Chlorobenzene Solution Research Articles

Biocatalytic degradation of environmental endocrine disruptor chlorobenzene via surfactant-optimized laccase-mediator system.

The emergence of environmental endocrine disruptor chlorobenzene (CB) in surface water and its potential environmental impacts have attracted serious global attention. It is still very difficult to achieve effective degradation of it by catalytic oxidation process under mild conditions. Here, an optimized method for degrading CB in aqueous solution using Trametes versicolor laccase and surfactant-assisted laccase-mediator (SALM) system was investigated. The use of a Tween 80 surfactant enhanced the solubility of CB and promoted its efficient degradation. Under favorable conditions, the SALM system yielded a degradation efficiency of 43.5% and a dechlorination efficiency of 41.55% for CB (25mg/L) within 24h. The possible degradation pathway of CB by this system was speculated by detecting the intermediates produced during the reaction. The outcome of the proliferation assays on MCF-7 human breast cancer cells demonstrated a reduction in the estrogenic activity of the CB solution following treatment with the SALM system. Furthermore, the influence of the quantity and positional variation of chlorine substituents on the degradation process was methodically investigated. Moreover, molecular analyses were employed to study the detailed interaction mechanism between laccase and CB, which revealed that the hydrophobic interaction contributed dominantly to binding process. These findings provide an efficient and environmentally friendly degradation system for the development of purification strategies for halogenated pollutants.

Photovoltaic enhancement in OSCs based on PM6:Y7 when doping the active layer with Ag2S nanoparticles

Herein, silver sulfide (Ag2S) nanoparticles (NPs) with an average size of 31 nm ± 4 nm were synthesized using a simple, economic, and eco-friendly method assisted by ultrasonic bathing; the reaction was carried out in a non-polluting aqueous medium. These Ag2S NPs were suspended in ethanol and used to dope the active layer of Organic Solar Cells (OSCs) based on PM6 (donor) and Y7 (acceptor) by adding 2 v/v % of a suspension to the PM6:Y7 solution in chlorobenzene (CB). The entire fabrication process and testing was carried out under normal atmospheric conditions. Field's metal (FM) was used as the top electrode of the OSCs, which is a eutectic alloy of bismuth, indium, and tin (Bi 32.5 %, In 51 %, and Sn 16.5 %) with a melting point above 62 °C deposited by free evaporation techniques. The average Power Conversion Efficiency (PCE) for the reference and doped OSCs were 9.19 % (9.43 % the best) and 10.31 % (10.77 % the best), respectively; representing an increase of more than 14 % in the PCE value when Ag2S NPs are added to the active layer. It can be attributed to different optical phenomena, among which could be the enhance in the internal light reflection processes (scattering) and the Local Surface Plasmon Resonance (LSPR) effect.

Reduction of styrene compounds by hydrogen iodide

Reduction of styrene compounds was achieved by the simple method of adding more than 2.5 equivalents of an aqueous HI solution in chlorobenzene under refluxing conditions for 8 h to give the product in medium to excellent yields. There was no need to add further additional reagent and catalyst. HI was a specific reagent for this reduction reaction. Increment of the amount of HI was efficient to increase the yield rather than to elongate the reaction time. This reaction could be applied to compounds bearing halogen and sulfur atoms, which would act as reductive site and poisoning of the transition-metal catalyst, respectively. The yield was decreased in the case of the compounds bearing small substituent such as propyl and butyl groups on olefin. This reaction proceeded via the iodinated intermediate followed by the reduction of C-I bond. The reduction mechanism would contain the radical cleavage of the C-I bond.

Theoretical investigation on diastereoselective [2+2] cycloaddition and Pd-catalyzed enantioselective [3+2] cycloaddition for synthesis of cis-β-lactam and exo-furobenzopyranone

The mechanism is investigated for Wolff rearrangement/Staudinger [2+2] cycloaddition cascade and Pd-catalyzed, decarboxylative, formal [3+2] cycloaddition. Wolff rearrangement of 3-diazotetramic acid is determined to be rate-limiting step generates cyclic acyl ketene. The interaction of ketene with imine firstly results in zwitterion followed by conrotatory cyclization giving major cis-β-lactam. For synthesis of s-VECs, the epoxidation−cyclization cascade and hydrolysis give precursor of better performing exocyclic derivative. The reaction with 3-cyanochromone includes decarboxylation, nucleophilic attack and subsequent ring closure yielding 5-exo-trig furobenzopyranone. Based on the comparison between possible paths, the diastereoselectivity of cis over trans and regio-divergence of 5-exo-trig over 7-endo-trig are both kinetically controlled for [2+2] and [3+2] cycloaddition in common. The positive solvation effect is suggested by decreased absolute and activation energies in chlorobenzene and chloroform solution compared with in gas. These results are supported by Multiwfn analysis on FMO composition of specific TSs, and MBO value of vital bonding, breaking.

Solution processable Zn-salphen containing π-conjugated polymers with unique aggregation behavior as organic optoelectronic materials

Series of π-conjugated polymers containing electron-withdrawing Zn-Schiff base complex (Zn-salphen) were reported. These polymers can be easily obtained with controllable optical bandgap (Egopt) varying from 1.50 to 2.13 eV by changing the π-conjugated comonomers, and together with excellent thermal stabilities. It was found that the introduction of alkyl chains could provide good solution process-ability for these polymers in chlorobenzene solutions. All the polymers exhibit high hydrophilic characteristics compared to traditional semi-conducting polymers. This is caused by the large polarity of Zn-salphen, which results in strong inter-molecular interactions for the polymers analyzed based on their optical properties. Interestingly, these aggregation behaviors are highly dependent on the type of solvents and coordinating additives such as pyridine, which can be observed from their UV–vis absorption and photoluminescence (PL) spectra. In addition, the film morphologies of these polymers can be modified by using pre- and post-treatments such as thermal annealing, solvent annealing and additives. This work introduces a new strategy for constructing semi-conducting polymers by solving the problem of poor solubility of Zn-salphen complex, and preliminarily studies the feasibility of these Zn-salphen containing polymers regarding their solution process-ability, optical adjustment and morphology optimization. These polymers are considered potential candidates for applications in photoelectric devices.

N‐Pyridylureas as Masked Isocyanates Fort the Late‐Stage Diversification of Pyridine‐N‐Oxides

AbstractA new method for the synthesis of pyridine‐ and quinoline‐N‐oxides containing a ureido or carbamoyl fragment in position 2 has been developed. This method concluded in the oxidation of relatively readily available substituted N,N‐dimethyl‐N′‐(pyridine‐2‐yl)ureas to the corresponding N‐oxides, followed by modification of the dimethylureide moiety. Being heated to 90 °C in the presence of amines in a solution of DMF or chlorobenzene, N‐oxide of N,N‐dimethyl‐N′‐(pyridine‐2‐yl)urea undergoes a transamination reaction without loss of the N‐oxide function. This produces N‐oxides of N‐alkyl/aryl‐N’‐(pyridine‐2‐yl)ureas in 24–99 % yields, (about 30 examples). Values of the NH protons chemical shifts are a good criterion for the selectivity of the reaction. The reaction is also applicable to N‐oxides of ureas substituted in the pyridine ring and to the quinoline congener. N‐Oxides of pyridine/quinoline‐containing carbamates can be similarly prepared by heating N‐oxides of N,N‐dimethyl‐N′‐(pyridine‐2‐yl)/(quinoline‐2‐yl)‐urea in an appropriate alcohol solution at 120 °C.

Dielectric relaxation in solutions chlorobenzene–benzene and chlorobenzene–hexane

This paper presents the results of a study of the dielectric constant of solutions of a polar liquid in a nonpolar solvent: chlorobenzene–benzene, chlorobenzene–hexane. The measurements were carried out at a wavelength [Formula: see text][Formula: see text]cm in the temperature range from [Formula: see text]C to [Formula: see text]C. The studies were carried out using the dielectric spectroscopy method. This method allows a more detailed study of the dielectric properties of the objects of study due to the large equilibrium (“static”) dielectric constant of the object. The temperature dependence of the dielectric relaxation time of molecules in the liquid and solid states of the studied solutions is determined. It has been established that with increasing concentration (0.300, 0.562, 0.794, 1.000 for a chlorobenzene–hexane solution and 0.179, 0.368, 0.567, 0.778, 1.000 for a chlorobenzene–benzene solution) of the halogen substituent, the relaxation time increases. The measurement results of dielectric constant [Formula: see text] and absorption coefficient [Formula: see text] obtained for concentrated solutions chlorobenzene–benzene, chlorobenzene–n–hexane at wavelengths [Formula: see text], 80 and [Formula: see text][Formula: see text]cm at temperature [Formula: see text]C are given in the paper. The static dielectric constant is obtained at a frequency of 1[Formula: see text]MHz. The obtained experimental values [Formula: see text], [Formula: see text] and [Formula: see text] of investigated systems in ([Formula: see text], [Formula: see text]) plane locate on the semi-circle the center of which is on [Formula: see text] axis. In this case, the high-frequency limit value of [Formula: see text] dielectric coefficient exceeds the corresponding n2 refraction index square. The macroscopic and molecular relaxation times are calculated on the base of experimental data. The thermodynamic quantities characterizing the process of dielectric relaxation are calculated for solutions of chlorobenzene–benzene, chlorobenzene–hexane. It has been determined that the height of the potential barrier separating the two equilibrium positions of a polar molecule is greatest in the state of a pure polar liquid and decreases with dilution in a nonpolar solvent.

Improving stability and efficiency of three-dimensional perovskite solar cells with organophosphorus ligands

The core density of the defects in perovskite thin films will directly affect the properties of perovskite solar cells. On the other hand, interface engineering is usually being used to effectively improve the quality of perovskite thin films. In this sought of work, MAPbI3 perovskite thin films were modified by an antisolvent process using trioctylphosphine as a passivator. Trioctylphosphine is a kind of Lewis base and from the experimental results, it is noticed on being contribute to MAPbI3 grain growth and grain boundary passivation. Due to the grain boundary passivation and grain size increase, the intense defect density inside the grain and at the grain boundary of the MAPbI3 films is gradually reduced, thereby improving the carrier lifetime, while the hydrophobic property of octyl alkane makes the perovskite thin films less susceptible to air, water and oxygen degraded by the influence. The solar cell which are using the proposed films with the device structure configuration as ITO/SnO2/MAPbI3/spiro-OMeTAD/Ag and the perovskite layers were modified with trioctylphosphine. Among them, the perovskite thin films showcased to have a best performance when the trioctylphosphine chlorobenzene solution was about 0.15% and the PCE of the device reached for about 12.17%, an increase of 10% was compared with the standard device. In addition, the modified device exhibits good environmental stability, retaining about 90% of the initial efficiency for 100 h in a 70% humidity environment.

Heteropolymer improves p-i junction in perovskite solar cells

The p-i heterojunction imbedded underneath the perovskite layer plays a vital role in determining the efficiency and stability of inverted perovskite solar cells (PSCs). We found that poly[bis(4-phenyl) (2,4,6-trimethylphenyl) amine] (PTAA) suffers from the severely chain entanglement resulting in poor contact with perovskite. In this work, PTAA layer was treated by poly[(2,6-(4,8-bis(5-(2-ethylhexylthio)-4-fluorothiophen-2-yl)-benzo[1,2-b:4,5-b′] dithiophene))-alt-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis(2-ethylhexyl) benzo[1′,2′-c:4′,5′-c′] dithiophene-4,8-dione)] (PBDB-T-SF) diluted solution in chlorobenzene. PBDB-T-SF, which contains dual carbonyl groups in its backbones and suitable electronic levels, can spontaneously fill the voids in chlorobenzene-washed PTAA (nano-PTAA). This not only promotes the work function of the substrate but also strengthens the coherence between perovskite and the substrate. Blade coated PSC (0.09 cm2) containing PBDB-T-SF (s-PSCs) realized a power conversion efficiency (PCE) of 21.83 %. After aging for more than 2000 h, s-PSCs maintains 88 % of the initial efficiency which is only 59 % for the control devices.

Flexible all-organic photodetectors via universal water-assisted transfer printing

Transfer printing of small-molecular organic semiconductors often faces challenges due to surface adhesion mismatch. Here, we developed a sacrificing-layer-assisted transfer printing technique for the deposition of small-molecular thin films. High-boiling-point ethylene glycol (EG) was doped in aqueous solution poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as the sacrificing layer to manipulate residual water in film, which allowed chlorobenzene solution to spontaneously spread and form uniform film. The residual water guaranteed film delamination from the stamp, allowing for its transfer onto various substrates and seeding layers. As a proof of concept, laterally conductive organic photodetectors using recyclable EG-PEDOT:PSS electrodes and a small-molecular active layer were consecutively fabricated via transfer printing in ambient air. The resulting device exhibited a high on/off ratio of 711 and a fast rise time of 0.5ms. Notably, the polymer electrode and the bulk heterojunction demonstrated unique repairability and recyclability.

Effects of Cu substitution on photocatalytic performance of ZnO nanorods synthesised via hydrothermal route for the degradation of chlorobenzene

ABSTRACT In the present study, photocatalytic material ZnO nanorod and 20%Cu-substituted ZnO nanorod synthesised via hydrothermal route by using Zn(NO3)2.6 H2O and CuCl2.2 H2O as the source of zinc and copper, respectively. Cu present in 20%Cu-substituted ZnO NRs photocatalytic material led to reducing in the band gap of pure ZnO and enhanced the efficiency of photocatalytic material. Sample purity and crystallinity were investigated by XRD study. The surface study and extent of doping were examined by the SEM-EDX analysis.20%Cu-substituted ZnO NRs showed enriched degradation efficiency of 100 ppm chlorobenzene solution than ZnO NRs at pH 5 in 120 min under visible light.

In Situ Study the Dynamics of Blade‐Coated All‐Polymer Bulk Heterojunction Formation and Impact on Photovoltaic Performance of Solar Cells

All‐polymer solar cells (all‐PSCs) have achieved impressive progress by employing acceptors polymerized from well performing small‐molecule non‐fullerene acceptors. Herein, the device performance and morphology evolution in blade‐coated all‐PSCs based on PBDBT:PF5–Y5 blends prepared from two different solvents, chlorobenzene (CB), and ortho‐xylene (o‐XY) are studied. The absorption spectra in CB solution indicate more ordered conformation for PF5–Y5. The drying process of PBDBT:PF5–Y5 blends is monitored by in situ multifunctional spectroscopy and the final film morphology is characterized with ex situ techniques. Finer‐mixed donor/acceptor nanostructures are obtained in CB‐cast film than that in o‐XY‐cast ones, corresponding to more efficient charge generation in the solar cells. More importantly, the conformation of polymers in solution determines the overall film morphology and the device performance. The relatively more ordered structure in CB‐cast films is beneficial for charge transport and reduced non‐radiative energy loss. Therefore, to achieve high‐performance all‐PSCs with small energy loss, it is crucial to gain favorable aggregation in the initial stage in solution.

Accumulation and ordering of P3HT oligomers at the liquid-vapor interface with implications for thin-film morphology.

The morphology of semiconducting polymer thin films is known to have a profound effect on their opto-electronic properties. Although considerable efforts have been made to control and understand the processes which influence the structures of these systems, it remains largely unclear what physical factors determine the arrangement of polymer chains in spin-cast films. Here, we investigate the role that the liquid-vapor interfaces in chlorobenzene solutions of poly(3-hexylthiophene) [P3HT] play in the conformational geometries adopted by the polymers. Using all-atom molecular dynamics (MD), and supported by toy-model simulations, we demonstrate that, with increasing concentration, P3HT oligomers in solution exhibit a strong propensity for the liquid-vapor interface. Due to the differential solubility of the backbone and side chains of the oligomers, in the vicinity of this interface, hexyl chains and the thiophene rings, have a clear orientational preference with respect to the liquid surface. At high concentrations, we additionally establish a substantial degree of inter-oligomer alignment and thiophene ring stacking near the interface. Our results broadly concur with the limited existing experimental evidence and we suggest that the interfacial structure can act as a template for film structure. We argue that the differences in solvent affinity of the side chain and backbone moieties are the driving force for the anisotropic orientations of the polymers near the interface. This finer grained description contrasts with the usual monolithic characterization of polymer units. Since this phenomenon can be controlled by concurrent chemical design and the choice of solvents, this work establishes a fabrication principle which may be useful to develop more highly functional polymer films.

Conducting Electrospun Nanofibres: Monitoring of Iodine Doping of P3HT through Infrared (IRAV) and Raman (RaAV) Polaron Spectroscopic Features

Aligned polymer nanofibres are prepared by means of the electrospinning of a chlorobenzene solution containing regioregular poly(3-hexyltiophene-2,5-diyl), P3HT, and poly(ethylene oxide), PEO. The PEO scaffold is easily dissolved with acetonitrile, leaving pure P3HT fibres, which do not show structural modification. Polymer fibres, either with or without the PEO supporting polymer, are effectively doped by exposure to iodine vapours. Doping is monitored following the changes in the doping-induced vibrational bands (IRAVs) observed in the infrared spectra and by means of Raman spectroscopy. Molecular orientation inside the fibres has been assessed by means of IR experiments in polarised light, clearly demonstrating that electrospinning induces the orientation of the polymer chains along the fibre axis as well as of the defects introduced by doping. This work illustrates a case study that contributes to the fundamental knowledge of the vibrational properties of the doping-induced defects-charged polarons-of P3HT. Moreover, it provides experimental protocols for a thorough spectroscopic characterisation of the P3HT nanofibres, and of doped conjugated polymers in general, opening the way for the control of the material structure when the doped polymer is confined in a one-dimensional architecture.

Solvent‐Induced Polymorphism in Non‐Fullerene‐Based Organic Solar Cells

Organic photovoltaics have achieved breakthroughs in power conversion efficiency due to the superior aggregation and packing nature of non‐fullerene acceptors (NFAs). Solution processing and various treatments would tend to form distinct packing motifs for state‐of‐the‐art NFAs. Herein, the solvent‐induced polymorphism for 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophne) (ITIC) prepared by chloroform (CF) and chlorobenzene (CB) is revealed. The packing motif of ITIC exhibits dense π–π stacking from CF induction, which presents red‐shifted absorption and reversible high‐temperature crystallization and melting. Meanwhile, strong lamellar stacking and π–π stacking can be formed in the CB solution with unstable low‐temperature crystallization and melting. Combining in situ absorption spectra and interaction calculation, the stronger preaggregation of ITIC in the CF solution was found to be the main reason for forming a different packing motif from in the CB solution. The packing and thermodynamic features are retained in the PBDB‐T:ITIC blends, though good miscibility weakens characteristic features. Benefiting from the polymorph structure, CB‐processed devices denote more favorable performance but less thermal stability. This research indicates the significant effect of solvent induction for manipulating and optimizing the morphology of organic solar cell devices.

Impact of fluorination of central thiophene linking core in thermostable perylene-diimide-based dimeric acceptors on molecular configuration and photovoltaic performance

Fluorination was an easy and effective strategy to adjust the absorption, electronic energy level, molecular configuration and aggregation as well as charge mobility, miscibility, morphology and photovoltaic property. Herein, two perylene-diimide-based non-fullerene dimeric acceptors, called T-(PDI-HD)2 and 2FT-(PDI-HD)2, were obtained via Stille coupling reaction between bistin compounds (TSn and 2FTSn) and monobromide PDI-HDBr. The dramatically reduced twisted angle from 81.80o to 19.78o and strengthened molecular stacking both in chlorobenzene solution and solid film states were found after fluorination, resulting in an elevated thermostability and slightly enhanced electron mobility. Furthermore, fluorination led to the down-shifted ELUMO, worse miscibility and undesired microstructural morphology with oversized aggregation which impeded the exciton dissociation and restricted the photocurrent. As a consequence, the slightly declined VOC, 18.52% down-shifted JSC but 12.38% increased FF were found, leading to a 9.69% decline in PCE from 2.58% to 2.33% after bisfluorinating the central thiophene linking core, which was imputed to the deepened ELUMO, worse light-harvesting capability and undesired morphology as a result of fluorination regardless of the slightly elevated electron mobility. Our results have demonstrated that it was cautious that incorporating fluorine substituents into central linking core by virtue of tuning the twisting degree boosted the photovoltaic property in PDI-based dimeric acceptors.

Improving the Molecular Packing Order and Vertical Phase Separation of the P3HT:O-IDTBR Blend by Extending the Crystallization Period of O-IDTBR.

The morphology with strong molecular packing order and gradient vertical composition distribution associated with efficient charge transport and collection is critical to achieve high performance in nonfullerene solar cells. However, the rapid solidification process of the active layer upon the fast removal of solvent usually results in a kinetically trapped state with undesired morphology. Herein, we proposed a strategy to extend the crystal growth time of the acceptor via a high-boiling-point additive that selectively dissolved the acceptor. This was enabled by adding dibenzyl ether (DBE) to the poly(3-hexylthiophene) (P3HT):O-IDTBR blend in chlorobenzene (CB) solution. The combination of the kinetic study by time-resolved ultraviolet-visible (UV-vis) absorption spectra and detailed morphological characterization allows us to correlate the crystallization kinetics with the microstructural transition. The results show that the crystal growth time of O-IDTBR increases from 3 to 60 s upon the addition of 0.75% DBE, leading to further evolution of the molecular order of O-IDTBR during the DBE-dominated drying period. Meanwhile, O-IDTBR has more time to migrate toward the substrate owing to the larger surface energy. In addition, the onset of the crystallization process of P3HT is brought forward from 8 to 6 s due to the reduced solvent quality, which favors P3HT to crystallize into a fibril network. As a result, an optimized morphology that features the enhanced molecular packing order of P3HT and O-IDTBR as well as the vertical compositional gradient of O-IDTBR is obtained. Devices based on the optimized blend show more balanced charge transport and suppressed bimolecular recombination, giving rise to an improved power conversion efficiency (PCE) from 4.29 ± 0.04 to 7.30 ± 0.12%.

Charge-Separated Reactive Intermediates from the UV Photodissociation of Chlorobenzene in Solution.

Although ultraviolet (UV)-induced photochemical cleavage of carbon–halogen bonds in gaseous halocarbons is mostly homolytic, the photolysis of chlorobenzene in solution has been proposed to produce a phenyl cation, c-C6H5+, which is a highly reactive intermediate of potential use in chemical synthesis and N2 activation. Any evidence for such a route to phenyl cations is indirect, with uncertainty remaining about the possible mechanism. Here, ultrafast transient absorption spectroscopy of UV-excited (λ = 240 and 270 nm) chlorobenzene solutions in fluorinated (perfluorohexane) and protic (ethanol and 2,2,2-trifluoroethanol) solvents reveals a broad electronic absorption band centered at 540 nm that is assigned to an isomer of chlorobenzene with both charge-separated and triplet-spin carbene character. This spectroscopic feature is weaker, or absent, when experiments are conducted in cyclohexane. The intermediate isomer of chlorobenzene has a solvent-dependent lifetime of 30–110 ps, determined by reaction with the solvent or quenching to a lower-lying singlet state. Evidence is presented for dissociation to ortho-benzyne, but the intermediate could also be a precursor to phenyl cation formation.

Precursor formula engineering enabling high quality solution processed C60 films for efficient and stable inverted perovskite solar cells

Solution processed fullerene (C60) films as the electron transport layers (ETLs) promise to substantially reduce the cost of the perovskite solar cells (PSCs). However, the self-aggregation nature of C60 when dissolved in a solvent with high solubility (e.g., o-dichlorobenzene, o-DCB) makes the efficiency of the resulting PSCs lower than 18%. In this paper, we proposed a novel recipe of C60 precursor solutions (XP-C60) by using o-xylene (o-X) as the solvent and PCBM solution in chlorobenzene (CB) as the additive, which can simultaneously inhibit the aggregation of C60 and advocate fast solvent drying. Homogeneous C60 films of high quality from the new recipe solution can be readily fabricated at room temperatures, advocating the efficiency of the printed PSCs to over 17%. Finally, a champion efficiency of over 20% for the PSCs was achieved which is comparable to that of the PSCs with PCBM as the ETLs. XP-C60 based PSCs also show good stability, which sustain 85% of its initial efficiency as being exposed in air with a relative humidity (RH) of 50% for over 20 days. Our work helps to understand the film-formation dynamics of C60 by a solution method and cut the production cost of the PSCs to the bone.

Layered optimization strategy enables over 17.8% efficiency of layer-by-layer organic photovoltaics

In this work, layer-by-layer (LbL) type OPVs are constructed with wide bandgap polymer PNTB6-Cl as donor and nonfullerene material BTP-4F-12 as acceptor. The layered optimization strategy is employed via separately incorporating the diphenyl ether (DPE) and 1,8-diiodooctane (DIO) into PNTB6-Cl chlorobenzene solution and BTP-4F-12 chloroform solution. A power conversion efficiency (PCE) of 17.81% was achieved from the optimal LbL type OPVs with two solvent additives, which should be among the top level for LBL type binary OPVs. The incorporation of DPE and DIO can separately induce more ordered PNTB6-Cl and BTP-4F-12 orientation, which should contribute to charge transport with suppressed charge recombination in active layers. Meanwhile, BTP-4F-12 crystallization is strongly increased with the incorporation of DIO, which should facilitate more swell matrix for exciton diffusion in active layers. Over 13% PCE improvement can be realized in LbL type OPVs by incorporating two additives, benefiting from simultaneously improved short circuit current density (JSC) of 26.89 mA cm−2 and fill factor (FF) of 75.79%. Meanwhile, the PCE of optimized LbL type OPVs is higher than that of 17.33% for the optimized OPVs with bulk-heterojunction (BHJ) configuration, which reveals that layered optimization strategy should be a promising approach to achieve highly efficient LbL type OPVs.