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A facile method was introduced and demonstrated to synthesize zinc oxide (ZnO) nanorods (NRs) as an electron transporting layer (ETL) for organic solar cells (OSCs). Hydrothermal synthesis of the NRs showed a constant growth rate of 5.5 nm min−1 from germination to sub-micrometer length. The properties were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), absorption spectrophotometry and so on. Based on these measurements, the germinant growth mechanism and its corresponding orientation characteristics were investigated. As an ETL of the OSCs, ZnO NRs enhance the charge extraction from the active layer due to their increased interfacial surface area, but there is an optimal length because of the shunt path formation and UV absorption of long ZnO NRs. As a result, the OSC with the ZnO NRs as ETL shows power conversion efficiency (PCE) up to 6.2%. The J-V characteristics and incident photon-to-current conversion efficiency (IPCE) measurement also reveal that the efficiency enhancement is an assembly of individual results from optical, physical and electrical characteristic of the ZnO NRs.

We report newly synthesized fluorescence resonance energy transfer (FRET)-based green-, red-, and near-infrared (NIR)-emitting polymer dot (Pdot) probes. Fluorescent Pdots (∼60 nm) were prepared wi...

Driven by the exceptional success of 2,2′-bithiophene-3,3′-dicarboximide imide (BTI) for enabling high-performance polymer semiconductors, herein two BTI analogues 2,2′-bifuran-3,3′-dicarboximide (...

A planar backbone conformation is essential for enabling polymer semiconductors with high charge carrier mobility in organic thin-film transistors. Benefiting from the smaller van der Waals radius ...

Two carboxylate-functionalized wide band gap polymers, 2TC-TT-BDTFT and 2T-TTC-BDTFT, which feature a fluorinated benzodithiophene (BDTFT)-alt-2,5-di(thiophen-2-yl)thieno[3,2-b]thiophene (2T-TT) ba...

A new polymer acceptor poly{(N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5,5-(3,3'-didodecyl-2,2'-bifuran)} (NDI-BFR) made from naphthalenediimide (NDI) and furan-derived head-to-head-linked 3,3'-dialkyl-2,2'-bifuran (BFR) units is reported in this study. Compared to the benchmark polymer poly(naphthalenediimide-alt-bithiophene) (N2200), NDI-BFR exhibits a larger bathochromic shift of absorption maxima (842 nm) with a much higher absorption coefficient (7.2 × 104 m-1 cm-1 ), leading to an ultranarrow optical bandgap of 1.26 eV. Such properties ensure good harvesting of solar light from visible to the near-infrared region in solar cells. Density functional theory calculation reveals that the polymer acceptor NDI-BFR possesses a higher degree of backbone planarity versus the polymer N2200. The polymer NDI-BFR exhibits a decent electron mobility of 0.45 cm2 V-1 s-1 in organic thin-film transistors (OTFTs), and NDI-BFR-based all-polymer solar cells (all-PSCs) achieve a power conversion efficiency (PCE) of 4.39% with a very small energy loss of 0.45 eV by using the environmentally friendly solvent 1,2,4-trimethylbenzene. These results demonstrate that incorporating head-to-head-linked BFR units in the polymer backbone can lead to increased planarity of the polymer backbone, reduced optical bandgap, and improved light absorbing. The study offers useful guidelines for constructing n-type polymers with narrow optical bandgaps.

A new building block, 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP) with several desirable features such as high backbone planarity, suitably lying highest occupied molecular orbital (HOMO), and good solubility, was developed by inserting an electron-deficient difluorophenylene into the 3,3′-dialkoxy-2,2′-bithiophene (BTOR) unit. Three regioregular D-A1-D-A2 type polymers based on DOTFP and benzothiadiazole (BT) derivatives were synthesized and characterized by comparing with a D–A type BTOR-based polymer. The content of highly electron-rich alkoxythiophene is reduced by half in the DOTFP-based polymers versus that of the BTOR-based polymer analogue, which results in a deeper HOMO level and benefits high open-circuit voltage (Voc) in polymer solar cells (PSCs). Consequently, the DOTFP-ffBT-based solar cells exhibited a significantly improved power conversion efficiency (PCE) of 8.7% and an increased Voc of 0.84 V compared to the BTOR-ffBT-based solar cells with a PCE of 2.6% and a Voc of 0.49 V...

The rational design of new high performance materials for organic photovoltaic (OPV) applications is largely inhibited by a lack of design rules for materials that have slow bimolecular charge recombination. Due to the complex device physics present in OPVs, rigorous and reliable measurement techniques for charge transport and charge recombination are needed to construct improved physical models that can guide materials development and discovery. Here, we develop a new technique called impedance-photocurrent device analysis (IPDA) to quantitatively characterize the competition between charge extraction and charge recombination under steady state operational conditions. The measurements are performed on actual lab scale solar cells, have mild equipment requirements, and can be integrated into normal device fabrication and testing workflows. We perform IPDA tests on a broad set of devices with varying polymer:fullerene blend chemistry and processing conditions. Results from the IPDA technique exhibit significantly improved reliability and self-consistency compared to the open-circuit voltage decay technique (OCVD). IPDA measurements also reveal a significant negative electric field dependence of the bimolecular recombination coefficient in high fill factor devices, a finding which is inaccessible to most other common techniques and indicates that many of these techniques may overestimate the value that is most relevant for describing device performance. Future work utilizing IPDA to build structure–property relationships for bimolecular recombination will lead to enhanced design rules for creating efficient OPVs that are suitable for commercialization.

Due to their high-lying lowest unoccupied molecular orbitals (LUMOs), π-conjugated polymers based on benzothiadiazole and its derivatives typically are p-type. We report here the successful development of two narrow bandgap, ambipolar donor–acceptor copolymers, PDCNBT2T and PDCNBSe2T, which are based on new cyano-substituted strong electron acceptors, 4,7-dibromo-5,6-dicyano-2,1,3-benzothiadiazole (DCNBT) and 4,7-dibromo-5,6-dicyano-2,1,3-benzoselenadiazole (DCNBSe), respectively. Compared to their polymer analogues with fluorine substituents, the LUMO was lowered by a big margin of ca. 0.6 eV and the bandgap was reduced by 0.2–0.3 eV for the cyano-substituted polymers. Therefore, the cyano-substituted benzothiadiazole polymers showed very low-lying LUMO levels of ca. 4.3 eV. Benefiting from their narrow bandgaps of 1.1–1.2 eV and appropriately positioned LUMO levels, both polymers exhibit well balanced ambipolar transport characteristics in organic thin-film transistors, which differ from the p-type dominating transport properties of their fluorinated polymer analogues. A balanced hole/electron mobility of 0.59/0.47 cm2 V−1 s−1 was achieved for polymer PDCNBT2T, and a reduced hole/electron mobility of 0.018/0.014 cm2 V−1 s−1 was observed for the benzoselenadiazole-based PDCNBSe2T due to its lower crystallinity. These results show that the electron mobility can be enhanced by approximately two orders versus the electron mobility of the previously reported 4,7-di(thiophen-2-yl)-5,6-dicyano-2,1,3-benzothiadiazole-based polymer. This improvement was achieved by using the new acceptor units without additional electron-rich thiophene flanks, which allow a higher degree of freedom in selecting the donor co-unit and more effective tuning of energy levels of frontier molecular orbitals.

Two new bithiophene imide (BTI)-based n-type polymers were synthesized. f-BTI2-FT based on a fused BTI dimer showed a smaller band gap, a lower LUMO, and higher crystallinity than s-BTI2-FT containing a BTI dimer connected through a single bond. s-BTI2-FT exhibited a remarkable electron mobility of 0.82 cm2 V−1 s−1, and f-BTI2-FT showed a further improved mobility of 1.13 cm2 V−1 s−1 in transistors. When blended with the polymer donor PTB7-Th, f-BTI2-FT-based all-polymer solar cells (all-PSCs) attained a PCE of 6.85 %, the highest value for an all-PSC not based on naphthalene (or perylene) diimide polymer acceptors. However, s-BTI2-FT all-PSCs showed nearly no photovoltaic effect. The results demonstrate that f-BTI2-FT is one of most promising n-type polymers and that ring fusion offers an effective approach for designing polymers with improved electrical properties.

Building blocks having a high degree of backbone planarity, good solubilizing characteristics, and well-tailored physicochemical properties are highly desirable for constructing high-performance polymer semiconductors. Due to the detrimental steric hindrance created by alkyl chain substituents at the 3- and 3′-positions of bithiophene, “head-to-head” linkage containing 3,3′-dialkyl-2,2′-bithiophenes (BTR) are typically avoided in materials design. Replacing alkyl chains with less steric demanding alkynyl chains should greatly reduce steric hindrance by eliminating two H atoms at the sp-hybridized carbon center. Here we report the synthesis of a novel electron donor unit, 3,3′-dialkynyl-2,2′-bithiophene (BTRy), and its incorporation into conjugated polymer backbones. The alkynyl-functionalized head-to-head bithiophene linkage yields polymers with good solubility without sacrificing backbone planarity; the BTRy-based polymers show a high degree of conjugation with a narrow bandgap of ∼1.6 eV. When incorpora...

New small molecules having modified acceptor strength and π-conjugation length and containing dicyanovinylene (DCV) and tricyanovinylene (TCV) as a strongly electron-accepting unit with indacenodithiophene, IDT(DCV)2, IDT(TCV)2, and IDTT(TCV)2, were synthesized and studied in terms of their applicability to polymer solar cells with PTB7-Th as an electron-donating polymer. Intriguingly, the blended films containing IDT(TCV)2 and IDTT(TCV)2 exhibited superior shelf life stabilities of more than 1000 h without any reduction in the initial power conversion efficiency. The low-lying lowest unoccupied molecular orbital energy levels and robust internal morphologies of small TCV-containing molecules could afford excellent shelf life stability.

A series of D–A1–D–A2 type regioregular copolymers based on difluorobenzothiadiazole (DFBT) and dialkoxybenzothiadiazole (ROBT) structures was synthesized. The copolymers were prepared with different alkyl chain lengths and branching point positions. The weaker acceptor, ROBT, was incorporated as a solubilizing moiety, while the stronger acceptor, DFBT, was used to enhance intramolecular charge transfer interactions with low-lying frontier orbital levels. The design of DFBT–ROBT copolymers ensures good planarity via intrachain noncovalent F⋯S, S⋯O, and F⋯H coulombic interactions. Changing the alkyl chain branching point and length had pronounced effects on the interchain packing and charge carrier transport/recombination characteristics of the resultant polymers, which in turn influenced their photovoltaic performances. P2 (with 3-hexylundecyloxy) showed tight π–π stacking, high charge mobility, reduced bimolecular charge recombination, and an optimal nanoscale morphology compared to P1 (with 2-hexyldecyloxy). We prepared photovoltaic devices containing a blend of the copolymers with [6,6]-phenyl-C71-butyric acid methyl ester, and the resultant devices showed high power conversion efficiencies, 8.27% for P2, which is higher than that of P1 (6.87%). Furthermore, the alkyl side-chain length in P2 was varied systematically to study the correlation between the alkyl chain length in the interchain packing and photovoltaic performances. The variation in the alkyl chain branching was effective to modulate intermolecular packing to improve the photovoltaic performances. The optimum side chain length should be determined by carefully considering the solubility and interchain packing interactions.

A series of semi-crystalline, wide band gap (WBG) photovoltaic polymers were synthesized with varying number and topology of fluorine substituents. To decrease intramolecular charge transfer and to modulate the resulting band gap of D–A type copolymers, electron-releasing alkoxy substituents were attached to electron-deficient benzothiadiazole (A) and electron-withdrawing fluorine atoms (0–4F) were substituted onto a 1,4-bis(thiophen-2-yl)benzene unit (D). Intra- and/or interchain noncovalent Coulombic interactions were also incorporated into the polymer backbone to promote planarity and crystalline intermolecular packing. The resulting optical band gap and the valence level were tuned to 1.93–2.15 eV and −5.37 to −5.67 eV, respectively, and strong interchain organization was observed by differential scanning calorimetry, high-resolution transmission electron microscopy and grazing incidence X-ray scattering measurements. The number of fluorine atoms and their position significantly influenced the photophysical, morphological and optoelectronic properties of bulk heterojunctions (BHJs) with these polymers. BHJ photovoltaic devices showed a high power conversion efficiency (PCE) of up to 9.8% with an open-circuit voltage of 0.94–1.03 V. To our knowledge, this PCE is one of the highest values for fullerene-based single BHJ devices with WBG polymers having a band gap of over 1.90 eV. A tandem solar cell was also demonstrated successfully to show a PCE of 10.3% by combining a diketopyrrolopyrrole-based low band gap polymer.

In order to investigate the effect of the geometries of perylene diimide (PDI)-based small molecules, five different isomers were synthesized by using a cyclohexane core as a simple sp3-σ core. Diaminocylohexane is such an effective core for the systematic development of many kinds of isomers via geometric tuning as well as for reducing the self-aggregation tendency of PDIs. Depending on the anchoring position of the PDI units on the cyclohexane core (ortho-, meta- and para-), isomers exhibited differences in solubility and crystallinity. Among the studied isomers, ortho-substituted t-OCP was found to have a highly twisted molecular structure which minimizes the strong tendency towards crystallization due to individual PDI moieties. The unique geometrical nature of the t-OCP isomer led to the highest power conversion efficiency (PCE = 6.23%) of bulk heterojunction (BHJ) polymer solar cells (PSCs) with a higher short-circuit current density (Jsc) and fill factor (FF). It is mainly ascribed to the formation of a nanophase interpenetrating network with well-balanced carrier mobility in the blend film.

Three types of photoactive terpolymers (Random, Regular and Block) were synthesized by incorporating two electron-deficient moieties and one electron-rich moiety based on two parent donor polymers, poly[(2,5-bis(2-decyltetradecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBTDT) and poly[(2,5-bis(2-decyltetradecyloxy)phenylene)-alt-(5,6-dicyano-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2CNBT). All three terpolymers showed broad light absorption in the range of 300–850 nm covering the absorption of two parent polymers. Their optical, electrochemical, morphological and photovoltaic properties were compared and investigated in detail. Power conversion efficiencies (PCEs) of 5.63, 4.45 and 3.13% were obtained for PPDT2FBTDT-random-PPDT2CNBT, PPDT2FBTDT-regular-PPDT2CNBT and PPDT2FBTDT-block-PPDT2CNBT based photovoltaic devices, respectively. Through intensive investigation on charge carrier mobility, photocurrent and light intensity dependence of JSC, the random structure was proved to be the most effective molecular design in this series of terpolymers, showing weaker charge recombination and enhanced charge transport/extraction with well-distributed blend morphology. The fine modulation of different arrangements and compositions of the three monomers in a main chain is crucial for optimizing the terpolymeric structures as efficient photoactive materials.

Inspired by the excellent device performance of imide-functionalized polymer semiconductors in organic electronics, a novel imide-based building block, dithienylbenzodiimide (TBDI), with fused backbone is designed and synthesized. Single-crystal structure analysis reveals that the TBDI unit features non-planar backbone conformation but with a tight π-stacking distance of 3.36 A. By copolymerizing with various electron-rich co-units, a series of TBDI-based polymer semiconductors is synthesized and the optoelectronic, thermal, electrochemical and charge transport properties of the semiconductors are characterized. Attributed to the non-planar backbone and intrinsic electrical property of TBDI, all polymers exhibit wide bandgaps (∼2.0 eV) with low-lying HOMOs (

Polythiophenes, built on the electron-rich thiophene unit, typically possess high-lying energy levels of the lowest unoccupied molecular orbitals (LUMOs) and show hole-transporting properties. In this study, we develop a series of n-type polythiophenes, P1-P3, based on head-to-head-linked 3,3'-dialkoxy-4,4'-dicyano-2,2'-bithiophene (BTCNOR) with distinct side chains. The BTCNOR unit shows not only highly planar backbone conformation enabled by the intramolecular noncovalent sulfur-oxygen interaction but also significantly suppressed LUMO level attributed to the cyano-substitution. Hence, all BTCNOR-based polymer semiconductors exhibit low-lying LUMO levels, which are ∼1.0 eV lower than that of regioregular poly(3-hexylthiophene) (rr-P3HT), a benchmark p-type polymer semiconductor. Consequently, all of the three polymers can enable unipolar n-type transport characteristics in organic thin-film transistors (OTFTs) with low off-currents ( I

Two semicrystalline low band gap polymers based on highly electron-deficient 2,1,3-benzothiadiazole-5,6-dicarboxylicimide (BTI) were synthesized by considering the chain planarity via intrachain noncovalent coulombic interactions. The thiophene-BTI and thienothiophene-BTI based PPDTBTI and PPDTTBTI have a low band gap (∼1.5 eV) via strong intramolecular charge transfer interaction, showing a broad light absorption covering 300∼850 nm. Semicrystalline film morphology was observed for both polymers in the grazing incidence wide angle X-ray scattering measurements. Interestingly, PPDTBTI showed a pronounced edge on packing structure but PPDTTBTI showed predominantly a face on orientation in both pristine and blend films. Different packing patterns influenced significantly the charge carrier transport, recombination and resulting photovoltaic characteristics. The best power conversion efficiency was measured to be 5.47% for PPDTBTI and 6.78% for PPDTTBTI, by blending with the fullerene derivative, PC71BM. Compared to the PPDTBTI blend, PPDTTBTI: PC71BM suffered from the lower open-circuit voltage but showed the substantially higher hole mobility and short-circuit current density with smaller charge recombination, showing very good agreements with molecular structures and morphological characteristics. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016

A series of acceptor1–donor–acceptor2 (A1–D–A2)-type copolymers was designed and synthesized using thiophene as an electron-rich unit and benzothiadiazole (BT) and benzotriazole (BTz) as electron-deficient moieties. A weaker acceptor, BTz, was incorporated as a solubilizing moiety with three tetradecyl (or tetradecyloxy) side chains, and a stronger acceptor, BT, was substituted with different numbers of fluorines to modulate the intramolecular charge transfer interaction and the resulting electronic structures. The similar molecular structures of BT and BTz did not disrupt the interchain organization significantly, and the absence of solubilizing alkyl substituents on the electron-rich thiophene did not increase the highest occupied molecular orbital of the resulting polymers. The polymers showed broad absorption in the range of 350–750 nm. Intra- and/or interchain non-covalent coulombic interactions (for example, dipole–dipole interactions via S···O, S···F) ensured a planar backbone and a semi-crystalline morphology in the film. Bulk heterojunction polymer solar cells were fabricated using blends of the polymers and phenyl-C71-butyric acid methyl ester (PC71BM). For a difluoro-BT containing polymer (BTzDT2FBT), a power conversion efficiency up to 7% was achieved with a short circuit current density of 14.64 mA cm−2, open circuit voltage of 0.75 V and fill factor of 0.64. Three types of A1–D–A2 conjugated polymers were synthesized based on thiophene as an electron-rich unit and two similarly structured electron-deficient moieties of benzothiadiazole (BT) and benzotriazole (BTz). The weaker acceptor, BTz, with three alkyl (or alkyloxy) substituents took on a solubilizing role without deteriorating the chain planarity. The absence of alkyl substituents on thiophene induced a deep valence band. Increasing the number of fluorine substituents on BT decreased the frontier orbitals and enhanced the interchain packing. The chain planarity and crystalline interchain organization were facilitated via intra- and/or interchain non-covalent S···O and S···F coulombic interactions. The best power conversion efficiency of 7% was measured for BTzDT2FBT:PC71BM.

We investigate the photovoltaic properties and charge dynamics of all polymer solar cells (all-PSCs) based on 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)) and its fluorinated analogue, poly[(N,N′-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-5,5′-(3,3′-difluoro-2,2′-bithiophene)] (P(NDI2OD-T2F)), as the acceptor polymer and poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene-alt-5-octyl-4H-thieno[3,4-c]pyrrole-4,6(5H)-dione] (PBDTTTPD) as the donor polymer. The PBDTTTPD:P(NDI2OD-T2)-based device has a high open-circuit voltage (VOC) of 1.03 V but suffers from low power conversion efficiency (PCE) of 2.02% with a short-circuit current density (JSC) and fill factor (FF) of 4.45 mA cm–2 and 0.44, respectively. In a stark contrast, the PCE of PBDTTTPD:P(NDI2OD-T2F)-based PSC dramatically increases to 6.09% (VOC = 1.00 V, JSC = 11.68 mA cm–2, and FF = 0.52). These results are attributed...

Here, taking a polythiophene derivative (PBDD4T) as a starting polymer, we tried to increase the rotation barrier and hence stabilize its backbone conformation by introducing fluorine into the β- and β′-position of the α-linked bithiophene segments and then synthesized a new polymer named as PBDD4T-2F. Our results demonstrate that the rotation barrier between the α-linked bithiophene significantly increases after the fluorination, so PBDD4T-2F has a more stable backbone conformation than PBDD4T. Compared to PBDD4T, PBDD4T-2F shows stronger aggregation effect in solution state and more compact π–π stacking in solid thin film and also possesses deeper HOMO level. These properties make PBDD4T-2F being an ideal donor material in PSCs. When blended with PC71BM, a fullerene acceptor, the PBDD4T-2F-based device showed a power conversion efficiency (PCE) of 9.04%, which is 38% higher than that of the PBDD4T-based device; when blended with ITIC, a non-fullerene acceptor, the PBDD4T-2F-based device showed a PCE of ...

The detailed characterization of a dialkoxyphenylene-difluorobenzothiadiazole based conjugated polymer poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) is reported. PPDT2FBT closely tracks theoretical photocurrent production while maintaining a high fill factor in remarkably thick films. In order to understand the properties that enable PPDT2FBT to function with thick active layers, the effect of film thickness on the material properties and device parameters was carefully studied and compared to three benchmark polymers. Optical modeling, grazing incidence wide angle X-ray scattering, cross-sectional transmission electron microscopy, transient photoconductivity, and extensive device work were carried out and have clarified the key structural features and properties that allow such thick active layers to function efficiently. The unique behavior of thick PPDT2FBT films arises from high vertical carrier mobility, an isotropic morphology with strong, vertical π–π stacking, and a suitable energy band structure. These physical characteristics allow efficient photocurrent extraction, internal quantum efficiencies near 100% and power conversion efficiencies over 9% from exceptionally thick active layers in both conventional and inverted architectures. The ability of PPDT2FBT to function efficiently in thick cells allows devices to fully attenuate incident sunlight while providing a pathway to defect-free film processing over large areas, constituting a major advancement toward commercially viable organic solar cells.

Three types of linear and planar-structured donor (D)–acceptor (A) type alternating copolymers were synthesized by incorporating intrachain noncovalent Coulombic interactions, based on thieno[3,2-b]thiophene and benzothiadiazole (BT) moieties. The chain linearity and fine adjustment of interchain organization by the incorporation of different numbers of electronegative fluorine atoms onto BT, significantly affected the frontier energy levels, film morphology, and the resulting charge transport properties. The semi-crystalline morphology and charge carrier transport properties were studied by grazing incidence wide-angle X-ray scattering and polymer field-effect transistor (PFET) characteristic measurements. A hole mobility as high as 0.1 cm2 V−1 s−1 in PFET was obtained for poly[2,5-bis(decyltetradecyloxy)benzene-alt-4,7-bis(thieno[3,2-b]thiophene)-5,6-difluoro-2,1,3-benzothiadiazole] (PPDTT2FBT), suggesting a strong self-organization due to the linear chain configuration with conformation lock. The difluorinated PPDTT2FBT also showed the highest power conversion efficiency (PCE, 6.4%) by blending with PC71BM, but a poorer photovoltaic performance was obtained compared to the wavy-structured counterpart, poly[2,5-bis(2-hexyldecyloxy)phenylene-alt-5,6-difluoro-4,7-di(thiophen-2-yl)-2,1,3-benzothiadiazole] (PPDT2FBT), reported previously. The mainly edge-on orientation of PPDTT2FBT (with π–π stacking in both xy and z directions) is attributed to the moderate PCE in the blends. Fine modulation of chain linearity may suggest an effective way to control the desirable interchain ordering and bulk film morphology for specific application in polymer solar cells or field effect transistors.

A series of difluoroquinoxaline–thiophene based reduced band gap polymers was designed and synthesized by considering non-covalent coulombic interactions in a polymeric main chain. The insertion of different numbers of thiophene moieties allows for the adjustment of the absorption range, frontier energy levels, crystalline self-organization, film morphology and the resulting photovoltaic properties. A thick blend film of poly(thiophene-alt-(2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline)) (PDFQx-T):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) showed a rough, inhomogeneous and largely phase-separated surface morphology compared to a typical film with ∼100 nm thickness. A similar trend was observed in the surface morphology of a poly(2,2′-bithiophene-alt-(2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline)) (PDFQx-2T) blend film, showing deteriorated photovoltaic properties with increasing film thickness. In contrast, poly(2,2′:5′,2′′-terthiophene-alt-2,3-bis(3,4-bis(octyloxy)phenyl)-6,7-difluoroquinoxaline) (PDFQx-3T) had a similar blend film morphology for both thick and thin active layers, showing a homogeneous and smooth morphology with a face-on orientation and tight π–π stacking (d-spacing = 3.6 A). The optimized photovoltaic cell based on PDFQx-3T : PC71BM achieved a power conversion efficiency (PCE) of 8% with an open-circuit voltage of 0.74 V, a short-circuit current of 17.19 mA cm−2 and a fill factor of 0.63 at an active layer thickness of ∼270 nm. It is still a challenge to develop photovoltaic polymers which allow efficient charge transport and extraction at a device thickness of ∼300 nm. Fine-adjustment of intra- and interchain interactions must be considered carefully to achieve high device properties for thick devices without deterioration in the blend morphology and charge recombination. This high PCE at an active layer thickness of ∼300 nm may suggest great potential for the mass production of printed polymer solar cells via industrial solution processes.

New M- and V-shaped perylene diimide (PDI)-based small molecules using a non-conjugated 1,1-diphenylcyclohexane linker (CP-M and CP-V, respectively) were designed and synthesized as new n-type acceptors for nonfullerene-based polymer solar cells. The blended film with poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) and CP-V displayed a higher power conversion efficiency of 5.28% due to higher short circuit current and fill factor values.

Diketopyrrolopyrrole (DPP)-based copolymers have received considerable attention as promising semiconducting materials for high-performance organic thin-film transistors (OTFTs). However, these polymers typically exhibit p-type or ambipolar charge-transporting characteristics in OTFTs due to their high-lying highest occupied molecular orbital (HOMO) energy levels. In this work, a new series of DPP-based n-type polymers have been developed by incorporating fused bithiophene imide oligomers (BTIn) into DPP polymers. The resulting copolymers BTIn-DPP show narrow band gaps as low as 1.27 eV and gradually down-shifted frontier molecular orbital energy levels upon the increment of imide group number. Benefiting from the coplanar backbone conformation, well-delocalized π-system, and favorable polymer chain packing, the optimal polymer in the series shows promising n-type charge transport with an electron mobility up to 0.48 cm2 V-1 s-1 in OTFTs, which is among the highest values for the DPP-based n-type polymers reported to date. The results demonstrate that incorporating fused bithiophene imide oligomers into polymers can serve as a promising strategy for constructing high-performance n-type polymeric semiconductors.

We present here a series of wide-band-gap (Eg: >1.8 eV) polymer donors by incorporating thiophene-flanked phenylene as an electron-donating unit and quinoxaline as an electron-accepting co-unit to attain large open-circuit voltages (Vocs) and short-circuit currents (Jscs) in nonfullerene organic solar cells (OSCs). Fluorination was utilized to fine-tailor the energetics of polymer frontier molecular orbitals (FMOs) by replacing a variable number of H atoms on the phenylene moiety with F. It was found that fluorination can effectively modulate the polymer backbone planarity through intramolecular noncovalent S···F and/or H···F interactions. Polymers (P2–P4) show an improved molecular packing with a favorable face-on orientation compared to their nonfluorinated analogue (P1), which is critical to charge carrier transport and collection. When mixed with IDIC, a nonfullerene acceptor, P3 with two F atoms, achieves a remarkable Voc of 1.00 V and a large Jsc of 15.99 mA/cm2, simultaneously, yielding a power-con...

Ternary organic solar cells are promising alternatives to the binary counterpart due to their potential in achieving high performance. Although a growing number of ternary organic solar cells are recently reported, less effort is devoted to morphology control. Here, ternary organic solar cells are fabricated using a wide-bandgap polymer PBT1-C as the donor, a crystalline fused-ring electron acceptor ITIC-2Cl, and an amorphous fullerene derivative indene-C60 bisadduct (ICBA) as the acceptor. It is found that ICBA can disturb π-π interactions of the crystalline ITIC-2Cl molecules in ternary blends and then help to form more uniform morphology. As a result, incorporation of 20% ICBA in the PBT1-C:ITIC-2Cl blend enables efficient charge dissociation, negligible bimolecular recombination, and balanced charge carrier mobilities. An impressive power conversion efficiency (PCE) of 13.4%, with a high fill factor (FF) of 76.8%, is eventually achieved, which represents one of the highest PCEs reported so far for organic solar cells. The results manifest that the adoption of amorphous fullerene acceptor is an effective approach to optimizing the ternary blend morphology and thereby increases the solar cell performance.

Development of high-performance unipolar n-type organic semiconductors still remains as a great challenge. In this work, all-acceptor bithiophene imide-based ladder-type small molecules BTIn and semiladder-type homopolymers PBTIn (n = 1–5) were synthesized, and their structure–property correlations were studied in depth. It was found that Pd-catalyzed Stille coupling is superior to Ni-mediated Yamamoto coupling to produce polymers with higher molecular weight and improved polymer quality, thus leading to greatly increased electron mobility (μe). Due to their all-acceptor backbone, these polymers all exhibit unipolar n-type transport in organic thin-film transistors, accompanied by low off-currents (10–10–10–9 A), large on/off current ratios (106), and small threshold voltages (∼15–25 V). The highest μe, up to 3.71 cm2 V–1 s–1, is attained from PBTI1 with the shortest monomer unit. As the monomer size is extended, the μe drops by 2 orders to 0.014 cm2 V–1 s–1 for PBTI5. This monotonic decrease of μe was al...

A face-on oriented and p-doped semicrystalline conjugated polymer, poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]-thiadiazole)] (PPDT2FBT), was studied as a hole-transport layer (HTL) in methylammonium lead triiodide-based perovskite solar cells (PVSCs). PPDT2FBT exhibits a mid-band gap (1.7 eV), high vertical hole mobility (7.3 × 10–3 cm2/V·s), and well-aligned frontier energy levels with a perovskite layer for efficient charge transfer/transport, showing a maximum power conversion efficiency (PCE) of 16.8%. Upon doping the PPDT2FBT HTL with a nonhygroscopic Lewis acid, tris(pentafluorophenyl)borane (BCF, 2–6 wt %), the vertical conductivity was improved by a factor of approximately 2, and the resulting PCE was further improved up to 17.7%, which is higher than that of standard PVSCs with 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-OMeTAD) as an HTL. After BCF doping, the clearly enhanced carrier diffusion coefficient, diffu...

A series of polymer semiconductors incorporating 2,1,3-benzothiadiazole-5,6-dicarboxylicimide (BTZI) as strong electron-withdrawing unit and an alkoxy-functionalized head-to-head linkage containing bithiophene or bithiazole as highly electron-rich co-unit are designed and synthesized. Because of the strong intramolecular charge transfer characteristics, all three polymers BTZI-TRTOR (P1), BTZI-BTOR (P2), and BTZI-BTzOR (P3) exhibit narrow bandgaps of 1.13, 1.05, and 0.92 eV, respectively, resulting in a very broad absorption ranging from 350 to 1400 nm. The highly electron-deficient 2,1,3-benzothiadiazole-5,6-dicarboxylicimide and alkoxy-functionalized bithiophene (or thiazole) lead to polymers with low-lying lowest unoccupied molecular orbitals (−3.96 to −4.28 eV) and high-lying highest occupied molecular orbitals (−5.01 to −5.20 eV). Hence, P1 and P3 show substantial and balanced ambipolar transport with electron mobilities/hole mobilities of up to 0.86/0.51 and 0.95/0.50 cm2 V–1 s–1, respectively, and ...

Owing to their low cost, easy processing, and the possibility of flexible fabrication, polymer light-emitting diodes (PLEDs) are emerging as an important class of materials. Despite promising characteristics, the relatively easy ionization of the well-known low-work-function cathodes such as Ca and Ba prevents the full usage of these materials. Herein, we report the syntheses of three alcohol-soluble conjugated polymers with different conjugation lengths and electron affinities as electron injection and transport materials for PLEDs: poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-tetrafluorobenzene] (PFOH-1), poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-thiophene] (PFOH-2), and poly[9,9-bis(2-dihexylaminoethoxy)fluorene-co-benzo-thiadiazole] (PFOH-3). For comparison, devices using Al, Ca, and Al cathodes were also fabricated. The device based on the Al cathode showed lower performance with a luminescence efficiency of 0.93 cd/A and a luminance of 248 cd/m2; that based on the low-work-function metal Ca as the cathode showed a near-threefold increase in luminescence efficiency at 2.51 cd/A and brightness at 856 cd/m2 owing to greatly enhanced electron injection from the cathode; and the device employing the PFOH-3/Al cathode exhibited a luminescence efficiency of 2.35 cd/A and a brightness of 667 cd/m2 at a current density of 35 mA/cm2, which is comparable with the performance of the device with the Ca cathode.

Four different kinds of photovoltaic polymers were synthesized by controlling the intrachain noncovalent coulomb interactions through the incorporation of alkoxy- or alkylthio-substituted phenylene, 4,7-di(furan-2-yl)benzothiadiazole, and 4,7-di(thiophen-2-yl)benzothiadiazole as a building block. Fine modulation of the interplay of dipole–dipole, H-bond, and chalcogen–chalcogen interactions (O···S, O···H, S···S, S···F, etc.) along the polymeric backbone influenced the chain planarity, interchain organization, film morphology, and electrical and photovoltaic properties significantly. By replacing the alkoxy substituents with alkylthio groups, the torsional angle increased (136–168°) due to the absence of an O···S attractive coulomb interaction (and/or increased S···S steric hindrance), enhancing the amorphous nature with hindered interchain packing. The alkoxy-substituted polymers exhibited nanofibrillar structures, showing strong interlamellar scattering peaks up to (300) with tight face-on π–π stacking i...

Three kinds of donor–acceptor (D–A) type photovoltaic polymers were synthesized based on 2,7-carbazole and thieno[3,4-c]pyrrole-4,6-dione (TPD). The conjugation of weakly electron (e)-donating 2,7-carbazole and strongly e-accepting TPD moieties yielded a deep highest occupied molecular orbital (HOMO) and its energy level was fine-controlled to be −5.72, −5.67 and −5.57 eV through the incorporation of thiophene (T), thieno[3,2-b]thiophene (TT) and bithiophene (BT) as a π-bridge. Polymer:[6,6]-phenyl-C71 butyric acid methyl ester (PC71BM) based bulk heterojunction solar cells exhibited a high open-circuit voltage (VOC) in the range, 0.86–0.94 V, suggesting good agreement with the measured HOMO levels. Despite the high VOC, the thiophene (or thienothiophene)-containing PCTTPD (or PCTTTPD) showed poor power conversion efficiency (PCE, 1.14 and 1.25%) because of the very low short-circuit current density (JSC). The voltage-dependent photocurrent and photoluminescence quenching measurements suggested that hole transfer from PC71BM to polymer depends strongly on the HOMO level of the polymer. The PCTTPD and PCTTTPD devices suffered from electron–hole recombination at the polymer/PC71BM interfaces because of the insufficient energy offset between the HOMOs of the polymer and PC71BM. The PCBTTPD:PC71BM device showed the best PCE of 3.42% with a VOC and JSC of 0.86 V and 7.79 mA cm−2, respectively. These results show that photovoltaic polymers should be designed carefully to have a deep HOMO level for a high VOC and sufficient energy offset for ensuring efficient hole transfer from PC71BM to the polymer.

The electronic properties of the donor–acceptor (DA) polymer poly{5,6-bis(octyloxy)-4-(thiophen-2-yl)benzo[c]-1,2,5-thiadiazole} (PTBT) have been investigated using spectroscopic and computational techniques. Electronic absorption and emission spectra reveal the presence of an ordered and a disordered phase in solution. Franck–Condon modeling of the ordered phase yields Huang–Rhys factors of 0.55 (20 °C) and 0.51 (−180 °C), indicating little structural distortion between ground and excited state. DFT calculations with resonance Raman spectroscopy are consistent with a lowest energy excited state that is electronically delocalized and has little charge-transfer character, unexpected for a copolymer with a low bandgap (∼1.8 eV). Transient absorption spectroscopy of PTBT:fullerene blends reveals near-unity internal charge-transfer yields in both ordered and disordered film morphologies. In the disordered blend, charge transfer is complete within the laser pulse (100 fs), whereas the ordered blend also featur...

The molecular weight of a conjugated polymer is one of the key factors determining the electrical, morphological, and mechanical properties as well as its solubility in organic solvents and miscibility with other polymers. In this study, a series of semicrystalline poly[(2,5-bis(2-hexyldecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBT) polymers with different number-average molecular weights (M(n)'s) (PPDT2FBT(L), M(n) = 12 kg/mol; PPDT2FBT(M), M(n) = 24 kg/mol; PPDT2FBT(H), M(n) = 40 kg/mol) were synthesized, and their photovoltaic properties as electron donors for all-polymer solar cells (all-PSCs) with poly[[N,N'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)] (P(NDI2OD-T2)) acceptor were studied. The M(n) effect of PPDT2FBT on the structural, morphological, electrical, and photovoltaic properties was systematically investigated. In particular, tuning the M(n) induced dramatic effects on the aggregation behaviors of the polymers and their bulk heterojunction morphology of all-PSCs, which was thoroughly examined by grazing incident X-ray scattering, resonant soft X-ray scattering, and other microscopy measurements. High M(n) PPDT2FBT(H) promoted a strong "face-on" geometry in the blend film, suppressed the formation of an excessively large crystalline domain, and facilitated molecularly intermixed phases with P(NDI2OD-T2). Therefore, the optimized all-PSCs based on PPDT2FBT(H)/P(NDI2OD-T2) showed substantially higher hole and electron mobilities than those of PPDT2FBT(L)/P(NDI2OD-T2), leading to a power conversion efficiency exceeding 5%, which is one of the highest values for all-PSCs reported thus far.

When aqueous conjugated-polyelectrolyte colloidal solutions containing an adequate amount of surfactant with an appropriate hydrophile-lipophile balance were sprayed onto latent fingerprints (LFPs), the polymer nanoparticles were readily transferred to the LFPs to reveal highly distinguishable fluorescent images, while the LFPs themselves remained intact.

Alkyl side chains play critical roles in the molecular design of conjugated polymers for applications in bulk-heterojunction (BHJ) polymer solar cells (PSCs). Recently, the introduction of alkylthio substituents onto poly(benzo[1,2-b:4,5-b′]dithiophene-alt-thieno[3,4-b]thiophene) (PBDTTT)-based conjugated polymers has been proved to be an effective method to improve the photovoltaic properties of the polymers. In this contribution, three alkylthiothiophene-substituted benzodithiophene (BDT-TS) based polymers, named PBDT-TS1, PBDT-TS2 and PBDT-TS3, were synthesized and applied as donor materials in PSCs. In these three polymers, octyl, 2-ethylhexyl and 3,7-dimethyloctyl are used on their BDT units, respectively. The polymers were characterized in parallel by absorption spectroscopy, thermogravimetric analysis (TGA), electrochemical cyclic voltammetry (CV) and grazing-incidence wide-angle X-ray scattering (GI-WAXS), and also their photovoltaic properties in PSCs were studied and compared. The results reveal that the alkyls have little influence on absorption spectra and molecular energy levels of the polymers. The GI-WAXS results show that PBDT-TS1 has stronger and tighter π–π stacking than the other two polymers, implying that linear alkyls may reduce steric hindrance than branched alkyl chains in an aggregation state. As a consequence of the strong π–π inter-chain packing of PBDT-TS1, an increased short circuit current density (JSC) and fill factor (FF) as well as a power conversion efficiency of over 9.5% are achieved in single-cell BHJ devices, which are obviously higher than those for devices based on the other two polymers. Overall, the results of this work suggest that alkyl side groups play an important role in affecting the π–π stacking of the conjugated polymers, i.e., the linear octyl has weaker steric hindrance for the inter-chain π–π stack than the branched 2-ethylhexyl and 3,7-dimethyloctyl, and for the highly efficient polymer based on the 2-alkylthiothiophene-substituted BDT, PBDT-TS1 has the optimal structure.

The coexistence of intermixed amorphous polymer : fullerene phases alongside pure semicrystalline polymer and fullerene phases provides a plausible explanation for effective charge separation in organic photovoltaic blends by providing a cascaded energy landscape. We sought to test this proposal by spectroscopically tracking charge dynamics in 3-phase blends compared with binary counterparts and linking these dynamics to free charge yields. Our study applies broadband transient absorption spectroscopy to a series of closely related alternating thiophene–benzothiadiazole copolymers in which the tuned curvature of the polymer backbone controls the nature and degree of polymer–fullerene intermixing. Free charge generation is most efficient in the 3-phase morphology that features intimately mixed polymer : PCBM regions amongst neat polymer and PCBM phases. TA spectral dynamics and polarization anisotropy measurements reveal the sub-nanosecond migration of holes from intermixed to pure polymer regions of such blends. In contrast, 2-phase blends lack the spectral dynamics of this charge migration process and suffer from severe geminate recombination losses. These results provide valuable spectroscopic evidence for an efficient charge separation pathway that relies on the 3-phase morphology.

A series of thienothiophene-benzotriazole-based semicrystalline copolymers, PTTBTz, PTTBTz-F, and PTTBTz-OR, were synthesized by considering chain linearity, planarity and inter-chain packing by virtue of non-covalent attractive interaction. Fluorine and alkoxy substituents were introduced to modulate the intra- and inter-chain coulombic interactions and crystalline ordering. The fluorine and alkoxy-substituted PTTBTz-F and PTTBTz-OR showed pronounced inter-chain packing with edge-on orientation confirmed by UV-vis absorption and X-ray diffraction measurements. The well-resolved diffraction patterns were obtained for PTTBTz-F and PTTBTz-OR, showing (100)∼(500) inter-lamellar scattering peaks (d-spacing, 17∼18 Å) in the out-of-plane direction and a π-π stacking peak (d-spacing, 3.5∼4.1 Å) in the in-plane direction. Organic field effect transistor (OFET) devices were fabricated with a bottom gate and top contact geometry. PTTBTz-F (μh = 4.49 × 10–2 cm2 V–1 s–1, on/off ratio = 1.13 × 107) and PTTBTz-OR (μh = 8.39 × 10–3 cm2 V–1 s–1, on/off ratio = 2.98 × 104) showed nearly 3 and 2 orders of magnitude higher hole mobility upon annealing at 305 and 260 °C, with compared to the unsubstituted PTTBTz.

We report a series of benzotriazole-based semicrystalline π-conjugated polymers with noncovalent conformational locks for applications in polymer field-effect transistors. The benzotriazole moiety is a versatile electron-deficient building block that offers two chemically functionalizable sites, 2(N) and 5, 6(C) positions, allowing easy modulation of the solution processability and electronic structures of the resulting polymers. Fluorine or alkoxy substituents were introduced to the benzotriazole unit to enhance the molecular ordering through intra- and intermolecular F···S, F···H–C, C–F···πF, or S···O attractive interactions. The fluorinated polymer (PTBTz-F) showed remarkably enhanced hole mobility (μh = 1.9 cm2/(V·s), on/off ratio = 8 × 107) upon thermal annealing at 305 °C, compared to the unsubstituted one (PTBTz) (μh = 7.0 × 10–3 cm2/(V·s), on/off ratio = 3 × 106). Alkoxy unit substitution (PTBTz-OR) also improved the carrier mobility up to 0.019 cm2/(V·s) with an on/off ratio of 4 × 105. Fluorine ...

We report a series of semi-crystalline, low band gap (LBG) polymers and demonstrate the fabrication of highly efficient polymer solar cells (PSCs) in a thick single-cell architecture. The devices achieve a power conversion efficiency (PCE) of over 7% without any post-treatment (annealing, solvent additive, etc.) and outstanding long-term thermal stability for 200 h at 130 °C. These excellent characteristics are closely related to the molecular structures where intra- and/or intermolecular noncovalent hydrogen bonds and dipole–dipole interactions assure strong interchain interactions without losing solution processability. The semi-crystalline polymers form a well-distributed nano-fibrillar networked morphology with PC70BM with balanced hole and electron mobilities (a h/e mobility ratio of 1–2) and tight interchain packing (a π–π stacking distance of 3.57–3.59 A) in the blend films. Furthermore, the device optimization with a processing additive and methanol treatment improves efficiencies up to 9.39% in a ∼300 nm thick conventional single-cell device structure. The thick active layer in the PPDT2FBT:PC70BM device attenuates incident light almost completely without damage in the fill factor (0.71–0.73), showing a high short-circuit current density of 15.7–16.3 mA cm−2. Notably, PPDT2FBT showed negligible changes in the carrier mobility even at ∼1 μm film thickness.