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.     

Solid Additive Delicately Controls Morphology Formation and Enables High-Performance in Organic Solar Cells

Volatile solid additives are an effective strategy for optimizing morphology and improving the power conversion efficiencies (PCEs) of organic solar cells (OSCs). Much research has been conducted to understand the role of solid additives in active layer morphology. However, it is crucial to delve deeper and understand how solid additives affect the entire morphology evolution process, from the solution state to the film state and the thermal annealing stage, which remains unclear. Herein, the use of a highly crystalline solid additive, phenoxathiin (Ph), in D18-Cl:N3-based OSCs and study its impact on morphology formation and photovoltaic performance is presented. Owing to its good miscibility with the acceptor N3, Ph additive can not only extend the time for the active layer to form from the solution state to the film state, but also provide sufficient time for acceptor aggregation. After thermal annealing, Ph solid additive volatilizes better aligned the N3 molecules and formed a favorable hybrid morphology. Consequently, the D18-Cl:N3–based OSC exhibited an outstanding PCE of 18.47%, with an enhanced short-circuit current of 27.50 mA cm⁻² and a fill factor of 77.82%. This research is spurring the development of high-performance OSCs using solid additives that allow fine control during morphology development.     

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.     

Performance improvement of conventional and inverted polymer solar cells with hydrophobic fluoropolymer as nonvolatile processing additive

The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells.     

Improving the fill factor of N2200-based all polymer solar cells by introducing EPPDI as a solid additive

A cheap and commercially available small molecule (namely EPPDI) is introduced to the active layer of N2200-based all polymer solar cells as a solid additive. EPPDI at the optimal ratio can improve the D-A nano-scale morphology and reduce trap density of the active layer by filling morphological spaces. As a result, the photovoltaic performance of the resulting devices based on PF2:N2200 are increased from 6.28% to 7.03% with significantly enhanced fill factor. This work demonstrates a facile approach for improving the performance of all polymer solar cells.     

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.     

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-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.     

Towards improved efficiency of bulk-heterojunction solar cells using various spinel ferrite magnetic nanoparticles

A detailed study of organic solar cells (OSC) doped with various ferromagnetic and superparamagnetic (Fe₃O₄, ZnFe₂O₄ NiFe₂O₄) nanoparticles (MNPs) is presented. Additionally to previously used magnetite nanoparticles, various magnetic moment spinel ferrites were applied. By impedance spectroscopy (IS) analysis it is shown how the doping with various MNPs influences solar cells' performance by the charge carrier effective lifetime extension. In this regard, we introduced a convenient illustrative method to define time constants from the impedance measurements. It is also shown that, photovoltaic performance of the solar cells directly depends on the magnetic moment and alignment of the superparamagnetic single-domain MNPs. Alignment of the MNPs within the OSCs' active layer results in MNPs dipole-dipole interaction, thus further-improves photovoltaic performance due to efficient charge collection at the short-circuit condition. OSC doping with ferromagnetic MNPs showed negative influence on the device performance, however in dark conditions, devices doped with CoFe₂O₄ showed higher forward current presumably due to leakage current through the large MNP aggregation or electron-polaron hopping.     

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.     

Superficial fluoropolymer layers for efficient light-emitting diodes

Fluoropolymers are characterized by high chemical inertness and, when in solid state, by superficial dipoles due to the C–F bond where the charge density is strongly displaced. These two characteristics are exploited here for fine control of charge balance in organic light-emitting devices and for preventing electrochemical interaction between heterogeneous layers. The insertion of a thin layer of polytetrafluoroethylene, PTFE, at the interface between poly(ethylene dioxythiophene):poly(styrene sulfonic acid), PEDOT:PSS, and an electroluminescent polymer leads to improved device efficiency and longevity. The presence of the superficial dipole increases the effective work function of the anode and improves the charge balance which enhances the external quantum efficiency, EQE, of the devices by up to a factor of two without significant effects on the luminance levels. The insertion of the PTFE layer reduces the photoluminescence quenching at the PEDOT:PSS/polymer interface, however we show that the EQE enhancement is mainly due to a better confinement of minority carrier electrons in the active layer. The lifetime of the devices shows a remarkable increase correlated with the insertion of the PTFE layer. Such improvements are ascribed to the reduced electrochemical interaction between the electroluminescent polymer and PEDOT:PSS due to the chemically inert nature of PTFE. The PTFE acts as a chemical zipper of two heterogeneous media with the added functionality of control over the charge balance.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

Morphology Control in Solution‐Processed Bulk‐Heterojunction Solar Cell Mixtures

The efficiency of bulk‐heterojunction solar cells is very sensitive to the nanoscale structure of the active layer. In the past, the final morphology in solution‐processed devices has been controlled by varying the casting solvent and by curing the layer using heat tempering or solvent soaking. A recipe for making the “best‐performing” morphology can be achieved using these steps. This article presents a review of several new techniques that have been developed to control the morphology in polymer/fullerene heterojunction mixtures. The techniques fall into two broad categories. First, the morphology can be controlled by preparing nanoparticle suspensions of one component. The size and shape of the nanoparticles in solution determine the size and shape of the domain in a mixed layer. Second, the morphology can be controlled by adding a secondary solvent or an additive that more strongly affects one component of the mixture during drying. In both cases, the as‐cast efficiency of the solar cell is improved with respect to the single‐solvent case, which strongly argues that morphology control is an issue that will receive increasing attention in future research.     

Naphthalene tetracarboxylic diimide (NDI)-based polymer solar cells processed by non-halogenated solvents

Two non-fullerene acceptors, PNDIT-20 and PNDIT-16, based on naphthalenediimide (NDI) and thiophene comonomers, have been synthesized for all polymer solar cells (all-PSCs) application. The incorporation of long alkyl chains onto the NDI units endows the polymers with excellent solubility in both halogen and non-halogen solvents. Halogen-free solvents, e.g. 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), and 1,2-dimethylbenzene (1,2-DMB), have been employed to fabricate all-PSCs based on PNDIT-20 or PNDIT-16 paired with a donor polymer PTB7-Th without use of additives or post-treatment. The devices using 1,2-DMB as the solvent demonstrated PCEs of 3.88% and 4.94% for PNDIT-20 and PNDIT-16, respectively, which are among the highest values reported for PNDIT-based all-PSCs produced using environmentally friendly solvent. The performance is superior than the control device fabricated from conventional but hazardous 1,2-dichlorobenzene (1,2-DCB). Space-charge-limited current (SCLC) measurements and active layer morphological investigation revealed that non-halogenated solvent processed devices show higher and more balanced hole and electron mobilities as well as favorable surface morphology for charge transfer. The results reported in this work suggest that non-halogenated solvents for all-PSCs processing are greatly promising for the development of high performance all-PSCs.     

Influence of Ion Induced Local Coulomb Field and Polarity on Charge Generation and Efficiency in Poly(3‐Hexylthiophene)‐Based Solid‐State Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSC) are a realistic option for converting light to electrical energy. Hybrid architectures offer a vast materials library for device optimization, including a variety of metal oxides, organic and inorganic sensitizers, molecular, polymeric and electrolytic hole‐transporter materials. In order to further improve the efficiency of solid‐state dye‐sensitized solar cells, recent attention has focused on using light absorbing polymers such as poly(3‐hexylthiophene) (P3HT), to replace the more commonly used “transparent” 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)9,9′spiro‐bifluorene (spiro‐OMeTAD), in order to enhance the light absorption within thin films. As is the case with spiro‐OMeTAD based solid‐state DSSC, the P3HT‐based devices improve significantly with the addition of lithium bis(trifluoromethylsulfonyl)imide salts (Li‐TFSI), although the precise role of these additives has not yet been clarified in solid‐state DSCs. Here, we present a thorough study on the effect of Li‐TFSI in P3HT based solid‐state DSSC incorporating an indolene‐based organic sensitizer termed D102. Employing ultrafast transient absorption and cw‐emission spectroscopy together with electronic measurements, we demonstrate a fine tuning of the energetic landscape of the active cell components by the local Coulomb field induced by the ions. This increases the charge transfer nature of the excited state on the dye, significantly accelerating electron injection into the TiO₂. We demonstrate that this ionic influence on the excited state energy is the primary reason for enhanced charge generation with the addition of ionic additives. The deepening of the relative position of the TiO₂ conduction band, which has previously been thought to be the cause for enhanced charge generation in dye sensitized solar cells with the addition of lithium salts, appears to be of minor importance in this system.     

Softening temperature on sputtered ZnO interfacial barrier layer for an efficient charge transfer P3HT/ZnO and better interfacial stability in plastic organic photovoltaic devices

We demonstrate the usefulness of RF magnetron sputtering ZnO thin film at softening temperature, as interfacial barrier layer in air stable flexible inverted organic photovoltaic devices. We investigate the influence of annealing on the ZnO crystallinity, on the ITO substrate morphology and charge transport at the ZnO/active layer interface. The photo-physical and structural characteristics of P3HT beside ZnO interfacial layer and the photovoltaic device performances were also studied using UV–vis spectroscopy, photoluminescence (PL) and J-V characteristic. Finally, we study the interfacial stability of devices with and without ZnO interfacial layer in both normal and inverted structure OPVs. We show that under optimized sputtering conditions, higher order and orientation structure of P3HT, the ZnO thermally annealed beside active layer offers better efficiency of contact between the active layer and interfacial layer. We also show that ZnO annealed at a softening temperature of 180 °C is functional for both photovoltaic devices (rigid and plastic substrates), leading to improved performance and stability of plastic solar cell devices.     

Additive-free organic solar cells with enhanced efficiency enabled by unidirectional printing flow of high shear rate

High-performance OSCs prepared by scalable techniques without additives are highly desirable because residual additives may cause gradual deterioration of the photoactive-layer morphology and device performance. Printing flows with high shear rate have the potential to replace additives by inducing higher degree of ordered stacking and crystallinity of organic molecules, as well as favorable phase separation. Here, PTQ10:Y6 organic solar cells (OSCs) without any additives were fabricated by a scalable and robust processing approach termed as soft porous blade printing (SPBP). The fluid flow and drying process of the wet films made by SPBP, blade coating and spin coating are visualized by high speed imaging, which reveals that the blade coating and SPBP introduce unidirectional flow while the wet film interference pattern of spin coating is irregular and random. The simplified flow model of SPBP suggests that the shear rate could be as high as ~1000 s⁻¹. The additive-free SPBP produces photoactive-layer with adequate morphology, which could be attributed to three intrinsic properties of SPBP: very high shear rate, flow assisted crystallizations induced by microstructures of the soft porous blade, and numerous nucleation sites generated as the liquid contact line follows the motion of the blade. The additive-free SPBP device demonstrates weaker charge recombination, higher and more balanced charge transport, and consequently better device performance than the spin-coated and blade-coated devices with 0.25 vol% 1,8-diioctane (DIO). SPBP achieved power conversion efficiency (PCE) of 16.45%, which is higher than those of spin-coated and blade-coated counterparts doped with DIO.     

Controlling the morphology of nanofiber-P3HT:PCBM blends for organic bulk heterojunction solar cells

Within the field of organic bulk heterojunction solar cells, the morphology of the active layer has a key role in obtaining high power conversion efficiencies. P3HT nanofibers, obtained in highly concentrated solutions, are able to give controlled morphologies directly upon deposition. Since the solar cell efficiency of fiber solar cells depends on the fiber content of the casting solution, it is important to control this parameter. Here, we demonstrate an easy way to control the fiber content in the casting solution, i.e. changing the solution temperature. By using solution heating, the overall molecular weight of the polymer in the blend is kept constant, fiber isolation is not needed and the use of solvent mixtures is avoided. The obtained optimal power conversion efficiency is shown to be linked to the morphology of the active layer, which is studied with Transmission Electron Microscopy (TEM).     

Development of bulk heterojunction morphology by the difference of intermolecular interaction behaviors

The morphology of a bulk heterojunction can be controlled by adding a processing additive in order to improve its power conversion efficiency (PCE) in photovoltaic devices. The phase-separated morphologies of blends of PONTBT or P3HT with fullerene derivatives are systematically examined in the presence of processing additives that possess various alkane alkyl chain lengths or end-group electronegativities. We determined the morphologies of the bulk heterojunction layers by using atomic force microscopy (AFM) and grazing incidence wide angle X-ray scattering (GIWAXS). The photocurrent–voltage characteristics of the bulk heterojunction solar cells were found to be strongly dependent on the intermolecular interactions between the conjugated polymers, the fullerene derivatives, and the processing additives in the photoactive layer. The optimal PONTBT:fullerene derivative blend morphology was obtained with a processing additive, 1,3-diiodopropane (1,3-DIP), that possesses a short alkyl chain and an end group with weak electronegativity, and was found to exhibit a high fill factor (FF) and a high current density (J_SC). In contrast, in blends of P3HT with the fullerene derivative, PCEs with higher FF and J_SC values were achieved by incorporating the processing additive, 1,8-dibromooctane (1,8-DBrO), which has a long alkyl chain and a strong electronegative end group. Thus the selection of the processing additive with the aim of enhancing photovoltaic performance needs to take into account the intermolecular interaction of the conjugated polymer.     

Enhanced Performance in Polymer Solar Cells by Surface Energy Control

Enhanced performance of an inverted‐type polymer solar cell is reported by controlling the surface energy of a zinc oxide (ZnO) buffer layer, on which a photoactive layer composed of a polymer:fullerene‐derivative bulk heterojunction is formed. With the approach based on a mixed self‐assembled monolayer, the surface energy of the ZnO buffer layer can be controlled between 40 mN m^?1 and 70 mN m^?1 with negligible changes in its work function. For the given range of surface energy the power conversion efficiency increases from 3.27% to 3.70% through enhanced photocurrents. The optimized morphology obtained by surface energy control results in the enhanced photocurrent and transmission electron microscopy analysis verifies the correlation between the surface energy and the phase morphology of the bulk heterojunction. These results demonstrate that surface energy control is an effective method for further improving the performance of polymer solar cells, with potentially important implications for other organic devices containing an interface between a blended organic active layer and a buffer or an electrode layer.