DOY-C4 retain 98% of the initial PCE after 2000 consecutive bending cycles, showing greater mechanical stability than the reference device (maintaining 89% of initial PCE). After careful investigation, it is hypothesized that the enhancement in mechanical properties is mainly due to the formation of tie chains or entanglement in the ternary blend films. These results demonstrate that DOAs have great potential for achieving high-performance flexible OSCs.

Modulation of the Fluorination Site on Side-Chain Thiophene Improved Efficiency in All-Small-Molecule Organic Solar Cells.

Fine-tuning the phase-separated morphology is of great importance to achieve efficient all-small-molecule organic solar cells (ASM-OSCs). In this work, a pair of isomers are designed and synthesized, namely, BDT-UF and BDT-DF, in which the fluorine atom in BDT-UF is close to the alkyl chain of side-chain thiophene, while that in BDT-DF is close to the center core. Owing to the noncovalent interaction between fluorine and hydrogen, BDT-DF shows a smaller dihedral angle between the thiophene side chain and the BDT core, which causes better molecular planarity. When mixed with N3, BDT-UF shows better miscibility, higher crystallinity, and more ordered molecule stacking in the blend film. Finally, the device of BDT-DF:N3 gains a power conversion efficiency (PCE) of 14.5%, while that of BDT-UF:N3 shows an increase in Voc, Jsc, and FF and gains a PCE of 15.1%. Our work exhibits a way of adjusting the substitution site of fluorine atoms to improve the PCE of ASM-OSCs.

High-Efficiency Thermal-Annealing-Free Organic Solar Cells Based on an Asymmetric Acceptor with Improved Thermal and Air Stability.

The stability of organic solar cells (OSCs) is an urgent problem for commercialization. In this work, a novel asymmetric molecule TB-4Cl was designed and synthesized. Quantum chemical computations revealed that TB-4Cl has a larger dipole moment of 1.98 Debye than that of Y6, which can induce a stronger intermolecular interaction. Without thermal annealing, devices based on PM6:TB-4Cl achieved a higher efficiency of 14.67%. Impressively, all of the devices showed a negligible difference in power conversion efficiency (PCE) before and after thermal-annealing treatment. Compared to the unencapsulated PM6:Y6-based devices, PM6:TB-4Cl-based devices exhibited improved thermal and air stability, evidenced by retaining around 75% (TB-4Cl) and 60% (Y6) after being heated at 100 °C in nitrogen for 110 h and 65% (TB-4Cl) and 50% (Y6) in air for 92 h. This work indicates that an A-D1A'D2-A asymmetric molecule can be a promising candidate for achieving stable OSCs with high efficiency.

Colorful Squaraines Dyes for Efficient Solution-Processed All Small-Molecule Semitransparent Organic Solar Cells.

Semitransparent organic solar cells (ST-OSCs) exhibit highly promising applications to develop integrated photovoltaics and power-generating windows. However, the development of ST-OSCs is significantly lagging behind opaque OSCs, especially for all small-molecule ST-OSCs. Here, four unique squaraines dyes (IDPSQ, SQ-BP, D-BDT-SQ, and AzUSQ) were successfully used as donors in ST-OSCs, whose colors can be tuned from purple to blue, green, and dark green, respectively. While using ultrathin Ag as a transparent electrode, the ST-OSCs fabricated using IDPSQ:PC71BM, SQ-BP:PC71BM, D-BDT-SQ:PC71BM, and AzUSQ:PC71BM yield power conversion efficiencies (PCEs) of 2.96, 4.36, 4.91, and 1.71%, respectively, and their colors are purple, cyan, brown, and light brown, respectively. Compared to their opaque OSCs (PCEs of 3.95, 5.45, 5.84, and 1.91%, respectively), the reduction in the PCEs are as low as 25, 20, 16, and 10%, respectively. Furthermore, each of these ST-OSCs exhibit good average visible transmittance (AVT) of 25-30%, favorable CIE color coordinates, and a color rendering index (CRI) of 71-97%. Finally, by changing the thickness of the Ag electrode, an impressive PCE of 4.9% along with an AVT of 25% and a CRI of 97% can be obtained in D-BDT-SQ:PC71BM-based ST-OSCs, which is the highest PCE among all small-molecule ST-OSCs.

Asymmetrical squaraines for high-performance small-molecule organic solar cells with a short circuit current of over 12 mA cm(-2).

An asymmetrical squaraine dye (Py-3) with its two electron-donating aryl groups directly linked to the electron-withdrawing squaric acid core possesses an ideal bandgap of 1.33 eV, together with an intense and broad absorption band in the range 550-950 nm. Hence, the resulting solution-processed solar cells display an impressive Jsc of 12.03 mA cm(-2) and a PCE of 4.35%.

Asymmetrical Squaraines Bearing Fluorine-Substituted Indoline Moieties for High-Performance Solution-Processed Small-Molecule Organic Solar Cells.

Two novel asymmetrical squaraines based on the indoline unit, ASQ-5-F and ASQ-5-DF, with one and two fluorine substituents, have been developed to investigate the effect of fluorine substituted on small-molecule bulk-heterojunction (BHJ) organic solar cells (OSCs). In comparison with non-fluorine-substituted ASQ-5, both fluorine-substituted ASQ-5-F and ASQ-5-DF possess analogous absorption band gaps but 0.05 and 0.10 eV lowered highest occupied molecular orbital (HOMO) energy levels, respectively. Single-crystal analysis exhibits that ASQ-5-DF shows more desirable intermolecular packing patterns for the hole-carrier collection than ASQ-5 does; hence, higher hole mobility could be acquired. Therefore, solution-processed small-molecule BHJ OSCs fabricated with ASQ-5-F/PC71BM and ASQ-5-DF/PC71BM blends exhibit extremely higher power conversion efficiency (PCE; 5.0% and 6.0%, respectively) than that of ASQ-5/PC71BM (4.5%). The much improved PCE could be attributed to the simultaneously enhanced Voc, Jsc, and FF relative to those of the ASQ-5-based device. To our knowledge, this is the highest PCE (6.0%) among squaraine-based solution-processed BHJ OSCs and the highest PCE in OSCs based on the fluorinated donor segment of small molecules.

A low bandgap asymmetrical squaraine for high-performance solution-processed small molecule organic solar cells.

A novel asymmetrical squaraine ASQ-5 bearing indoline as an end capper exhibits a low bandgap of 1.43 eV and a broad absorption band in the Vis-NIR region of 550-850 nm in thin films, hence renders solution-processed organic solar cells with an impressive Jsc of up to 11.03 mA cm(-2) and an excellent PCE of 4.29%.

Novel high performance asymmetrical squaraines for small molecule organic solar cells with a high open circuit voltage of 1.12 V.

An asymmetrically substituted squaraine ASQC bearing a 9-carbazyl substituent exhibits an extremely deep HOMO energy level of -5.46 eV and a relatively low bandgap of 1.65 eV, hence renders solution-processed organic solar cells with an impressive Voc of up to 1.12 V and a PCE of 2.82%.