Novel Polyelectrolytes Based on Naphthalene Diimide with Different Counteranions for Cathode Interlayers in Polymer Solar Cells.

We synthesized novel polyelectrolytes based on naphthalene diimide with quaternary amine featuring hydroxyl groups at the side chain, along with different counteranions (PF-NDIN-Br-OH and PF-NDIN-I-OH) for polymer solar cell (PSC) application as the interlayer. The polyelectrolytes establish a beneficial interface dipole through the ionic moieties and synergistic effects arising from the hydroxyl groups located at the side chain. Incorporating polyelectrolytes as the cathode interlayer resulted in an enhancement of the power conversion efficiency (PCE). The PCE of the device with PF-NDIN-Br-OH increased from 8.96% to 9.51% compared to the ZnO-only device. The best PCE was obtained with the device based on PF-NDIN-I-OH, up to 9.59% resulting from the Jsc enhancement. This outcome implies a correlation between the performance of the device and the synergistic effects observed in polyelectrolytes containing hydroxyl groups in the side chain, along with larger anions when employed in PSCs.

Biological/metal oxide composite transport layers cast from green solvents for boosting light harvesting response of organic photovoltaic cells indoors.

Organic solar cells with biological/metal-oxide electron transport layers (ETLs), consisting of a ZnO compact layer covered by a thin DNA layer, both of which deposited with green solvents (water or water/alcohols mixtures) are presented for application under low intensity indoor lighting. Under white LED lamp (200, 400 lx), photovoltaic cells with P3HT:PC70BM polymer semiconductor blends delivered an average maximum power density (MPD) of 8.7µW cm-2, corresponding to a power conversion efficiency, PCE, of = 8.56% (PCE of best cell was 8.74%). The ZnO/DNA bilayer boosted efficiency by 68% and 13% in relative terms compared to cells made with DNA-only and ZnO-only ETLs at 400 lx. Photovoltaic cells with ZnO/DNA composite ETLs based on PTB7:PC70BM blends, that absorb a broader range of the indoor lighting spectrum, delivered MPDs of 16.2µW cm-2with an estimated average PCE of 14.3% (best cell efficiency of 15.8%) at 400 lx. The best efficiencies for cells fabricated on flexible plastic substrates were 11.9% at 400 lx. This is the first report in which polymer photovoltaics incorporating biological materials have shown to increment performance at these low light levels and work very efficiently under indoor artificial light illumination. The finding can be useful for the production of more bio-compatible photovoltaics as well as bio-sensing devices based on organic semiconductors.

Medium Bandgap Polymers for Efficient Non-Fullerene Polymer Solar Cells-An In-Depth Study of Structural Diversity of Polymer Structure.

A series of medium bandgap polymer donors, named poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)thiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(thiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione) (IND-T-BDTF), poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)-4-hexylthiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(4-hexylthiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND-HT-BDTF), and poly(1-(5-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo [1,2-b:4,5-b']dithiophen-2-yl)-6-octylthieno [3,2-b]thiophen-2-yl)-5-((4,5-dihexylthiophen-2-yl)methylene)-3-(6-octylthieno [3,2-b]thiophen-2-yl)-4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND-OTT-BDTF), are developed for non-fullerene acceptors (NFAs) polymer solar cells (PSCs). Three polymers consist of donor-acceptor building block, where the electron-donating fluorinated benzodithiophene (BDTF) unit is linked to the electron-accepting 4H-cyclopenta[c]thiophene-4,6(5H)-dione (IND) derivative via thiophene (T) or thieno [3,2-b]thiopene (TT) bridges. The absorption range of the polymer donors based on IND in this study shows 400~800 nm, which complimenting the absorption of Y6BO (600~1000 nm). The PSC's performances are also significantly impacted by the π-bridges. NFAs inverted type PSCs based on polymer donors and Y6BO acceptor are fabricated. The power conversion efficiency (PCE) of the device based on IND-OTT-BDTF reaches up to 11.69% among all polymers with a short circuit current of 26.37 mA/cm2, an open circuit voltage of 0.79 V, and a fill factor of 56.2%, respectively. This study provides fundamental information on the invention of new polymer donors for NFA-based PSCs.

Enhanced Hole Transport in Ternary Blend Polymer Solar Cells.

Recently, ternary blend polymer solar cells have attracted great attention to improve a short-circuit current density (JSC ) effectively, because complementary absorption bands can harvest the solar light over a wide wavelength range from visible to near-IR region. Interestingly, some ternary blend solar cells have shown improvements not only in JSC but also in fill factor (FF). Previously, we also reported that a ternary blend solar cell based on a low-bandgap polymer (PTB7-Th), a wide-bandgap polymer (PDCBT), and a fullerene derivative (PCBM) exhibited a higher FF than their binary analogues. Herein, we study charge transport in PTB7-Th/PDCBT/PCBM ternary blend films to address the origin of the improvement in FF. We found that hole polarons are located in PTB7-Th domains and their mobility is enhanced in the ternary blend film.

A Green Route to Conjugated Polyelectrolyte Interlayers for High-Performance Solar Cells.

Synthesis of fluorene-based conjugated polyelectrolytes was achieved via Suzuki polycondensation in water and completely open to air. The polyelectrolytes were conveniently purified by dialysis and analysis of the materials showed properties expected for fluorene-based conjugated polyelectrolytes. The materials were then employed in solar cell devices as an interlayer in conjunction with ZnO. The double interlayer led to enhanced power conversion efficiency of 10.75 % and 15.1 % for polymer and perovskite solar cells, respectively.

Transfer-printing of active layers to achieve high quality interfaces in sequentially deposited multilayer inverted polymer solar cells fabricated in air.

Polymer solar cells (PSCs) are greatly influenced by both the vertical concentration gradient in the active layer and the quality of the various interfaces. To achieve vertical concentration gradients in inverted PSCs, a sequential deposition approach is necessary. However, a direct approach to sequential deposition by spin-coating results in partial dissolution of the underlying layers which decreases the control over the process and results in not well-defined interfaces. Here, we demonstrate that by using a transfer-printing process based on polydimethylsiloxane (PDMS) stamps we can obtain increased control over the thickness of the various layers while at the same time increasing the quality of the interfaces and the overall concentration gradient within the active layer of PSCs prepared in air. To optimize the process and understand the influence of various interlayers, our approach is based on surface free energy, spreading parameters and work of adhesion calculations. The key parameter presented here is the insertion of high quality hole transporting and electron transporting layers, respectively above and underneath the active layer of the inverted structure PSC which not only facilitates the transfer process but also induces the adequate vertical concentration gradient in the device to facilitate charge extraction. The resulting non-encapsulated devices (active layer prepared in air) demonstrate over 40% increase in power conversion efficiency with respect to the reference spin-coated inverted PSCs.

Synthesis of a Conjugated D-A Polymer with Bi(disilanobithiophene) as a New Donor Component.

A new conjugated donor-acceptor (D-A) polymer pDSBT2-BT containing bi(disilano-bisthiophene) and benzothiadiazole as donor and acceptor units, respectively, was prepared. The polymer showed a broad UV-vis absorption band at λmax = 599 nm in chlorobenzene. The absorption band was shifted to λmax = 629 nm when the polymer was measured as a film, indicating enhanced interchain interactions of the polymer. Bulk hetero-junction polymer solar cells (BHJ-PSCs) were fabricated using pDSBT2-BT and PC71BM as host and guest materials, respectively. Optimization of cell fabrication conditions provided a maximal power conversion efficiency of 3.3% and the following cell parameters: Voc = 0.86 V, Jsc = 7.56 mA/cm², and FF = 0.51. Although the efficiency still leaves much to be desired, these data underscore the potential of pDSBT2-BT as a high-voltage polymer solar cell material.

Flexible graphene electrode-based organic photovoltaics with record-high efficiency.

Advancements in the field of flexible high-efficiency solar cells and other optoelectronic devices will strongly depend on the development of electrode materials with good conductivity and flexibility. To address chemical and mechanical instability of currently used indium tin oxide (ITO), graphene has been suggested as a promising flexible transparent electrode but challenges remain in achieving high efficiency of graphene-based polymer solar cells (PSCs) compared to their ITO-based counterparts. Here we demonstrate graphene anode- and cathode-based flexible PSCs with record-high power conversion efficiencies of 6.1 and 7.1%, respectively. The high efficiencies were achieved via thermal treatment of MoO3 electron blocking layer and direct deposition of ZnO electron transporting layer on graphene. We also demonstrate graphene-based flexible PSCs on polyethylene naphthalate substrates and show the device stability under different bending conditions. Our work paves a way to fully graphene electrode-based flexible solar cells using a simple and reproducible process.

Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene-Quinoxaline Polymers.

Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (∼-5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N'-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (VOC) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high VOC.

Dual Polymerized Y-Acceptors of Distinct-Dimensionality Create Neuron-Like Interpenetrating Hierarchical Network towards Efficient and Stable All-Polymer Solar Cells.

All-polymer solar cells have garnered particular attention thanks to their superior thermal, photo, and mechanical stabilities for large-scale manufacturing, yet the performance enhancement remains largely restrained by inherent morphological challenges of the bulk-heterojunction active layer. Herein, a 3D Y-branched polymerized small-molecule acceptor named PYBF, characteristic of high molecular weight and glass transition temperature, is designed and synthesized by precisely linking C3h-symmetric benzotrifuran with Y6 acceptors. In comparison to the benchmark thiophene-bridged linear PYIT acceptor, an optical blue-shift absorption is observed for PYBF yet a slightly higher power conversion efficiency (PCE) of 15.7% (vs 15.14%) is obtained when paired with polymer donor PM6, which benefit from the more crystalline and face-on-oriented PYBF domains. However, the star-like bulky structure of PYBF results in the nucleation-growth dominant phase-separation in polymeric blends, which generates stumpy droplet-like acceptor fibrils and impairs the continuity of acceptor phases. This issue is however surprisingly resolved by incorporating a small amount of PYIT, which leads to the formation of the more interconnective neuron-like dual-acceptor domains by long-chain entanglements of linear acceptors and alleviates bimolecular recombination. Thus, the champion device realizes a respectable PCE of up to ≈17% and importantly exhibits thermal and storage stabilities superior to the linear counterpart.

An Investigation of the Inverted Structure of a PBDB:T/PZT:C1-Based Polymer Solar Cell.

Based on experimental results, this theoretical study presents a new approach for investigating polymers' solar cells. P-type PZT:C1 and N-type PBDB:T were used to construct a blend for use as a photoactive layer for the proposed all-polymer solar cell. Initially, an architecture of an ITO/PEDOT:PSS/PBDB:T/PZT:C1/PFN-Br/Ag all-polymer solar device calibrated with experimental results achieved a PCE of 14.91%. A novel inverted architecture of the same solar device, proposed for the first time in this paper, achieved a superior PCE of 19.92%. Furthermore, the optimization of the doping of the transport layers is proposed in this paper. Moreover, the defect density and the thickness of the polymer are studied, and a PCE of 22.67% was achieved by the optimized cell, which is one of the highest PCEs of polymer solar devices. Finally, the optimized polymer solar cell showed good stability amidst temperature variations. This theoretical study sheds light on the inverted structure of all-polymer solar devices.

All-Polymer Solar Cells and Photodetectors with Improved Stability Enabled by Terpolymers Containing Antioxidant Side Chains.

It is of vital importance to improve the long-term and photostability of organic photovoltaics, including organic solar cells (OSCs) and organic photodetectors (OPDs), for their ultimate industrialization. Herein, two series of terpolymers featuring with an antioxidant butylated hydroxytoluene (BHT)-terminated side chain, PTzBI-EHp-BTBHTx and N2200-BTBHTx (x = 0.05, 0.1, 0.2), are designed and synthesized. It was found that incorporating appropriate ratio of benzothiadiazole (BT) with BHT side chains on the conjugated backbone would induce negligible effect on the molecular weight, absorption spectra and energy levels of polymers, however, which would obviously enhance the photostability of these polymers. Consequently, all-polymer solar cells (all-PSCs) and photodetectors were fabricated, and the all-PSC based on PTzBI-EHp-BTBHT0.05: N2200 realized an optimal power conversion efficiency (PCE) approaching ~ 10%, outperforming the device based on pristine PTzBI-EHp: N2200. Impressively, the all-PSCs based on BHT-featuring terpolymers displayed alleviated PCEs degradation under continuous irradiation for 300 h due to the improved morphological and photostability of active layers. The OPDs based on BHT-featuring terpolymers achieved a lower dark current at - 0.1 bias, which could be stabilized even after irradiation over 400 h. This study provides a feasible approach to develop terpolymers with antioxidant efficacy for improving the lifetime of OSCs and OPDs.

Enhanced Efficiency and Stability of Novel Pseudo-ternary Polymer Solar Cells Enabled by a Conjugated Donor Block Copolymer.

The recent breakthrough in power conversion efficiencies (PCEs) of polymer solar cells (PSCs) that contain an active layer of a ternary system has achieved values of 18-19%; this has sparked interest for further research. However, this system has difficulties in optimizing the composition and controlling the interaction between the three active materials. In this study, we investigated the use of a donor1 (D1)-donor2 (D2) conjugated block copolymer (CBP), PM6-b-TT, to replace the physical blend of two donors. PM6-b-TT, which exhibits an extended absorption range, was synthesized by covalently bonding PM6, a medium-band gap polymer, with PBDT-TT, a wide-band gap polymer. The blend films containing PM6-b-TT and Y6-BO acceptor, demonstrated excellent crystallinity and a film morphology favorable for PSCs. The corresponding pseudo-ternary PSC exhibited significantly higher PCE and thermal stability than the PM6:PBDT-TT-based ternary device. This study unambiguously demonstrates that the novel D1-D2 CBP strategy, combined with the conventional binary and ternary system advantages, is a promising material production strategy that can boost the performance of future PSCs.

Plasmonic Effects of Au@Ag Nanoparticles in Buffer and Active Layers of Polymer Solar Cells for Efficiency Enhancement.

Embedding nanoparticles (NPs) in the buffer layer of bulk heterojunction polymer solar cells (BHJ PSCs) excites the surface plasmonic polaritons and enhances the pathlength of the light in the solar cells. On the other hand, embedding NPs in the active layer significantly improves absorption and increases the production of electron-hole (e-h) pairs in BHJ PSCs. Increasing the volume ratio of NPs embedded in BHJ PSCs enables the direct interfacing of the NPs with the active layer, which then serves as a charge recombination center. Therefore, this study integrates the aforementioned phenomena by exploiting the effects of embedding plasmonic Au@Ag NPs in the buffer and active layers of PSC and then determining the optimum volume ratio of Au@Ag NPs. The results show the absorption is increased across the 350-750 nm wavelength region, and the PCE of the device with embedded Au@Ag in two locations is enhanced from 2.50 to 4.24%, which implies a 69.6% improvement in the PCE in comparison to the reference cell. This improvement is contributed by the combined localized surface plasmon resonance (LSPR) effects of multi-positional Au@Ag NPs, spiky durian-shaped morphology of Au@Ag NPs, and optimized volume ratio of Au@Ag NPs embedded in the PEDOT: PSS and PTB7:PC71BM layers.

High Performance Polymer Solar Cells Using Grating Nanostructure and Plasmonic Nanoparticles.

This work introduces a high-efficiency organic solar cell with grating nanostructure in both hole and electron transport layers and plasmonic gold nanoparticles (Au NPs) distributed on the zinc oxide (ZnO) layer. The periods of the grating structure in both hole and electro transport layers were optimized using Lumerical finite difference time domain (FDTD) solution software. The optimum AuNP radius distributed on the ZnO layer was also simulated and analyzed before studying the effect of changing the temperature on the solar cell performance, fill factor, and power conversion efficiency. In addition, optical and electrical models were used to calculate the short circuit current density, fill factor, and overall efficiency of the produced polymer solar cell nanostructure. The maximum obtained short circuit current density and efficiency of the solar cell were 18.11 mA/cm2 and 9.46%, respectively, which gives a high light absorption in the visible region. Furthermore, the effect of light polarization for incident light angles from θ = 0° to 70° with step angle 10° on the electrical and optical parameters were also studied. Finally, optical power, electric field, and magnetic field distribution inside the nanostructure are also illustrated.

Improved Stability of All-Polymer Solar Cells Using Crosslinkable Donor and Acceptor Polymers Bearing Vinyl Moieties in the Side-Chains.

Crosslinkable polymers have attracted tremendous attention in various fields of science and technology, owing to their potential utilization in applications requiring dimensional and morphological stability under thermal and mechanical stress. In this study, random terpolymers were successfully synthesized by introducing thiophene-based monomers bearing vinyl functional groups in the side-chain of the polymer donor (PBDBT-BV20) and polymer acceptor (N2200-TV10) structures. The physical properties of the blend films of PBDBT-BV20 and N2200-TV10 before and after thermal crosslinking were extensively investigated and compared to those of the homogeneous individual polymer films. The results revealed that a network polymer with donor and acceptor polymer chains, which can lock the internal morphology, could be achieved by inducing crosslinking between the vinyl groups in the mixed state of PBDBT-BV20 and N2200-TV10. In addition, the power conversion efficiency (PCE) of the polymer solar cells (PSCs) containing the blend films that were crosslinked by a two-step thermal annealing process was improved. The enhanced PCE could be attributed to the individual crystallization of PBDBT-BV20 and N2200-TV10 in the blend phase at 120 °C and then thermal crosslinking at 140 °C. In addition, the PSCs with the crosslinked blend film exhibited an excellent shelf-life of over 1200 h and a thermally stable PCE. Furthermore, the crosslinked blend film exhibited excellent mechanical stability under bending stress in flexible PSCs using plastic substrates.

Ultrasonically Processed WSe2 Nanosheets Blended Bulk Heterojunction Active Layer for High-Performance Polymer Solar Cells and X-ray Detectors.

Two-dimensional (2D) tungsten diselenide (WSe2) has attracted considerable attention in the field of photovoltaic devices owing to its excellent structure and photoelectric properties, such as ordered 2D network structure, high electrical conductivity, and high mobility. For this test, we firstly prepared different sizes (NS1-NS3) of WSe2 nanosheets (NSs) through the ultrasonication method and characterized their structures using the field emission scanning electron microscope (FE-SEM), Raman spectroscopy, and X-ray powder diffraction. Moreover, we investigated the photovoltaic performance of polymer solar cells based on 5,7-Bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione(PBDB-T):(6,6)-phenyl-C71 butyric acid methyl ester (PCBM) with different WSe2 NSs as the active layer. The fabricated PBDB-T:PCBM active layer with the addition of NS2 WSe2 NSs (1.5 wt%) exhibited an improved power conversion efficiency (PCE) of 9.2%, which is higher than the pure and NS1 and NS3 WSe2 blended active layer-encompassing devices. The improved PCE is attributed to the synergic enhancement of exciton dissociation and an improvement in the charge mobility through the modified active layer for polymer solar cells. Furthermore, the highest sensitivity of 2.97 mA/Gy·cm2 was achieved for the NS2 WSe2 NSs blended active layer detected by X-ray exposure over the pure polymer, and with the NS1 and NS2 WSe2 blended active layer. These results led to the use of transition metal dichalcogenide materials in polymer solar cells and X-ray detectors.

Enhancement of All-Polymer Solar Cells by Addition of a Chlorinated Polymer and Formation of an Energy Cascade in a Nonhalogenated Solvent.

Ternary organic solar cells (OSCs) containing a three-component photoactive layer with cascading energy alignments could benefit the charge transfer and improve the open-circuit voltage and power conversion efficiency. Herein, we report the incorporation of a derived chlorinated polymer, J52-Cl, as a guest donor into the donor J52 and acceptor N2200 blend film. The lowest unoccupied molecular orbital and the highest occupied molecular orbital levels of J52-Cl are between the corresponding energy levels of J52 and N2200, and this leads to generation of a cascade of energy levels. Photoluminescence measurements and the J-V of devices containing the donors indicated that this incorporation of J52-Cl could promote the charge transfer of the solar cells. The contribution from J52-Cl reduced the energy loss of J52-based binary devices significantly from 0.932 to 0.797 eV and the nonradiative energy loss from 0.399 to 0.269 eV, leading to an enhancement of Voc from 0.79 to 0.93 V. This introduction of chlorinated polymers also improves the intermolecular interactions and leads to a favorable morphology with appropriate phase separation and interpenetrating networks. As expected, the power conversion efficiency of ternary all-polymer solar cells (all-PSCs) processed in o-xylene solvent was increased from 8.55 to 11.02%. These results indicate that the ternary devices with the appropriate cascade of energy levels can fine tune the device's open-circuit voltage and finally improve the photovoltaic performance of OSCs.

The Crystallinity Control of Polymer Donor Materials for High-Performance Organic Solar Cells.

Bulk heterojunction (BHJ) organic solar cells (OSCs) can be regarded as one of the most promising energy generation technologies for large-scale applications. Despite their several well-known drawbacks, the devices where polymers are employed as the donor are still leading the OSC universe in terms of performance. Such performance generally depends upon various critical factors such as the crystallinity of the material, the crystallization process during the film formation, and also the final film morphology. Despite a few reviews on the structure of the polymer donor materials and device performance, not enough attention has been paid toward the crystallinity problem. Herein, the structure and crystallinity of the representative polymer donor materials and the corresponding device properties have been briefly reviewed. Furthermore, several typical methods for controlling the crystallinity of materials have been summarized and illustrated as well. Moreover, the obstacles lying in the way of successful commercialization of such polymer solar cells have been systematically discussed. The in-depth interpretation of the crystallinity of the polymer donors in this article may stimulate novel ideas in material design and device fabrication.

Synergistic Effect of Alkyl Chain and Chlorination Engineering on High-Performance Nonfullerene Acceptors.

In this work, three new nonfullerene acceptors (BT6IC-BO-4Cl, BT6IC-HD-4Cl, and BT6IC-OD-4Cl), which comprise a central fused benzothiadiazole core and two dichlorinated end groups and substituted with different branched alkyl chains [2-butyloctyl (BO), longer 2-hexyldecyl (HD), and 2-octyldodecyl (OD)], are successfully designed and prepared. The influences of the branched alkyl chain with different lengths on the electronic/optoelectronic property, electrochemistry, and photovoltaic performance are systematically investigated. It has been revealed that BT6IC-HD-4Cl, which had the medium alkyl chain (2-hexyldecyl) length, has the best photovoltaic performance when using PDBT-TF as the electron donor. The BT6IC-HD-4Cl-based device shows an impressive power conversion efficiency of 14.90%, much higher than BT6IC-BO-4Cl (14.45%)- and BT6IC-OD-4Cl (9.60%)-based devices. All these evidence shows that the subtle changes in the alkyl substituent of these high-performance chlorinated acceptors can have a big impact on the structural order and molecular packing of the resultant nonfullerene acceptors and ultimately on the photovoltaic performance of the final solar devices.