Effect of Alkylsilyl Side‐Chain Structure on Photovoltaic Properties of Conjugated Polymer Donors

Side‐chain engineering is an important strategy for optimizing photovoltaic properties of organic photovoltaic materials. In this work, the effect of alkylsilyl side‐chain structure on the photovoltaic properties of medium bandgap conjugated polymer donors is studied by synthesizing four new polymers J70 , J72 , J73 , and J74 on the basis of highly efficient polymer donor J71 by changing alkyl substituents of the alkylsilyl side chains of the polymers. And the photovoltaic properties of the five polymers are studied by fabricating polymer solar cells (PSCs) with the polymers as donor and an n‐type organic semiconductor (n‐OS) m‐ITIC as acceptor. It is found that the shorter and linear alkylsilyl side chain could afford ordered molecular packing, stronger absorption coefficient, higher charge carrier mobility, thus results in higher J_sc and fill factor values in the corresponding PSCs. While the polymers with longer or branched alkyl substituents in the trialkylsilyl group show lower‐lying highest occupied molecular orbital energy levels which leads to higher V_oc of the PSCs. The PSCs based on J70 :m‐ITIC and J71 :m‐ITIC achieve power conversion efficiency (PCE) of 11.62 and 12.05%, respectively, which are among the top values of the PSCs reported in the literatures so far.     

Side‐Chain Engineering for Fine‐Tuning of Energy Levels and Nanoscale Morphology in Polymer Solar Cells

A series of four polymers containing benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and 5,6‐difluoro‐4,7‐diiodobenzo[c][1,2,5]thiadiazole (2FBT), PBDT2FBT, PBDT2FBT‐O, PBDT2FBT‐T, and PBDT2FBT‐T‐O, are synthesized with their four different side chains, alkyl‐, alkoxy‐, alkylthienyl‐, and alkoxythienyl. Experimental results and theoretical calculations show that the molecular tuning of the side chains simultaneously influences the solubilities, energy levels, light absorption, surface tension, and intermolecular packing of the resulting polymers by altering their molecular coplanarity and electron affinity. The polymer solar cell (PSC) based on a blend of PBDT2FBT‐T/[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) exhibits the best photovoltaic performance of the four PBDT2FBT derivatives, with a high open‐circuit voltage of 0.98 V and a power conversion efficiency of 6.37%, without any processing additives, post‐treatments, or optical spacers. Furthermore, PBDT2FBT‐T‐O, which has a novel side chain alkoxythienyl, showed promising properties with the most red‐shifted absorption and strong intermolecular packing property in solid state. This study provides insight into molecular design and fabrication strategies via structural tuning of the side chains of conjugated polymers for achieving highly efficient PSCs.     

Cyclopenta[c]thiophene‐4,6‐dione‐Based Copolymers as Organic Photovoltaic Donor Materials

A class of “push‐pull” conjugated copolymers based on cyclopenta[c]thiophene‐4,6‐dione (CTD) and benzodithiophene (BDT) is synthesized for application as an electron donor in organic photovoltaics (OPV). Given the diverse electronic and structural tunability of the CTD unit, specific CTD‐containing copolymers are chosen with the aid of theoretical calculations from a broad array of potential candidate materials. Evaluation of the chosen materials as OPV absorbers includes characterization of the optical, electronic, and structural properties of the polymer films using UV‐vis absorbance, photoluminescence, cyclic voltammetry, and X‐ray diffraction techniques. In addition, the contactless time‐resolved microwave conductivity (TRMC) technique is used to measure the photoconductance of polymer/fullerene blends. Excellent correlation between measured photoconductance and OPV device efficiency is demonstrated with these materials and TRMC is discussed as a tool for screening potential active layer materials for OPV devices.     

Conformational Disorder Enhances Solubility and Photovoltaic Performance of a Thiophene–Quinoxaline Copolymer

The side‐chain architecture of alternating copolymers based on thiophene and quinoxaline (TQ) is found to strongly influence the solubility and photovoltaic performance. In particular, TQ polymers with different linear or branched alkyloxy‐phenyl side chains on the quinoxaline unit are compared. Attaching the linear alkyloxy side‐chain segment at the meta‐ instead of the para‐position of the phenyl ring reduces the planarity of the backbone as well as the ability to order. However, the delocalisation across the backbone is not affected, which permits the design of high‐performance TQ polymers that do not aggregate in solution. The use of branched meta‐(2‐ethylhexyl)oxy‐phenyl side‐chains results in a TQ polymer with an intermediate degree of order. The reduced tendency for aggregation of TQ polymers with linear meta‐alkyloxy‐phenyl persists in the solid state. As a result, it is possible to avoid the decrease in charge‐transfer state energy that is observed for bulk‐heterojunction blends of more ordered TQ polymers and fullerenes. The associated gain in open‐circuit voltage of disordered TQ:fullerene solar cells, accompanied by a higher short‐circuit current density, leads to a higher power conversion efficiency overall. Thus, in contrast to other donor polymers, for TQ polymers there is no need to compromise between solubility and photovoltaic performance.     

Side‐Chain Impact on Molecular Orientation of Organic Semiconductor Acceptors: High Performance Nonfullerene Polymer Solar Cells with Thick Active Layer over 400 nm

A new n‐type organic semiconductor (n‐OS) acceptor IDTPC with n‐hexyl side chains is developed. Compared to side chains with 4‐hexylphenyl counterparts (IDTCN), such a design endows the acceptor of IDTPC with higher electron mobility, more ordered face‐on molecular packing, and lower band gap. Therefore, the IDTPC‐based polymer solar cells (PSCs) with a newly developed wide bandgap polymer PTQ10 as donor exhibit the maximum power conversion efficiency (PCE) of 12.2%, a near 65% improvement in PCE relative to the IDTCN‐based control device. Most importantly, the IDTPC‐based device is insensitive to the thickness of the active layer from 70 to 505 nm, which still gives a PCE of 10.0% with the active‐layer thickness of 400 nm. To the best of the authors' knowledge, a PCE of 10.0% is the highest value for the nonfullerene PSCs with an active layer thicker than 400 nm. These results reveal that the blend of PTQ10 and IDTPC exhibits great potential for highly efficient nonfullerene PSCs and large‐area device fabrication.     

Enhanced Photovoltaic Performance of Amorphous Donor–Acceptor Copolymers Based on Fluorine‐Substituted Benzodioxocyclohexene‐Annelated Thiophene

Donor–acceptor (D‐A) type π‐conjugated copolymers with crystalline behavior have been extensively investigated as donor semiconductors in organic photovoltaics (OPVs). On the other hand, the development of high‐performance amorphous donor materials is still behind. The amorphous donor copolymer DTS‐C₀(F₂) consisting of dithieno[3,2‐b:2′,3′‐d]silole ( DTS ) donor unit and the recently developed fluorine‐substituted naphtho[2,3‐c]thiophene‐4,9‐dione ( C₀(F₂) ) acceptor unit shows moderate photovoltaic performance upon blending with PC₇₁BM. In this work, to enhance the hole‐transporting characteristics, a 3‐hexylthiophene ( HT ) spacer unit is integrated into the conjugated backbone, resulting in a new amorphous copolymer DTS‐HT‐C₀(F₂) . The strong electron‐accepting nature of C₀(F₂) allows the introduction of the HT spacer without affecting the frontier orbital energies and thus the D‐A character. Without using solvent additives and thermal annealing, OPVs based on DTS‐HT‐C₀(F₂) and [6,6]‐phenyl‐C71‐butyric acid methyl ester PC₇₁BM show an improved power conversion efficiency of 9.12%. Investigation of the device physics unambiguously reveals that the hole mobility of the copolymer in the blend is increased by an order of magnitude by the introduction of HT , while keeping an amorphous film nature, leading to higher short‐circuit current density and fill factor. These results demonstrate the realization of high‐performance OPVs based on amorphous active layers.     

High‐Performance and Stable All‐Polymer Solar Cells Using Donor and Acceptor Polymers with Complementary Absorption

To explore the advantages of emerging all‐polymer solar cells (all‐PSCs), growing efforts have been devoted to developing matched donor and acceptor polymers to outperform fullerene‐based PSCs. In this work, a detailed characterization and comparison of all‐PSCs using a set of donor and acceptor polymers with both conventional and inverted device structures is performed. A simple method to quantify the actual composition and light harvesting contributions from the individual donor and acceptor is described. Detailed study on the exciton dissociation and charge recombination is carried out by a set of measurements to understand the photocurrent loss. It is unraveled that fine‐tuned crystallinity of the acceptor, matched donor and acceptor with complementary absorption and desired energy levels, and device architecture engineering can synergistically boost the performance of all‐PSCs. As expected, the PBDTTS‐FTAZ:PNDI‐T10 all‐PSC attains a high and stable power conversion efficiency of 6.9% without obvious efficiency decay in 60 d. This work demonstrates that PNDI‐T10 can be a potential alternative acceptor polymer to the widely used acceptor N2200 for high‐performance and stable all‐PSCs.     

Understanding the Impact of Oligomeric Polystyrene Side Chain Arrangement on the All‐Polymer Solar Cell Performance

The introduction of oligomeric polystyrene (PS) side chains into the conjugated backbone is proven to enhance the processability and electronic properties of semiconducting polymers. Here, two series of donor and acceptor polymers are prepared with different molar percentages of PS side chains to elucidate the effect of their substitution arrangement on the all‐polymer solar cell performance. The observed device performance is lower when the PS side chains are substituted on the donor polymer and higher when on the acceptor polymer, indicating a clear arrangement effect of the PS side chain. The incorporation of PS side chains to the acceptor polymer contributes to the decrease in phase separation domain size in the blend films. However, the reduced domain size was still an order of magnitude larger than the typical exciton diffusion length. A detailed morphological study together with the estimation of solubility parameter of the pristine PS, donor, and acceptor polymers reveals that the relative value of solubility parameter of each component dominantly contributes to the purity of the phase separated domain, which strongly impacts the amount of generated photocurrent and overall solar cell performance. This study provides an understanding of the design strategies to improve the all‐polymer solar cells.     

High‐Performance Wide Bandgap Copolymers Using an EDOT Modified Benzodithiophene Donor Block with 10.11% Efficiency

Newly developed benzo[1,2‐b:4,5‐b′]dithiophene (BDT) block with 3,4‐ethylenedioxythiophene (EDOT) side chains is first employed to build efficient photovoltaic copolymers. The resulting copolymers, PBDTEDOT‐BT and PBDTEDOTFBT, have a large bandgap more than 1.80 eV, which is attributed to the increased steric hindrance between the BDT and EDOT skeletons. Both copolymers possess the satisfied absorptions, low‐lying highest occupied molecular orbital (HOMO) levels and high crystallinity. Using the fluorination strategy, PBDTEDOT‐FBT exhibits a wider and stronger absorption and a deeper HOMO level than those of PBDTEDOT‐BT. PBDTEDOT‐FBT:[6,6]‐Phenyl C₇₁ butyric acid methyl ester (PC₇₁BM) blend also shows the higher hole mobility and better surface morphology compared with the PBDTEDOTBT:PC₇₁BM blend. Combination of above advantages, PBDTEDOT‐FBT devices exhibit much higher power conversion efficiency (PCE) of 10.11%, with an improved open circuit voltage (V_oc) of 0.86 V, short circuit current densities (J_sc) of 16.01 mA cm^?2, and fill factor (FF) of 72.6%. This work not only provides a newly efficient candidate of BDT donor block modified with EDOT conjugated side chains, but also achieves high‐performance large bandgap copolymers for polymer solar cells (PSCs) via the synergistic effect of fluorination and side chain engineering strategies.     

Semi‐Transparent Tandem Organic Solar Cells with 90% Internal Quantum Efficiency

Semi‐transparent (ST) organic solar cells with potential application as power generating windows are studied. The main challenge is to find proper transparent electrodes with desired electrical and optical properties. In this work, this is addressed by employing an amphiphilic conjugated polymer PFPA‐1 modified ITO coated glass substrate as the ohmic electron‐collecting cathode and PEDOT:PSS PH1000 as the hole‐collecting anode. For active layers based on different donor polymers, considerably lower reflection and parasitic absorption are found in the ST solar cells as compared to solar cells in the standard geometry with an ITO/PEDOT:PSS anode and a LiF/Al cathode. The ST solar cells have remarkably high internal quantum efficiency at short circuit condition (～90%) and high transmittance (～50%). Hence, efficient ST tandem solar cells with enhanced power conversion efficiency (PCE) compared to a single ST solar cell can be constructed by connecting the stacked two ST sub‐cells in parallel. The total loss of photons by reflection, parasitic absorption and transmission in the ST tandem solar cell can be smaller than the loss in a standard solar cell based on the same active materials. We demonstrate this by stacking five separately prepared ST cells on top of each other, to obtain a higher photocurrent than in an optimized standard solar cell.     

Harmonious Compatibility Dominates Influence of Side‐Chain Engineering on Morphology and Performance of Ternary Solar Cells

A growing number of recent studies have demonstrated the substantial impact of the alkyl side chains on the device performance of organic semiconductors. However, detailed investigation of the effect of side‐chain engineering on the blend morphology and performance of ternary organic solar cells (OSCs) has not yet been undertaken. In this study, the performance of ternary OSCs is investigated in a given poly(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)):[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PTB7‐Th:PC₇₁BM) host set by introducing various small molecule donors (SMDs) with different terminal side‐chain lengths. As expected, the performance of binary OSCs with SMDs depends greatly on the side‐chain length. In contrast, it is observed that all SMD‐based ternary OSCs exhibit almost identical and high power‐conversion efficiencies of 12.0–12.2%. This minor performance variation is attributed to good molecular compatibility between the two donor components, as evidenced by in‐depth electrical and morphological investigations. These results highlight that the alloy‐like structure formed due to the high compatibility of the donor molecules has a more significant effect on the overall performance than the side‐chain length, offering a new guideline for pairing donor components for achieving high‐performance ternary OSCs.     

Effect of Molecular Orientation of Donor Polymers on Charge Generation and Photovoltaic Properties in Bulk Heterojunction All‐Polymer Solar Cells

All‐polymer solar cells (all‐PSCs) utilizing p‐type polymers as electron‐donors and n ‐typepolymers as electron‐acceptors have attracted a great deal of attention, and their efficiencies have been improved considerably. Here, five polymer donors with different molecular orientations are synthesized by random copolymerization of 5‐fluoro‐2,1,3‐benzothiadiazole with different relative amounts of 2,2′‐bithiophene (2T) and dithieno[3,2‐b;2′,3′‐d]thiophene (DTT). Solar cells are prepared by blending the polymer donors with a naphthalene diimide‐based polymer acceptor (PNDI) or a [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor and their morphologies and crystallinity as well as optoelectronic, charge‐transport and photovoltaic properties are studied. Interestingly, charge generation in the solar cells is found to show higher dependence on the crystal orientation of the donor polymer for the PNDI‐based all‐PSCs than for the conventional PC₇₁BM‐based PSCs. As the population of face‐on‐oriented crystallites of the donor increased in PNDI‐based PSC, the short‐circuit current density (J_SC) and external quantum efficiency of the devices are found to significantly improve. Consequently, device efficiency was enhanced of all‐PSC from 3.11% to 6.01%. The study reveals that producing the same crystal orientation between the polymer donor and acceptor (face‐on/face‐on) is important in all‐PSCs because they provide efficient charge transfer at the donor/acceptor interface.     

Impact of Noncovalent Sulfur–Fluorine Interaction Position on Properties,Structures, and Photovoltaic Performance in Naphthobisthiadiazole‐Based Semiconducting Polymers

Controlling the energetics and backbone order of semiconducting polymers is essential for the performance improvement of polymer‐based solar cells. The use of fluorine as the substituent for the backbone is known to effectively deepen the molecular orbital energy levels and coplanarize the backbone by noncovalent interactions with sulfur of the thiophene ring. In this work, novel semiconducting polymers are designed and synthesized based on difluoronaphthobisthiadiazole (FNTz) as a new family of naphthobisthiadiazole (NTz)–quaterthiophene copolymer systems, which are one of the highest performing polymers in solar cells. The effect of the fluorination position on the energetics and backbone order is systematically studied. It is found that the dependence of the solar cell fill factor on the active layer thickness is very sensitive to the fluorination position. It is thus further investigated and discussed how the structural features of the polymers influence the photovoltaic parameters as well as the diode characteristics and bimolecular recombination. Further, the polymer with fluorine on both the naphthobisthiadiazole and quaterthiophene moieties exhibits a quite high power conversion efficiency of 10.8% in solar cells in combination with a fullerene. It is believed that the results would offer new insights into the development of semiconducting polymers.