Dual-Additive-Driven Morphology Optimization for Solvent-Annealing-Free All-Small-Molecule Organic Solar Cells

All-small-molecule organic solar cells (ASM-OSCs), which consist of small-molecule donors and acceptors, have recently been studied extensively to eliminate the batch-to-batch variation from polymer-based donor or acceptor. On the other hand, the control of their active layer morphology is more challenging due to the similar chemical structure and miscibility of small-molecule donor and small-molecule accepter. Hence, this study develops a dual-additive-driven morphology optimization method for ASM-OSCs based on BTR-Cl:Y6. One solid additive – 1,4-diiodobenzene (DIB) and one liquid additive – diiodomethane (DIM) are selected, making use of their distinct interaction mechanisms with Y6 and BTR-Cl. It is found that DIB can form a eutectic phase with Y6, which can increase the intermolecular interactions and modulate the acceptor phase separation, while the simultaneous volatilization of DIM suppresses the over-aggregation of BTR-Cl during the film casting process. As a result of the synergistic morphology tuning, the optimized device delivers a power conversion efficiency (PCE) as high as 15.2%, among the highest PCE reported to date for binary ASM-OSCs without solvent annealing treatment. This work demonstrates the potential of morphology tuning via the incorporation of dual additives into ASM-OSCs, enabling them to achieve comparable efficiencies to those of conventional polymer/small-molecule based OSCs.     

High-Efficiency (16.93%) Pseudo-Planar Heterojunction Organic Solar Cells Enabled by Binary Additives Strategy

Acquiring precision adjustable morphology of the blend films to improve the efficiency of charge separation and collection is a constant goal of organic solar cells (OSCs). Here, the above problem is improved by synergistically combining the sequential deposition (SD) method and the additive general strategy. By adding one additive 1,10-decanediol (DDO) into PM6 and another 1-chloronaphthalene (CN) into Y6, the molecule orientation of PM6 and the crystallite texture of the Y6 all become order. During the SD processing, a vertical phase separation OSCs device is formed where the donor enrichment at the anode and acceptor enrichment at the cathode. In comparison, the SD OSCs device with only CN additive still displays the bulk-heterojunction morphology similar to PM6:Y6 blend film. The morphology with vertical phase distribution can not only inhibit charge recombination but also facilitate charge collection, finally enhancing the fill factor (FF) and photocurrent in binary additives SD-type OSCs. As a result, the binary additives SD-type OSCs with blend film PM6 + DDO/Y6 + CN exhibit a high FF of 77.45%, enabling a power conversion efficiency as high as 16.93%. This work reveals a simple but effective approach for boosting high-efficiency OSCs with ideal morphologies and demonstrates that the additive is a promising processing alternative.     

Anthracene-Assisted Morphology Optimization in Photoactive Layer for High-Efficiency Polymer Solar Cells

Currently, morphology optimization methods for the fused-ring nonfullerene acceptor-based polymer solar cells (PSCs) empirically follow the treatments originally developed in fullerene-based systems, being unable to meet the diverse molecular structures and strong crystallinity of the nonfullerene acceptors. Herein, a new and universal morphology controlling method is developed by applying volatilizable anthracene as solid additive. The strong crystallinity of anthracene offers the possibility to restrict the over aggregation of fused-ring nonfullerene acceptor in the process of film formation. During the kinetic process of anthracene removal in the blend under thermal annealing, donor can imbed into the remaining space of anthracene in the acceptor matrix to form well-developed nanoscale phase separation with bi-continuous interpenetrating networks. Consequently, the treatment of anthracene additive enables the power conversion efficiency (PCE) of PM6:Y6-based devices to 17.02%, which is a significant improvement with regard to the PCE of 15.60% for the reference device using conventional treatments. Moreover, this morphology controlling method exhibits general application in various active layer systems to achieve better photovoltaic performance. Particularly, a remarkable PCE of 17.51% is achieved in the ternary PTQ10:Y6:PC₇₁BM-based PSCs processed by anthracene additive. The morphology optimization strategy established in this work can offer unprecedented opportunities to build state-of-the-art PSCs.     

Bifunctional Bis-benzophenone as A Solid Additive for Non-Fullerene Solar Cells

Simultaneously improving efficiency and stability is critical for the commercial application of non-fullerene acceptor polymer solar cells (NFA-PSCs). Multifunctional solid additives have been considered as a potential route to tune the morphology of the active layer and optimize performance. In this work, photoinitiator bifunctional bis-benzophenone (BP-BP) is used as a solid additive, replacing solvent additives, in the PBDB-T:ITIC NFA system. With the addition of BP-BP, the intermolecular π–π stacking of PBDB-T and morphology is improved, leading to more balanced carrier transport and more effective exciton dissociation. Devices fabricated with BP-BP show a power conversion efficiency (PCE) of 11.89%, with enhanced short-circuit current (J_sc), and fill factor (FF). Devices optimized with BP-BP show excellent reproducibility, insensitivity to thickness, and an improved thermal stability under atmospheric conditions without encapsulation. This work provides a new strategy for the application of solid additives in NFA-PSCs.     

High performance organic solar cells enabled by an iodinated additive

Additive engineering is a simple and effective strategy to enhance the efficiency of organic solar cells (OSCs). However, traditional additives such as 1,8-diiodooctane (DIO) or 1-chloronaphthalene (CN), suffer from inferior stability, concentration sensitivity, and need additional thermal treatments, which are not desirable for industrial application. Here we introduce a simple, effective and versatile solid additive 1,3-diiodobenzene (1,3-DIB) into the OSCs. In comparison to the control devices, the 1,3-DIB treated OSCs exhibit significantly improved performance with a power conversion efficiency (PCE) of 16.90% for polymer OSCs and a PCE of 14.35% for binary all-small-molecule OSCs. Mechanism studies reveal that 1,3-DIB can improve charge transport and extraction, decrease charge recombination, enhance crystallinity and improve the phase separation. Furthermore, no thermal annealing is needed in PM6:Y6 based OSCs and the 1,3-DIB treated devices show excellent stability and reproducibility in both polymer and small molecule OSCs. Our results demonstrated that additive engineering is a powerful method to enhance the OSC performance.     

Novel brominated compounds using in binary additives based organic solar cells to achieve high efficiency over 10.3%

Solvent additives have been considered as a simple and efficient method to increase the performance of bulk-heterojunction (BHJ) organic solar cells, in which, the morphology of the active layer could obtain further improvements by using the binary solvent additives. In this paper, a series of brominated compounds, 1-Bromo-4-butylbenzene (Brbb), 1-Bromo-4-n-hexylbenzene (Brbh) and 1-Bromo-4-n-octylbenzene (Brbo), have been respectively incorporated with 1, 8-diiodooctane (DIO) and regarded as binary solvent additives to fabricate highly efficient bulk heterojunction (BHJ) organic solar cells (OSCs). Compared with the BHJ film based on single additive, the binary additives contained BHJ film shows increased optical absorption, efficient charge transport and better active layer morphology, leading to an enhancement of short-circuit current (J_SC) together with a higher achieved fill factor (FF). The conventional BHJ device using PTB7: PC₇₁BM or PTB7-th: PC₇₁BM with the binary solvent additives exhibit enhanced PCE of 8.13% and 10.31%, respectively, which is much higher than that of single additive based devices (7.04% for PTB7 and 8.73% for PTB7-th). The optimized performance of BHJ devices indicates that these brominated compounds are promising additives to improve device efficiency.     

Enhancing efficiency for additive–free blade–coated small–molecule solar cells by thermal annealing

Blade coating was successfully applied to realise high-efficiency small-molecule organic solar cells (OSCs) with a solution-processed active layer comprising a small organic molecule DR3TBDTT with a benzo[1,2–b:4,5–b′]dithiophene (BDT) unit as the central building block as the donor and [6,6]–phenyl–C71–butyric acid methyl ester (PC₇₁BM) as the acceptor. Using chloroform as the solvent, a DR3TBDTT/PC₇₁BM blend active layer without an additive was effectively formed through blade coating. The power conversion efficiency (PCE) of small organic molecule solar cells was enhanced by 3.7 times through thermal annealing at 100 °C. This method produces OSCs with a high PCE of up to 6.69%, with an open circuit voltage (V_oc) of 0.97 V, a short-circuit current density (J_sc) of 12.60 mA/cm², and a fill factor (FF) of 0.55.     

Effects of exciton blocking layer and cathode electrode work function on the performance of polymer solar cells

In this study the effects of some important processing and post-processing treatments on the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT):[6,6]-phenyl-C₆₁-butyric acid methyl ester ([60]PCBM) solar cells were investigated. These parameters included the active layer film formation period, thermal annealing, electrical treatment, cathode work function modification, and exciton blocking layer type and thickness. Polymer bulk heterojunction solar cells having a glass/indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM/(Ca or LiF)/Al structure were fabricated. The morphology of the active layer was investigated using atomic force microscopy. The results showed that the morphology state of the active layer exactly after spin coating process was very important parameter, which could dictate different responses of solar cells to a certain treatment. Using solvent additives to prolong the film formation period and storing in small dish could reach the morphology of the active layer near its best state in which there was no need to apply common post-treatment processes. A thickness at about 20 nm was required for Ca layer to effectively act as exciton blocking layer while LiF with 1 nm thickness worked better.     

Real-Time Probing and Unraveling the Morphology Formation of Blade-Coated Ternary Nonfullerene Organic Photovoltaics with In Situ X-Ray Scattering

Characterizing the bulk heterojunction (BHJ) morphology of the active layer is essential for optimizing blade-coated organic solar cells (OSCs). Here, the morphology evolution of a highly efficient ternary polymer:nonfullerene blend PM6:N3:N2200 under different blade coating conditions is probed in real-time by in situ synchrotron X-ray scattering and in situ ultraviolet-visible (UV-vis) spectroscopy. Besides, the morphology of blade-coated blend films at different conditions is detailed by ex situ X-ray scattering and microscopic imaging. The ternary blend film exhibited optimized morphology, such as superior molecular stacking structure and appropriate phase separation structure, and boosted photovoltaic performance of the binary blend, as adding a second polymer component to the host polymer:nonfullerene system can balance nucleation and crystallization of polymers and small molecules, facilitating molecular rearrangement to perfect crystallization. Both binary and ternary blends obtained optimized morphology and photovoltaic properties at medium coating speed, mainly attributed to the movement of the polymer and small molecules at the long crystallization and aggregation stage. These findings help understand morphology formation under film drying and provide guidance for optimizing the morphology in blade-coated OSCs.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

Efficient Large Area All-Small-Molecule Organic Solar Cells Fabricated by Slot-Die Coating with Nonhalogen Solvent

The commercialization of organic solar cells (OSCs) requires the use of roll-to-roll coating technology. However, it is generally believed that all-small-molecule (ASM) systems cannot form high-quality films in most film-fabrication technologies except for spin coating, mainly due to their strong crystallinity and low solution viscosity. Herein, it is found that the small molecule donor and acceptor system with strong intermolecular interaction can weaken the molecular self-aggregation during film formation. As a result, all-small-molecule organic solar cells (ASM-OSCs) are successfully fabricated using the green solvent tetrahydrofuran via spin coating as well as slot-die coating technology. Under the optimal conditions, the devices achieve power conversion efficiency (PCE) of 14.05% and 13.41% prepared by spin coating and slot-die coating, respectively. Moreover, a large-area device with an area of 1 cm² achieve a PCE of 10.65% by slot-die coating. The study of the device performance and the active layer morphology reveal a unique film optimization mechanism in ASM-OSCs. In the slot-die coating process, a high-quality film is formed due to the significantly suppressed crystallinity of the small molecule donor; with further thermal annealing, the crystallization-induced phase separation enables an optimized morphology. This study proves that high-performance ASM-OSCs can be fabricated by the industrial-compatible method.     

P3HT/PCBM Bulk Heterojunction Solar Cells: Impact of Blend Composition and 3D Morphology on Device Performance

The performance of polymer solar cells (PSC) strongly depends on the 3D morphological organization of the donor and acceptor compounds within the bulk heterojunction active layer. The technique of electron tomography is a powerful tool for studying 3D morphology of the layers composed of poly(3‐hexylthiophene) (P3HT) and a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester; PCBM), especially to quantify the amount and distribution of fibrillar P3HT nanocrystals throughout the volume of the active layer. In this study, electron tomography is used to characterize P3HT/PCBM layers with different blend compositions, both before and after thermal annealing. The power conversion efficiency of the corresponding PSCs is strongly dependent on the overall crystallinity of P3HT and the way P3HT crystals are distributed throughout the thickness of the active layer.     

Solid Solvation Assisted Electrical Doping Conserves High-Performance in 500 nm Active Layer Organic Solar Cells

Organic solar cells (OSCs) process fascinating solution-printing capability to achieve low-cost and large-scale manufacture. However, the rapid power conversion efficiency (PCE) decay with active layer thickness enlargement inhibits the implement of OSCs’ potential advantages. To overcome the bottlenecks of PCE decay in thick active layer OSCs, the electrical doping with componential selectivity in bulk heterojunction (BHJ) film is achieved by introducing a solid solvation additive. Benefiting from the higher exciton splitting efficiency together with the longer drift (L_dr) and diffusion (L_diff) lengths, an OSC with 100 nm BHJ film demonstrates a PCE increment from 16.44% to 18.24% with prolonged dark and illuminated storage stabilities. Applying the solid solvation assisted (SSA) doping method in the OSCs with 500 nm active layer, the PCE significantly increases by 31.9%, from the original value of 11.79% to 15.55%. It further improves to 15.84% in a ternary blend thick-film device, which is the record value to the best of our knowledge. Besides, the SSA doping narrows the PCE gap between the 0.04 and 1 cm² devices. All improvements demonstrate the great potential of SSA doping for OSC commercial manufacture, since it optimizes the photovoltaic performance under all practical conditions of long-term, thick-film, and large-area.     

Effects of Solvent Mixtures on the Nanoscale Phase Separation in Polymer Solar Cells

The mixed solvent approach has been demonstrated as a promising method to modify nanomorphology in polymer solar cells. This work aims to understand the unique role of the additive in the mixture solvent and how the optimized nanoscale phase separation develops laterally and vertically during the non‐equilibrium spin‐coating process. We found the donor/acceptor components in the active layer can phase separate into an optimum morphology with the additive. Supported by AFM, TEM and XPS results, we proposed a model and identified relevant parameters for the additive such as solubility and vapor pressures. Other additives are discovered to show the ability to improve polymer solar cell performance as well.     

Quadrupole Moment Induced Morphology Control Via a Highly Volatile Small Molecule in Efficient Organic Solar Cells

Developing novel solid additives has been regarded as a promising strategy to achieve highly efficient organic solar cells with good stability and reproducibility. Herein, a small molecule, 2,2′-(perfluoro-1,4-phenylene)dithiophene (DTBF), designed with high volatility and a strong quadrupole moment, is applied as a solid additive to implement active layer morphology control in organic solar cells. Systematic theory simulations have revealed the charge distribution of DTBF and its analog and their non-covalent interaction with the active layer materials. Benefitting from the more vital charge–quadrupole interaction, the introduction, and volatilization of DTBF effectively induced more regular and condensed molecular packing in the active layer, leading to enhanced photoelectric properties. Thus, high efficiency of over 17% is obtained in the DTBF-processed devices, which is higher than that of the control devices. Further application of DTBF in different active layer systems contributed to a deeper comprehension of this type of additive. This study highlights a facile approach to optimizing the active layer morphology by finely manipulating the quadrupole moment of volatile solid additives.     

Revealing the effect of donor/acceptor intermolecular arrangement on organic solar cells performance based on two-dimensional conjugated small molecule as electron donor

A series of solution processed organic solar cells (OSCs) were fabricated with a two-dimensional conjugated small molecule SMPV1 as electron donor and fullerene derivatives PC₇₁BM or ICBA as electron acceptor. The champion power conversion efficiency (PCE) of OSCs arrives to 7.05% for the cells with PC₇₁BM as electron acceptor. A relatively large open circuit voltage (V_OC) of 1.15 V is obtained from cells using ICBA as electron acceptor with an acceptable PCE of 2.54%. The fill factor (FF) of OSCs is 72% or 61% for the cells with PC₇₁BM or ICBA as electron acceptor, which is relatively high value for small molecule OSCs. The relatively low performance of OSCs with ICBA as electron acceptor indicates that ICBA cannot play positive role in photoelectric conversion processes, which is very similar to the phenomenon observed from the OSCs with high efficient narrow band gap polymers other than P3HT as electron donor, the underlying reason is still in debate. The SMPV1 has strong self-assemble ability to form an ordered two dimensional lamellar structure, which provides an effective platform to investigate the effect of electron acceptor chemical structure on the performance of OSCs. Experimental results exhibit that ICBA molecules may prefer to vertical cross-intercalation among side chains of SMPV1, PC₇₁BM molecules may have better miscibility with SMPV1 in the active layer. The different donor/acceptor (D/A) intermolecular arrangement strongly influences photon harvesting, exciton dissociation and charge carrier transport, which may provide a new sight on performance improvement of OSCs by adjusting D/A intermolecular arrangements.     

Solution-processable tetrazine and oligothiophene based linear A–D–A small molecules: Synthesis,hierarchical structure and photovoltaic properties

A series of high coplanar alternative linear small molecules with acceptor–donor–acceptor (A–D–A) structure containing electron-accepting tetrazine (Tz) moiety and electron-donating oligothiophenes (OTs) moiety, alkylated thiophene attached to both sides of the Tz moiety were designed and synthesized. The influences of varied oligothiophene length on small molecules’ optical and electrochemical properties, crystallization, self assembling morphology in blend film with (6,6)-phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM), and photovoltaic properties for the application as donor materials in organic solar cells (OSCs) were studied. The optical and electrochemical properties of small molecules showed that the HOMO and LUMO energy levels were determined by the number of OTs moiety and electron-accepting ability of Tz in the alternative small molecules, respectively. Meanwhile, the varied OT moieties can significantly affect the hierarchical structures when mixed with PC₆₁BM. The molecule with intermediate conjugate moity length showed the highest ordering in its crystalline state, as revealed by differential scanning calorimetry (DSC) and X-ray diffraction experiments, and best photovoltaic properties when blended together with PC₆₁BM or (6,6)-phenyl-C₇₁-butyric acid methyl ester (PC₇₁BM) as active layer in photovoltaic devices. The results indicate that hierarchical structures controlled by adjusting the conjugate moity length of small molecules is an effective way to improve the performance of OSCs. The photovoltaic device based on TT(HTTzHT)₂:PC₇₁BM with 1% DIO additives showed the best performance, with a J_sc of 7.87 mA/cm² and a PCE of 3.24%.     

In situ monitoring of photovoltaic properties in organic solar cells during thermal annealing

This paper reports a simple and useful technique that monitors the changes of poly(3-hexylthiophene) (P3HT):1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C₆₁-based organic solar cells (OSCs) during thermal annealing in situ. Thermal annealing was divided into five stages in which the variations of the cell parameters were obtained in detail. Annealing temperature that was higher than the glass transition temperature of P3HT (127 °C) was found critical to the improvement of open-circuit voltage. The initial rise of the short-circuit current was explained by in situ monitoring of the transport behaviors of electrons and holes. Finally, in situ monitoring was adopted to compare OSCs that were or were not solvent-annealed, indicating the effectiveness in optimizing, modeling and understanding in depth the effects of the thermal annealing of OSC with a blended active layer.     

Hydrogen Bond Induced Green Solvent Processed High Performance Ternary Organic Solar Cells with Good Tolerance on Film Thickness and Blend Ratios

For comprehensive development of organic solar cells (OSCs), some factors such as environmental stability, low cost, insensitive film thickness, component contents tolerance, and green preparation processes are equally crucial to achieve high power conversion efficiencies (PCEs). In this work, a small molecule 3‐(diethylamino)‐7‐imino‐7H‐benzo[4,5]imidazo[1,2‐a]chromeno[3,2‐c]pyridine‐6‐carbonitrile (DIBC), which is commercially available at low cost, is utilized to realize high‐performance ternary OSCs. Demonstrated via Fourier transform infrared and 2D‐¹HNMR, DIBC can form hydrogen bond interactions with [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) in solid films. Further electrostatic potential (ESP) calculations indicate that the hydrogen bond interaction enhances the ESP of PC₇₁BM and accelerates charge transport between donor and acceptor. As a result, poly(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b0]dithiophene‐2,6‐diylalt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl (PTB7‐Th):DIBC:PC₇₁BM‐based ternary OSC achieves a maximum efficiency of 12.17%, which is the best result of green solvent processed fullerene OSCs at present. It is noteworthy that the ternary OSCs also show great tolerance to film thickness and blend ratios. These unique properties are attributed to the hydrogen‐bond‐linked DIBC and PC₇₁BM, which modulates molecule distribution and improves film morphology with an interpenetrating network structure. Furthermore, the DIBC containing device also exhibits good thermal and light radiation stability. These results illustrate that intermolecular hydrogen bond interaction has great potential for realizing high‐performance OSCs.