BDT-based Polymers Research Articles

Recent Advances of Benzodithiophene-Based Donor Materials for Organic Solar Cells.

Recently, the power conversion efficiency (PCE) of organic solar cells (OSCs) has increased dramatically, making a big step toward the industrial application of OSCs. Among numerous OSCs, benzodithiophene (BDT)-based OSCs stand out in achieving efficient PCE. Notably, single-junction OSCs using BDT-based polymers as donor materials have completed a PCE of over 19%, indicating a dramatic potential for preparing high-performance large-scale OSCs. This paper reviews the recent progress of OSCs based on BDT polymer donor materials (PDMs). The development of BDT-based OSCs is concisely summarized. Meanwhile, the relationship between the structure of PDMs and the performance of OSCs is further described in this review. Besides, the development and prospect of single junction OSCs are also discussed.

Electrostatic force promoted intermolecular stacking of polymer donors toward 19.4% efficiency binary organic solar cells

Conjugated polymers are generally featured with low structural order due to their aromatic and irregular structural units, which limits their light absorption and charge mobility in organic solar cells. In this work, we report a conjugated molecule INMB-F that can act as a molecular bridge via electrostatic force to enhance the intermolecular stacking of BDT-based polymer donors toward efficient and stable organic solar cells. Molecular dynamics simulations and synchrotron X-ray measurements reveal that the electronegative INMB-F adsorb on the electropositive main chain of polymer donors to increase the donor-donor interactions, leading to enhanced structural order with shortened π-π stacking distance and consequently enhanced charge transport ability. Casting the non-fullerene acceptor layer on top of the INMB-F modified donor layer to fabricate solar cells via layer-by-layer deposition evidences significant power conversion efficiency boosts in a range of photovoltaic systems. A power conversion efficiency of 19.4% (certified 18.96%) is realized in PM6/L8-BO binary devices, which is one of the highest reported efficiencies of this material system. The enhanced structural order of polymer donors by INMB-F also leads to a six-fold enhancement of the operational stability of PM6/L8-BO organic solar cells.

Biaxially extended side-chain conjugation of benzodithiophene-based polymer dots for superior photocatalytic stability under visible-light irradiation

Conjugated polymer dots (Pdots) based on a series of BDT-based polymers with varied biaxially extended side-chain conjugations were prepared and employed for photocatalytic hydrogen production under visible light irradiation from aqueous solutions. The BDT-based polymers consisted of a dithiophedifluorobenzo[c][1,2,5]thiadiazole (DFBT) moiety as the acceptor unit and a BDT unit with different biaxially extended side-chains, including a alkyl-monothienyl group (T), a linear alkyl-dithiophene (2T) group, a branched alkyl-terthiophene (3T) group, and a fused alkyl-benzotrithiophene (B3T) group. The as-prepared Pdots based on these four polymers (PBDT-T, PBDT-2T, PBDT-3T, and PBDT-B3T) showed varied photophysical and electrochemical properties along with distinctive photocatalytic activity and long-term stability. Among them, the PBDT-B3T Pdots were showed to deliver a high photocatalytic efficiency of 14.1 mmol g−1 h−1 and a superior photocatalytic stability over 375 h in the presence of Pt as cocatalyst and ascorbic acid as sacrificial electron donors. Our results revealed that varying the structures of the biaxially extended side-chains endows a great flexibility in the photocatalytic activity of the polymers and the biaxially-extended conjugated side-chains can be a promising design strategy for the conjugated polymer to enhance the photocatalytic activity and stability.

Developing Wide Bandgap Polymers Based on Sole Benzodithiophene Units for Efficient Polymer Solar Cells.

In this work, a series of sole benzodithiophene-based wide band gap polymer donors, namely PBDTT, PBDTS, PBDTF and PBDTCl, were developed for efficient polymer solar cells (PSCs) by varying the heteroatoms into the conjugated side chains. The effects of sulfuration, fluorination and chlorination were also investigated systematically on the overall properties of these BDT-based polymers. The HOMO levels could be lowered gradually by introducing sulfur, fluorine and chlorine atoms into the side chains, which contributed to the stepwise increased Voc (from 0.78 V to 0.84 V) in the related PSCs using Y6 as the electron acceptor. This side-chain engineering strategy could promote the polymer chain interactions and fine-tune the phase separation of active blends, leading to enhanced absorption, ordered molecular packing and crystallinity. Among them, the chlorinated PBDTCl exhibited not only high level absorption and crystallinity, but also the most balanced hole/electron charge transport and the most optimized morphology, giving rise to the best PCE of 13.46 % with a Voc of 0.84 V, a Jsc of 23.16 mA cm-2 and an FF of 69.2 %. The chlorination strategy afforded PBDTCl synthetic simplicity but high efficiency, showing its promising photovoltaic applications for realizing low-cost practical PSCs in near future.

1 V high open-circuit voltage fluorinated alkoxybiphenyl side-chained benzodithiophene based photovoltaic polymers

Utilizing two-dimensional (2-D) conjugated structure and extending two-dimensional π-conjugation system with benzene can improve the performance of the BDT-based polymer solar cells (PSCs). In this work, combining with strong electron-drawing ability of fluorine atom, a new monomer BBFBDT with fluorinated alkoxybiphenyl unit as side-chain was designed and synthesized to construct medium band-gap donor (D) - acceptor (A) copolymer P1 with a benzo[1,2- c:4,5-c’]dithiophene-4,8-dione (BDD) acceptor. Blending with a classical non-fullerene acceptor ITIC, the P1-based PSCs reached a power conversion efficiency (PCE) of 4.16% and when coupled with a fullerene acceptor PC71BM, the PCE of PSCs reached 4.66% with an open-circuit voltage (Voc) of 0.93 V, a short-circuit current density (Jsc) of 9.83 mA cm−2 and a fill factor (FF) of 50.97%. The relatively poor Jsc of P1-based devices may be caused by the bad complementarity of absorption spectra. Furthermore, a wide band-gap D-A copolymer P2, with a electron-deficient 4,7-bis(5-bromothiophen-2-yl)-2-((2-ethylhexyl)oxy)-5,6-difluoro-2H-benzo[d][1,2,3]triazole (TZ) as the acceptor unit, was synthesized to match the absorption spectra of ITIC. Finally, the efficiency achieved 6.59% with Voc of 0.99 V, Jsc of 14.37 mA cm−2 and FF of 46.32%.

Phthalimide-Based High Mobility Polymer Semiconductors for Efficient Nonfullerene Solar Cells with Power Conversion Efficiencies over 13.

Highly efficient nonfullerene polymer solar cells (PSCs) are developed based on two new phthalimide‐based polymers phthalimide‐difluorobenzothiadiazole (PhI‐ffBT) and fluorinated phthalimide‐ffBT (ffPhI‐ffBT). Compared to all high‐performance polymers reported, which are exclusively based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT), both PhI‐ffBT and ffPhI‐ffBT are BDT‐free and feature a D‐A1‐D‐A2 type backbone. Incorporating a second acceptor unit difluorobenzothiadiazole leads to polymers with low‐lying highest occupied molecular orbital levels (≈−5.6 eV) and a complementary absorption with the narrow bandgap nonfullerene acceptor IT‐4F. Moreover, these BDT‐free polymers show substantially higher hole mobilities than BDT‐based polymers, which are beneficial to charge transport and extraction in solar cells. The PSCs containing difluorinated phthalimide‐based polymer ffPhI‐ffBT achieve a substantial PCE of 12.74% and a large V oc of 0.94 V, and the PSCs containing phthalimide‐based polymer PhI‐ffBT show a further increased PCE of 13.31% with a higher J sc of 19.41 mA cm−2 and a larger fill factor of 0.76. The 13.31% PCE is the highest value except the widely studied BDT‐based polymers and is also the highest among all benzothiadiazole‐based polymers. The results demonstrate that phthalimides are excellent building blocks for enabling donor polymers with the state‐of‐the‐art performance in nonfullerene PSCs and the BDT is not necessary for constructing such donor polymers.

A novel naphthyl side-chained benzodithiophene polymer for efficient photovoltaic cells with a high fill factor of 75%

Introducing alkoxynaphthyl into benzodithiophene (BDT) is more effective in improving the photovoltaic properties of BDT-based polymers.

Highly efficient two-dimensional conjugated benzodithiophene-based photovoltaic polymers

In order to improve the photovoltaic properties of polymer solar cells (PSC), varieties of donor and acceptor units were designed and synthesized to construct the highly efficient conjugated polymers. Recent years, materials based on benzo [1.2-b:4,5-b ¢ ]dithiophene (BDT) units have showed promising applications in the field of organic photovoltaics for its excellent properties. As compared to BDT-based polymers with flexible side chains, polymers based on two-dimensional conjugated BDT (2D-BDT) usually had better thermal stability, slightly red-shifted of absorption spectra, lower HOMO levels, higher hole mobility and consequently improved photovoltaic properties. By using novel 2D-BDT-based polymers, the power conversion efficiency (PCE) of the PSC devices has been boosted to over 10%. In this article, we first briefly introduce the synthesis methods of 2D-BDT unit, and then focus our attention to summarize the numerous of 2D-BDT-based polymers and their applications in highly efficient PSC devices.

High-Performance Photovoltaic Polymers Employing Symmetry-Breaking Building Blocks.

Two 1D-2D asymmetric benzodithiophenes (BDTs) as donor building blocks are designed and synthesized, combining the advantages of both 1D and 2D symmetric BDTs. The photovoltaic properties of the asymmetric BDT-based polymers are improved greatly in comparison with corresponding symmetric BDT-based polymers. This work provides a new approach to design prospective organic optoelectronic materials employing the symmetry-breaking strategy.

Molecular Design of Benzodithiophene-Based Organic Photovoltaic Materials.

Advances in the design and application of highly efficient conjugated polymers and small molecules over the past years have enabled the rapid progress in the development of organic photovoltaic (OPV) technology as a promising alternative to conventional solar cells. Among the numerous OPV materials, benzodithiophene (BDT)-based polymers and small molecules have come to the fore in achieving outstanding power conversion efficiency (PCE) and breaking 10% efficiency barrier in the single junction OPV devices. Remarkably, the OPV device featured by BDT-based polymer has recently demonstrated an impressive PCE of 11.21%, indicating the great potential of this class of materials in commercial photovoltaic applications. In this review, we offered an overview of the organic photovoltaic materials based on BDT from the aspects of backbones, functional groups, alkyl chains, and device performance, trying to provide a guideline about the structure-performance relationship. We believe more exciting BDT-based photovoltaic materials and devices will be developed in the near future.

Single precursor for the synthesis of donor and acceptor units of the low band gap polymers: synthesis of benzodithiophene and thienopyrroledione from maleic anhydride

An efficient route was developed to synthesize dimethyl thiophene-3,4-dicarboxylate from maleic anhydride. Dimethyl thiophene-3,4-dicarboxylate was used as a single precursor for synthesis of benzo[1,2-b:4,5-b′]dithiophene (BDT) and Thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives. BDT and TPD derivatives have been highly exploited as donor and acceptor units, respectively, to synthesize important donor–acceptor (D–A) conjugated polymers. BDT-based polymers were found to be one of the most efficient conjugated polymers for organic photovoltaic application. Synthesis of quinone precursor of the dihydroxybenzothiophene was accomplished by a new and unconventional methodology which includes reaction of 3,4-thiophene dicarboxylate with sodium hydride in THF. Dithienobenzoquinone dicarboxylate and dihydroxybenzodithiophene dicarboxylate were characterized structurally by single-crystal X-ray diffraction. Both compounds show strong π-stacking interaction and arrange in the parallel molecular sheets in the crystals.

Design and synthesis of the polymers based on alkylthiophenyl side chains and variant acceptor moieties for polymer solar cells

Three new BDT-based polymers with alkylthiophenyl side chains and the relationship between the acceptor structure and the photovoltaic performance.

Efficient all polymer solar cells employing donor polymer based on benzo[1,2-b:4,5-b’]dithiophene unit

We reported all polymer solar cells (all-PSCs) employing BDT-based donor–acceptor (D–A) polymers composed of benzo[1,2-b:4,5-b’]dithiophene (BDT) and thiadiazolo[3,4-c]pyridine (PyTZ) (PBPT-8 and PBPT-12) as donor and NDI-based n-type polymer Poly{[N,N’-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bithiophene)} (P(NDI2OD-T2)) (N2200) as acceptor. The influence of thermal annealing on the performance of all-PSCs was systematically investigated and discussed. It was found that the pre-annealing of the active blend films could significantly improve the all-PSCs performance. Both PBPT-8/PBPT-12:N2200 systems can deliver promising PCEs (4.12% and 4.25%) at the optimal annealing temperature of 160 oC due to the promoted film quality and charge transport properties. Morphology investigation and carrier mobility measurements have been carried out to analyze the effect of thermal annealing. This study suggests that BDT-based polymer:N2200 systems can be promising candidates for all-PSCs, with thermal annealing as an effective approach to promote the device performance.

Synthesis and characterization of fluorine atom substituted new BDT-based polymers for use in organic solar cells

A series of benzo[1,2-b:4,5-b′]dithiophene (BDT)-based donor–acceptor conjugated polymers were synthesized using a Stille cross-coupling reaction. The new fluorinated polymer (PBDTFT-ttTPD) contained 3,4-difluoroalkylthienyl benzo[1,2-b:4,5-b′]dithiophene (BDTFT) donor units and thienothienylthieno[3,4-c]pyrrole-4,6-dione (ttTPD) as acceptor units. A nonfluorinated alkylthienyl-substituted BDT-based polymer (PBDTT-ttTPD) was synthesized and its optoelectronic and photovoltaic properties were compared with those of PBDTFT-ttTPD. The number-averaged molecular weights (Mn) of PBDTT-ttTPD and PBDTFT-ttTPD were found to be 22,500 and 24,100g/mol, with dispersities of 2.3 and 2.0, respectively. The band gap energies of PBDTT-ttTPD and PBDTFT-ttTPD were 1.87eV and 1.89eV, respectively. The HOMO levels of PBDTT-ttTPD and PBDTFT-ttTPD were −5.68eV and −5.78eV, respectively. These results indicated that the inclusion of 3,4-difluorothienyl-BDT units in the polymers provided a very effective approach to lowering the HOMO and LUMO energy levels. The field-effect mobilities of PBDTT-ttTPD and PBDTFT-ttTPD were determined to be 9.2×10−4cm2V−1s−1 and 2.7×10−4cm2V−1s−1, respectively. A polymer solar cell device prepared using PBDTFT-ttTPD as the active layer was found to exhibit a power conversion efficiency (PCE) of 3.27% with an open circuit voltage of 0.79V under AM 1.5G (100mW/cm2) conditions.

Naphthodithiophene-Based Conjugated Polymer with Linear, Planar Backbone Conformation and Strong Intermolecular Packing for Efficient Organic Solar Cells.

Two donor-acceptor copolymers, PBDT and PNDT, containing 4,8-bis(2-ethylhexyloxy)benzo[1,2-b:3,4-b']dithiophene (BDT) and 4,9-bis(2-ethylhexyloxy)naphtho[1,2-b:5,6-b']dithiophene (NDT), respectively, as an electron-rich unit and 5,6-difluoro-2,1,3-benzothiadiazole (2FBT) as an electron-deficient unit, were synthesized and compared. The introduction of the NDT core into the conjugated backbone was found to effectively improve both light harvesting and the charge carrier mobility by enhancing chain planarity and backbone linearity; the NDT copolymer has stronger noncovalent interactions and smaller bond angles than those of the BDT-based polymer. Moreover, the introduction of the NDT core brings about a drastic change in the molecular orientation into the face-on motif and results in polymer:PCBM blend films with well-mixed interpenetrating nanofibrillar bulk-heterojunction networks with small-scale phase separation, which produce solar cells with higher short-circuit current density and fill factor values. A conventional optimized device structure containing PNDT:PC71BM was found to exhibit a maximum solar efficiency of 6.35%, an open-circuit voltage of 0.84 V, a short-circuit current density of 11.92 mA cm(-2), and a fill factor of 63.5% with thermal annealing, which demonstrates that the NDT and DT2FBT moieties are a promising electron-donor/acceptor combination for high-performance photovoltaics.

Synthesis and characterization of benzo[1,2-b:4,5-b’]dithiophene-based copolymers for polymer solar cells

Two benzo[1,2-b:4,5-b’]dithiophene (BDT)-based copolymers, poly[4,8-bis(5-(2-ethylhexyl) thiophene-2-yl)benzo[1,2-b:4,5-b’]dithiophene-alt-5,8-(2,3-bis(4-octyloxy)phenyl)quinoxaline] (P1) and poly[4,8-bis(5-(2-ethylhexyl)thiophene-2-yl)benzo[1,2-b:4,5-b’]dithiophene-alt-5,7-(2,3-bis(4- octyloxy)phenyl)thieno[3,4-b]pyrazine] (P2), are synthesized and used as donor materials in polymer solar cells (PSCs). To obtain a low band gap polymer, we use a copolymerized donor-acceptor structure. The optical, electrochemical, and photovoltaic properties of the copolymers are investigated. The results indicate that the acceptor units in the copolymers influenced the band gap, electronic energy levels, and photovoltaic properties of the copolymers significantly. The band gaps of the copolymers are in the range 1.34 − 1.75 eV. Under optimized conditions, the BDT-based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range 1.46 − 2.05% under AM 1.5 illumination (100 mW/cm2).

Simultaneous Enhancement of Solar Cell Efficiency and Photostability via Chemical Tuning of Electron Donating Units in Diketopyrrolopyrrole-Based Push–Pull Type Polymers

We synthesized a series of push–pull-type copolymers by copolymerizing an electron-deficient diketopyrrolopyrrole with three electron-donating benzodithiophene (BDT) moieties. PDPPDTT, which incorporated a dithienothiophene (DTT), showed a higher power conversion efficiency (PCE) of 6.11% compared to 3.31% for the BDT-based polymer (PDPPBDT). PDPPDTBDT, which incorporated a dithienobenzodithiophene (DTBDT), also exhibited superior performance, with a PCE of 4.75% although this value was lower than that obtained for PDPPDTT. The presence of the DTT unit in the polymer backbone lowered the energy bandgap of the polymer and induced an optimal morphology in the polymer:PC71BM blend film, resulting in higher charge carrier generation. Furthermore, the effectively delocalized frontier orbitals of PDPPDTT enhanced intermolecular interactions between the polymer chains by favoring effective π–π stacking, which facilitated charge carrier transport. By contrast, PDPPDTBDT unexpectedly showed a low-crystallinity thin film despite its backbone planarity, which reduced the performance relative to that of PDPPDTT. Importantly, PDPPDTT exhibited significantly better device stability compared to the other polymers in a light soaking test due to the much higher photochemical stability of PDPPDTT. We demonstrated a systematic approach to simultaneously increasing the photovoltaic performances and device stability, and we explored the basis for the structure–property relationship that accompanied such improvements.

Molecular design toward highly efficient photovoltaic polymers based on two-dimensional conjugated benzodithiophene.

As researchers continue to develop new organic materials for solar cells, benzo[1,2-b:4,5-b']dithiophene (BDT)-based polymers have come to the fore. To improve the photovoltaic properties of BDT-based polymers, researchers have developed and applied various strategies leading to the successful molecular design of highly efficient photovoltaic polymers. Novel polymer materials composed of two-dimensional conjugated BDT (2D-conjugated BDT) have boosted the power conversion efficiency of polymer solar cells (PSCs) to levels that exceed 9%. In this Account, we summarize recent progress related to the design and synthesis of 2D-conjugated BDT-based polymers and discuss their applications in highly efficient photovoltaic devices. We introduce the basic considerations for the construction of 2D-conjugated BDT-based polymers and systematic molecular design guidelines. For example, simply modifying an alkoxyl-substituted BDT to form an alkylthienyl-substituted BDT can improve the polymer hole mobilities substantially with little effect on their molecular energy level. Secondly, the addition of a variety of chemical moieties to the polymer can produce a 2D-conjugated BDT unit with more functions. For example, the introduction of a conjugated side chain with electron deficient groups (such as para-alkyl-phenyl, meta-alkoxyl-phenyl, and 2-alkyl-3-fluoro-thienyl) allowed us to modulate the molecular energy levels of 2D-conjugated BDT-based polymers. Through the rational design of BDT analogues such as dithienobenzodithiophene (DTBDT) or the insertion of larger π bridges, we can tune the backbone conformations of these polymers and modulate their photovoltaic properties. We also discuss the influence of 2D-conjugated BDT on polymer morphology and the blends of these polymers with phenyl-C61 (or C71)-butyric acid methyl ester (PCBM). Finally, we summarize the various applications of the 2D-conjugated BDT-based polymers in highly efficient PSC devices. Overall, this Account correlates the molecular structures of the 2D-conjugated BDT-based polymers with their photovoltaic properties. As a result, this Account can guide the molecular design of organic photovoltaic materials and the development of organic materials for other types of optoelectronic devices.

Highly Conjugated Side-Chain-Substituted Benzo[1,2-b:4,5-b′]dithiophene-Based Conjugated Polymers for Use in Polymer Solar Cells

A series of novel benzo[1,2-b:4,5-b′]dithiophene (BDT)-based conjugated polymers were synthesized using a Stille cross-coupling reaction. These polymers contained dithienyl thieno[3,4-c]pyrrole-4,6-dione (DTTPD) as an acceptor. Alkylthienylenevinylene thiophene side groups were introduced into the BDT units, and the solubility, absorption spectra, energy levels, charge transport, blend film morphology, and photovoltaic properties of the resulting polymer (poly[4,8-bis{2,2′-(5-ethylhexyl)thienylenevinylenethiophene}benzo[1,2-b;3,4-b]dithiophene-2,6-diyl-alt-1,3-di(thien-5′-yl)-5-octyldodecyl[3,4-c]pyrrole-4,6-dione-2,2′-diyl], PBDTTVT-DTTPD) were investigated. In addition, an alkylthienyl-substituted BDT-based polymer (poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-1,3-di(thien-5′-yl)-5-octyldodecyl[3,4-c]pyrrole-4,6-dione-2,2′-diyl], PBDTT-DTTPD) was synthesized to compare the optoelectronic and photovoltaic properties of the polymers. The weight-averaged molecular ...

Enhanced and Tunable Open-Circuit Voltage using Dialkylthio Benzo[1,2-b:4,5-b′]dithiophene in Polymer Solar Cells

In this study, we explore the effect of the dialkoxy and dithioalkoxy side chains on the benzo [1,2-b:4,5-b′]dithiophene (BDT) unit by comparing the O-BDT homopolymer (O-PBDT), S-BDT homopolymer (S-PBDT), and S-BDT-alt-O-BDT copolymer (SO-PBDT) by computational calculations and experimental results. The polymers were prepared by Pd-catalyzed Stille coupling. Additionally, hole mobility and film morphology were studied by fabricating organic field effect transistors (OFETs) and using TappingMode AFM, respectively. The photovoltaic properties of the polymers were measured from fabricated PSC devices. The replacement of the alkoxy (−OR) groups with thioalkoxy (−SR) groups lowered the HOMO energy level of the conjugated polymers from 5.31 to 5.41 eV, and consequently enhanced Voc, while still preserving the excellent properties offered by the BDT-based polymers. Especially, high Voc of 0.99 V was achieved from S-PBDT polymer based PSC with up to 4.0% of PCE, which is one of the highest efficiencies reported from a homopolymer-based PSC without thermal/solvent annealing or incorporated additives.