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A new angular-shaped naphthodithiophene diimide (aNDTI) is designed and synthesized. The aNDTI-containing polymers are used as non-volatile additives to improve the efficiency of organic solar cells.

Tetraalkylammonium bromide is produced in situ. The effect of the length of bromoalkyl chains is recognized, indicating the importance of side-chain engineering. The hydrogen evolution rate is improved significantly by the presence of Pd.

Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared. Grignard metathesis of SSeI2, STeI2, SeTeI2, and SSeTeI2 occurred regioselectively at the lighter chalcogenophene site because of its relatively lower electron density and less steric bulk. Nickel-catalyzed Kumada catalyst-transfer polycondensation of these Mg species provided a new class of side-chain regioregular and main-chain AB-type alternating poly(bichalcogenophene)s—PSSe, PSTe, and PSeTe—through a chain-growth mechanism. The ring-walking of the Ni catalyst from the lighter to the heavier chalcogenophene facilitated subsequent oxidative addition, thereby suppressing the possibility of chain-transfer or chain-termination. More significantly, the Ni catalyst could walk over the distance of three rings (ca. 1 nm)—from a thiophene unit via a selenophene unit to a tellurophene unit—to form PSSeTe, the first ABC-type regioregular and periodic poly(terchalcogenophene) comprising three different types of 3-hexylchalcogenophenes., Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared to synthesize a new class of polychalcogenophenes with precisely controlled sequences by catalyst-transfer polycondensation.

A systematic methodology is developed to construct the angular-shaped β-form naphthodithiophene (β-aNDT) core with regiospecific substitution of two alkyl groups at its 4,9- or 5,10-positions via the base-induced double 6π-cyclization of dithienyldieneyne precursors, leading to the two isomeric 4,9-β-aNDT and 5,10-β-aNDT monomers. It is found that a more curved geometry of the β-aNDT units intrinsically increases the solubility and thus the solution-processability of the resultant polymers. Therefore, β-aNDT units are ideal for polymerization with an acceptor-containing monomer without the need for any solubilizing aliphatic side chains, which are considered the insulating portion that jeopardizes charge transport. Based on this consideration, the 4,9- and 5,10-dialkylated β-aNDT monomers are polymerized with the non-alkylated DTFBT acceptor to afford two P4,9-βNDTDTFBT and P5,10-βNDTDTFBT copolymers for head-to-head comparison of the 4,9-inner/5,10-outer isomeric alkylation effect. It is found that 4,9-β-aNDT adopts a twisted conjugated structure due to the intramolecular steric repulsion between the inner branched side chains and the β-hydrogens on the thiophene rings. The slightly twisted 4,9-β-aNDT moiety allows P4,9-βNDTDTFBT to have higher solubility upon polymerization and thus a higher molecular weight, which eventually induces a higher ordered packing structure in the thin film compared to P5,10-βNDTDTFBT. As a result, P4,9-βNDTDTFBT exhibits a higher OFET mobility of 0.18 cm2 V−1 s−1, and the P4,9-βNDTDTFBT:PC71BM-based solar cell device also achieves a higher PCE of 7.23%, which is even better than the corresponding P4,9-αNDTDTFBT-based device.

We have designed and synthesized a tricyclic diseleno[3,2-b:2′,3′-d]silole (DSS) wherein the 3,3′-position of a biselenophene is bridged by a dioctylsilyl moiety. The distannylated DSS was copolymerized with a diketopyrrolopyrrole (DPP) acceptor to form a donor–acceptor copolymer PDSSDPP. The thiophene-based dithieno[3,2-b:2′,3′-d]silole (DTS) monomer and its corresponding copolymer PDTSDPP are also prepared as references for investigation of the chalcogen effect. Compared to PDTSDPP, PDSSDPP exhibits a more red-shifted absorption spectrum, a higher-lying HOMO energy level, and closer interchain packing associated with the more polarizable Se atom to induce stronger intermolecular interactions. The selenophene-based PDSSDPP shows a mobility of 2.47 × 10−2 cm2 V−1 s−1, which is nearly one order magnitude higher than the thiophene-based PDTSDPP with a mobility of 3.89 × 10−3 cm2 V−1 s−1. This result suggests that the DSS unit and its polymers are promising for OFET applications.

We present a facile synthesis method to make a new ladder-type heptacyclic dithienobenzofluorene (DTBF) framework, where the central 2,7-fluorene unit is covalently fastened with two external thiophenes via two CC bridges. A dieneyne-containing precursor undergoes DBU-induced double benzannulation to regiospecifically introduce two solubilizing 2-octyldodecyl side chains at 5,10-positions of DTBF. The rigid and coplanar Br-DTBF monomer with sufficient solubility was copolymerized with 5,6-difluoro-4,7-bis(5-(trimethylstannyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (Sn-DTFBT) and 5,10-bis(5-(trimethylstannyl)thiophen-2-yl)naphtho[1,2-c:5,6-c′]bis([1,2,5]thiadiazole) (Sn-DTNT) via Stille coupling to furnish two donor–acceptor copolymers, PDTBFFBT and PDTBFNT, respectively. Their thermal, optical, electrochemical, molecular stacking and photovoltaic properties are investigated. PDTBFNT has a higher molecular weight, smaller optical and electrochemical band gaps, and stronger solid-state packing than PDTBFFBT. DFT calculations were carried out to gain insight into the electronic and structural properties of DTBF and its derivatives. Bulk heterojunction solar devices with the ITO/ZnO/polymers:PC71BM/MoO3/Ag configuration were fabricated. By adding 5 vol% diphenyl ether (DPE) as an additive, PDTBFNT:PC71BM and PDTBFFBT:PC71BM devices achieved the power conversion efficiencies of 5.22% and 2.68%, respectively. The superior efficiency of PDTBFNT over PDTBFFBT is attributed to the better LUMO energy alignment between PDTBFNT and PC71BM and the face-on π-stacking of PDTBFNT in the active layer. Moreover, PDTBFNT exhibited a higher field-effect transistor hole mobility of 1.90 × 10−2 cm2 V−1 s−1 than PDTBFFBT with a value of 3.96 × 10−3 cm2 V−1 s−1.

Non-conjugated triethylene glycol (3-EG), tetraethylene glycol (4-EG) and pentaethylene glycol (5-EG) are presented as new cathode modification materials to achieve high-performance inverted-PCSs. By spin-coating from a non-chlorinated solvent, these small molecules can self-assemble on ITO via surface coordination and hydrogen bonding to form an ultra-thin layer. Theoretical simulations reveal that the coordination of oxygen atoms in the EG molecules to indium moieties on the ITO surface is the major mechanism in inducing interfacial dipoles, thereby reducing the work function (WF) of ITO for efficient electron collection. Based on the PBDTTT-EFT:PC71BM blend, the bulk heterojunction device using the 5-EG layer exhibited a higher short-circuit current density (Jsc) of 15.27 mA cm−2, fill factor (FF) of 0.69, and power conversion efficiency (PCE) of 8.46%, which are better than those of the corresponding devices using either inorganic ZnO or non-conjugated poly(ethylene oxide) (PEO) as the cathode buffer layer. More importantly, this simple and expedited strategy is also demonstrated to be universally applicable to various p-type conjugated polymers. The EG oligomers with well-defined chemical structures have the advantages of easy availability, simple processability and good device reproducibility, which are crucial keys for future commercialization using large-scale roll-to-roll production.

A triarylamine-based material DVTPD containing two styryl groups has been developed. Upon isothermal heating at 180 °C for 30 min, DVTPD can be thermally cross-linked to form a solvent-resistant layer to realize the fabrication of solution-processed multilayer devices. The crosslinked DVTPD (denoted as X-DVTPD) layer possesses not only hole-collecting ability (HOMO = −5.3 eV) but also electron-blocking capability (LUMO = −2.2 eV). By incorporation of an ionic dopant, 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenylborate) (DPITPFB), into the X-DVTPD material (1 : 10 in wt%), a favourable morphology of the dopant/matrix layer was formed and the hole-mobility is significantly improved by three orders of magnitude compared to its non-doped state. This DPITPFB : X-DVTPD (1 : 10 in wt%) layer was employed as the hole-transporting layer to fabricate polymer solar cell devices (PSCs). The EHOMO of the polymer in the active layer relative to the EHOMO of the X-DVTPD (−5.3 eV) governs the hole transportation highly associated with the device performance. The higher-lying EHOMO (−5.0 eV) of P3HT causes a large energy barrier for the hole transportation at the interface, leading to an unsatisfactory efficiency. The EHOMO level of the PTB7 copolymer (−5.15 eV) is closer to −5.3 eV. As a result, the PTB7-based device can achieve 80% of the efficiency obtained from the corresponding PEDOT:PSS-based device. Furthermore, the PBDCPDTFBT copolymer has the same EHOMO (−5.3 eV) with X-DVTPD. Consequently, the PBDCPDTFBT-based device showed a comparable efficiency of 5.3% to the corresponding PEDOT:PSS-based device. More importantly, PNDTDTFBT having the lowest-lying EHOMO of −5.4 eV exhibits superior performance with a high PCE of 6.64%, outperforming its reference PEDOT:PSS-based device. This simple and useful hole-transporting system integrating the crosslinking and doping strategies to replace PEDOT:PSS can be widely used in solution-processed organic electronic devices.

A single isomer of fullerene bisadduct, PC61PF, was obtained from commercially available fullerene derivative, PC61BM, in one pot over two steps. The tether-directed remote functionalization approach provided a very simple and fast method to produce a single isomer of fullerene bisadduct with good yield and easy purification. Bulk heterojunction organic solar cells containing the bisadduct was fabricated and tested.

To obtain a poly(5,6-difluorobenzo-2,1,3-thiadiazole-4,7-diyl-alt-quaterchalcogenophene) (P(FBT-alt-CP4)) copolymer with a small optical band gap (Eg), and to achieve high short-circuit current (Jsc) in the P(FBT-alt-CP4) : PC71BM polymer solar cells (PSCs), P(FBT-alt-Se2Th2), which contains selenophene-2,5-diyl (–Se–) π-bridges, was synthesized. P(FBT-alt-Se2Th2) shows a Eg of 1.56 eV and is strongly aggregated in solution. Wide angle X-ray diffraction (WAXD) and grazing incidence X-ray diffraction (GI-XRD) results revealed the high solid-state order of P(FBT-alt-Se2Th2) and its edge-on orientation on the substrate. It delivered a high hole mobility (μh) of 0.36 cm2 V−1 s−1 in organic field-effect transistors (OFETs). The strong aggregation tendency of P(FBT-alt-Se2Th2) caused large segregation domains in the P(FBT-alt-Se2Th2) : PC71BM thin film, as is seen in the high-resolution transmission electron microscopy (HR-TEM) images. The addition of 8 vol% of 1-chloronaphthalene (1-CN) effectively suppressed the aggregation and led to more homogeneous active layer morphology. The improved morphology enhanced the Jsc of the PSCs. A superior PCE of 7.34% with a Voc of 0.70 V, a Jsc of 15.8 mA cm−2, and a FF of 66.4% was achieved in the inverted P(FBT-alt-Se2Th2) : PC71BM PSCs. The strong aggregation of P(FBT-alt-Se2Th2) is likely related to its more straight conjugated backbone according to the theoretical calculation results of the FBT-alt-Se2Th2 repeat unit.

Bulk heterojunction (BHJ) polymer solar cells (PSCs) on the basis of polymer:fullerene blends have delivered numerous impressive results in the last decade and thus have drawn much attention of the scientific and industrial communities. However, BHJ PSCs often suffer from several intrinsic problems, such as the low open-circuit voltage (Voc), energetically-unfavorable and chemically-incompatible interfaces, and morphological phase separation of the polymer:fullerene blend driven by thermal treatment, hindering further advancement. In this review, we summarize the recent progress on applications of fullerene-based materials in the BHJ PSCs. Bis-adduct fullerenes possessing high-lying LUMO energy levels can substitute for mono-substituted fullerenes and higher Voc values can thus be achieved. Incorporation of an n-type fullerene interlayer between inorganic and organic active layers in either inverted or conventional PSCs can help in minimization of charge recombination losses at the interface and improvement of charge transfer from the active layer to the inorganic layer, thus resulting in superior PCEs. The optimal active-layer morphology can be maintained through several approaches, such as in situ polymerization of cross-linkable fullerenes, suppression of large-scale PC61BM aggregation by a polyethylene glycol-functionalized fullerene, supramolecular pentafluorophenyl-fullerene stabilization, and light-induced oligomerization of fullerenes. The morphological phase separation of the active-layer materials can thus be minimized. The research of employing fullerene materials will continue playing a critical role in BHJ PSCs. With further investigation and advancement in this field, it is expected that the ultimate goal of commercialization can be realized.

We have developed a new ladder-type conjugated polymer PBDCPDT–FBT and a robust interconnecting layer (ICL) integrating a hole-collecting m-PEDOT:PSS layer with an electron-collecting ZnO layer. The inverted device using PBDCPDT–FBT exhibited a high power conversion efficiency (PCE) of 5.76% with a Voc of 0.81 V, a Jsc of 12.82 mA cm−2, and a FF of 55.5%. The inverted tandem device incorporating the PBDCPDT–FBT and ICL achieves a Voc of 1.62 V leading to a PCE of 7.08%.

A new design for constructing two-dimensional conjugated copolymers with the D1–A(D2) repeating pattern (A: acceptor, D1: donor 1, D2: donor 2; molecules enclosed in parentheses are pendant groups.), is proposed. D1 and A are employed to construct the linear main-conjugated polymer chain and D2 is situated at the conjugated side chains connected to A. We designed and synthesized a series of D1–A(D2)-type copolymers, in which D1 = diindeno[1,2-b:2′,1′-d]-thiophene (DIDT) or fluorene (F), A(D2) = bis-[4-(dioctylamino)-phenyl] quinoxaline (DOAQX) or bis-[4-(dioctylamino)-phenyl] thieno[3,4-b]pyrazine (DOATP), and D2 = N,N-dioctylanilines. The resultant copolymers, PDIDTDOAQX, PFDOAQX, PDIDTDOATP and PFDOATP, possess at least two strong ICT absorptions, thus resulting in better light harvesting. Their optical and electronic properties were thoroughly investigated experimentally and computationally. Bulk heterojunction photovoltaic cells on the basis of ITO/PEDOT:PSS/polymer:PC71BM/Ca/Al configuration were fabricated and characterized. The photovoltaic performances of the devices incorporating these polymers follow the sequence: PDIDTDOAQX > PFDOAQX > PDIDTDOATP > PFDOATP, which is in good agreement with the magnitude of their hole-mobilities.