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Biological compounds often provide clues to advance material designs. Replicating their molecular structure and functional motifs in artificial materials offers a blueprint for unprecedented functionalities. Here, we report a flexible biomimetic thermal sensing (BTS) polymer that is designed to emulate the ion transport dynamics of a plant cell wall component, pectin. Using a simple yet versatile synthetic procedure, we engineer the physicochemical properties of the polymer by inserting elastic fragments in a block copolymer architecture, making it flexible and stretchable. The thermal response of our flexible polymer outperforms current state-of-the-art temperature sensing materials, including vanadium oxide, by up to two orders of magnitude. Thermal sensors fabricated from these composites exhibit a sensitivity that exceeds 10 mK and operate stably between 15° and 55°C, even under repeated mechanical deformations. We demonstrate the use of our flexible BTS polymer in two-dimensional arrays for spatiotemporal temperature mapping and broadband infrared photodetection.

Silent communication based on biosignals from facial muscle requires accurate detection of its directional movement and thus optimally positioning minimum numbers of sensors for higher accuracy of speech recognition with a minimal person-to-person variation. So far, previous approaches based on electromyogram or pressure sensors are ineffective in detecting the directional movement of facial muscles. Therefore, in this study, high-performance strain sensors are used for separately detecting

Quinoxaline (Qx) derivatives are promising building units for efficient photovoltaic polymers owing to their strong light absorption and high charge-transport abilities, but they have been used exclusively in the construction of polymer donors. Herein, for the first time, Qx-based polymer acceptors (PA s) were developed by introducing electron-withdrawing cyano (CN) groups into the Qx moiety (QxCN). A series of QxCN-based PA s, P(QxCN-T2), P(QxCN-TVT), and P(QxCN-T3), were synthesized by copolymerizing the QxCN unit with bithiophene, (E)-1,2-di(thiophene-2-yl)ethene, and terthiophene, respectively. All of the PA s exhibited unipolar n-type characteristics with organic field-effect transistor (OFET) mobilities of around 10-2 cm2 V-1 s-1 . In space-charge-limited current devices, P(QxCN-T2) and P(QxCN-TVT) exhibited electron mobilities greater than 1.0×10-4 cm2 V-1 s-1 , due to the well-ordered structure with tight π-π stacking. When the PA s were applied in all-polymer solar cells (all-PSCs), the highest performance of 5.32 % was achieved in the P(QxCN-T2)-based device. These results demonstrate the significant potential of Qx-based PA s for high-performance all-PSCs and OFETs.

The recent evolution of new polymer acceptors (PAs) using small-molecule building blocks with high light absorption has significantly increased the power conversion efficiency (PCE) of all-polymer ...

In this study, two wide-bandgap PM7 polymer derivatives are developed via simple structural modification of the fused-accepting unit by incorporating ester groups on terthiophene at different positions (i.e., two ester groups on the outer thiophenes (PM7 D1) and on the central thiophene (PM7 D2)). This simple modification creates a higher-energy light absorption window, providing better complementary light harvesting with naphthalenediimide-based acceptor, P(NDI2HD-Se). As a result, PM7 D1-based all-polymer solar cells (all-PSCs) exhibit a high power conversion efficiency (PCE) of 9.13%, which outperforms that of the PM7-based all-PSC (PCE = 6.93%). Importantly, the ester structural modification has significant impact on the thin-film mechanical ductility and robustness. For example, elongation properties of PM7 D1 and PM7 D2 pristine films are significantly improved by ca. 2.5 times compared to that of PM7. This result is attributed to the flexible ester groups, which are able to effectively compensate for applied stress. The improved ductile properties of PM7 D1 and PM7 D2 also affect the mechanical ductility of the blend films, leading to 1.5-fold increase in crack onset strain compared with that of the PM7 blend film. Therefore, we demonstrate that the introduction of ester groups in conjugated polymers provides a simple and promising strategy for future stretchable electronics.

While the power conversion efficiencies (PCEs) of organic solar cells (OSCs) have been dramatically increased through the development of small molecular acceptors (SMAs), achieving eco-friendly solution processability of OSCs is a crucial prerequisite for their practical application. In this study, we develop three new, green solvent-processable SMAs (YSe–C3, YSe–C6, and YSe–C9) with different outer side-chains (n-propyl (C3), n-hexyl (C6), and n-nonyl (C9)), affording high-performance OSCs with non-halogenated solvent (o-xylene)-processed active layers. Also, the impact of both outer and inner side-chain engineering of these SMAs on the performance of eco-friendly fabricated OSCs is systematically investigated. The outer side-chain structure has a much more significant impact than the inner side-chain. For example, the PM6:YSe–C6 blend affords high-performance OSCs with a power conversion efficiency (PCE) of over 16%, whereas the PCEs of the YSe–C3- and YSe–C9-based OSCs are only 11–14%. The lower PCEs of PM6:YSe–C3 and C9 are mainly attributed to reduced electron mobility and increased charge recombination, resulting from aggregate-containing non-optimal blend morphologies. Interestingly, the well-optimized morphology of the YSe–C6-based blend also affords OSC devices with active layer thickness-independent PCEs, up to a thickness of >400 nm, demonstrating the great potential for large-area device manufacturing via an eco-friendly printing process. Thus, optimizing the outer side-chain structure of Y-series SMAs is essential for producing green solvent-processed high-performance OSCs.

In this work, the impact of temperature-dependent aggregation behaviors in benzodithiophene (BDT)-based polymer donors (PDs) on the electrical, morphological, and photovoltaic performances of all-p...

Despite the recent breakthroughs of polymer solar cells (PSCs) exhibiting a power conversion efficiency of over 17%, toxic and hazardous organic solvents such as chloroform and chlorobenzene are still commonly used in their fabrication, which impedes the practical application of PSCs. Thus, the development of eco-friendly processing methods suitable for industrial-scale production is now considered an imperative research focus. This Review provides a roadmap for the design of efficient photoactive materials that are compatible with non-halogenated green solvents (e.g., xylenes, toluene, and tetrahydrofuran). We summarize the recent development of green processing solvents and the processing methods to match with the efficient photoactive materials used in non-fullerene solar cells. We further review progress in the use of more eco-friendly solvents (i.e., water or alcohol) for achieving truly sustainable and eco-friendly PSC fabrication. For example, the concept of water- or alcohol-dispersed nanoparticles made of conjugated materials is introduced. Also, recent important progress and strategies to develop water/alcohol-soluble photoactive materials that completely eliminate the use of conventional toxic solvents are discussed. Finally, we provide our perspectives on the challenges facing the current green processing methods and materials, such as large-area coating techniques and long-term stability. We believe this Review will inform the development of PSCs that are truly clean and renewable energy sources.

We report highly efficient all-polymer solar cells with power conversion efficiencies of over 4.5% by highly intermixed blends of PTB7-Th donor and P(NDI2OD-T2) acceptor polymers. The low interfacial tension and the face-on π–π stackings of the all-polymer blends afforded desired nanophase morphology, which facilitates efficient charge transport from the active layer to each electrode. In addition, the incorporation of 1,8-diiodooctane additives was able to tune the degree of crystallinity and orientation of P(NDI2OD-T2) acceptors, resulting in remarkable enhancement of electron mobility, external quantum efficiency, and JSC values.

The effects of the position of alkoxy side chains in quinoxaline (Qx)-based polymer acceptors (PAs) on the characteristics of materials and the device parameters of all-polymer solar cells (all-PSCs) are investigated. The alkoxy side chains are selectively located at the meta, para, and both positions in pendant benzenes of Qx units, constructing PAs denoted as P(QxCN-T2)-m, P(QxCN-T2)-p, and P(QxCN-T2), respectively. Among them, P(QxCN-T2)-m exhibits the deepest energy levels owing to the enhanced electron-withdrawing effect of meta-positioned alkoxy chains, which is in contrast to P(QxCN-T2)-p where para-positioned alkoxy chains have an electron-donating property. In addition, the meta-positioned alkoxy chains induce good electron-conducting pathways, while the para-positioned ones significantly interrupt crystallization and intermolecular interactions between the conjugated backbones. Thus, when the PAs are applied to all-PSCs, a power conversion efficiency (PCE) of 5.07% is attained in the device using P(QxCN-T2)-m with efficient exciton dissociation and good electron-transporting ability. On the contrary, the P(QxCN-T2)-p-based counterpart has a PCE of only 1.62%. These results demonstrate that introducing alkoxy side chains at a proper location in the Qx-based PAs is crucial for their application to all-PSCs.

Eco-friendly polymer solar cells (eco-PSCs) based on aqueous-soluble conjugated materials have recently received great research attention. In this work, we report the development of an aqueous-processable C70-based fullerene derivative (PC71BO15) for eco-PSCs processed by water/ethanol co-solvents. The desirable aggregation behavior and enhanced light absorption ability of PC71BO15 have enabled the fabrication of PPDT2FBT-A:PC71BO15-based eco-PSCs with power conversion efficiencies (PCEs) of up to 2.51%, which is the highest value reported to date for aqueous-processed PSCs. These PPDT2FBT-A:PC71BO15 eco-PSCs exhibit significantly higher PCEs than those of the reference PPDT2FBT-A:PC61BO15 devices over all device-processable water/ethanol compositions. At the optimal water/ethanol composition (v/v = 15 : 85), the PCE of the PPDT2FBT-A:PC71BO15 eco-PSCs is 73% higher than that of the PC61BO15-based counterparts, as a result of enhanced light absorption. Importantly, the PC71BO15-based eco-PSCs show much higher tolerance in their PCEs to the water/ethanol composition. For example, the PCEs of the PPDT2FBT-A : PC71BO15 eco-PSCs at a 30 : 70 water/ethanol ratio maintain 89% of the optimal performance at a 15 : 85 ratio, whereas the PC61BO15-based devices only maintain 45%. This large difference in terms of water-tolerant behavior is mainly related to the different aggregation behaviors between PC71BO15 and PC61BO15 in blend films, which are carefully investigated using electrical, optical and morphological characterizations. This high water composition-tolerance affords an excellent reproducibility of the PC71BO15-based eco-PSCs with eco/human-friendly aqueous processing under ambient conditions.

A skin-like electronic health care patch is demonstrated with a stretchable organic light-emitting diode display and photodiode., Skin-like health care patches (SHPs) are next-generation health care gadgets that will enable seamless monitoring of biological signals in daily life. Skin-conformable sensors and a stretchable display are critical for the development of standalone SHPs that provide real-time information while alleviating privacy concerns related to wireless data transmission. However, the production of stretchable wearable displays with sufficient pixels to display this information remains challenging. Here, we report a standalone organic SHP that provides real-time heart rate information. The 15-μm-thick SHP comprises a stretchable organic light-emitting diode display and stretchable organic photoplethysmography (PPG) heart rate sensor on all-elastomer substrate and operates stably under 30% strain using a combination of stress relief layers and deformable micro-cracked interconnects that reduce the mechanical stress on the active optoelectronic components. This approach provides a rational strategy for high-resolution stretchable displays, enabling the production of ideal platforms for next-generation wearable health care electronics.

The control of molecular orientation and ordering of liquid crystal (LC) organic semiconductor (OSC) for high-performance and thermally stable organic thin-film transistors is investigated. A liquid crystalline molecule, 2-(4-dodecyl thiophenyl)[1]dibenzothiopheno[6,5-b:6',5'-f]-thieno[3,2-b]thiophene (C12-Th-DBTTT) is synthesized, showing the highly ordered smectic X (SmX) phase, demonstrating molecular reorganization via thermal annealing. The resulting thermally evaporated polycrystalline film and solution-sheared thin film show high charge carrier mobilities of 9.08 and 27.34 cm2 V-1 s-1, respectively. Atomic force microscopy and grazing-incidence X-ray diffraction analyses prove that the random SmA1-like structure (smectic monolayer) is reorganized to the highly ordered SmA2-like structure (smectic bilayer) of C12-Ph-DBTTT at the crystal-SmX transition temperature region. Because of the strong intermolecular interactions between rigid DBTTT cores, the thin film devices of C12-Th-DBTTT show excellent thermal stability up to 300 °C, indicating that LC characterization of conventional OSC materials can obtain high electrical performance as well as superior thermal durability.

This paper reports the distinct roles of Au and Ag nanoparticles (NPs) in organic light-emitting diodes (OLEDs) depending on their sizes. Au and Ag NPs that are 40 and 50 nm in size, respectively, are the most effective for enhancing the performance of green OLEDs. The external quantum efficiencies (EQEs) of green OLEDs doped with Au and Ag NPs (40 and 50 nm, respectively) are improved by 29.5% and 36.1%, respectively, while the power efficiencies (PEs) are enhanced by 47.9% and 37.5%, respectively. Furthermore, combining the Au and Ag NPs produces greater enhancements. The EQE and PE of the codoped OLEDs are improved by 63.9% and 68.8%, respectively, through the synergistic behavior of the different NPs. Finite-difference time-domain simulations confirm that the localized surface-plasmon resonance of the Au NPs near 580 nm improves the radiative recombination rate (krad) of green-light emitters locally (

A novel 56 π-electron fullerene acceptor material, benzocyclobutene-C 60 bisadducts (BCBCBA), was developed via the [2+2] cycloaddition of in-situ generated benzyne with C 60 to raise the lowest unoccupied molecular orbital (LUMO) energy level of the fullerene. This four-membered linkages to C 60 of BCBCBA resulted in the fullerene bisadducts with very addends, thus minimizing the adverse effects of their regioisomers on the intermolecular packing between fullerene bisadducts. In addition, the LUMO level of BCBCBA was as high as −3.70 eV, which is 0.16 eV higher than that of phenyl-C 61 -butyric acid methyl ester (PCBM) (−3.86 eV). This result indicates the significant potential for improving open-circuit voltage ( V OC ) values in polymer solar cells (PSCs). The poly(3-hexylthiophene) (P3HT):BCBCBA based PSCs show V OC of 0.73 and power conversion efficiency (PCE) of 3.51%, which are similar to the P3HT:bis-PCBM based PSCs.

We report a systematic investigation of the correlations between the electron mobility of polymer acceptors and the photovoltaic performances of all-polymer solar cells (all-PSCs) by using a series of naphthalene diimide (NDI)-based polymer acceptors. Polymer acceptors typically have much lower electron mobility than fullerenes, which is one of the main factors in limiting the performance of all-PSCs. In addition, the anisotropic charge transport properties of the polymers require careful control of their packing structure and orientation suitable for their use in all-PSCs. To control the planarity of the polymer backbone and enhance electron mobility, we introduce three different electron-rich units (i.e., thiophene (T), bithiophene (T2), and thienylene–vinylene–thienylene (TVT)) into the NDI-based polymers. Particularly, P(NDI2OD–TVT) polymers exhibit the highest electron mobility (2.31 cm2 V–1 s–1) in organic field-effect transistors owing to various factors including enhanced degree of coplanarity, st...

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.

Interfacial tension between two materials is a key parameter in determining their miscibility and, thus, their morphological behavior in blend films. In bulk heterojunction (BHJ)-type polymer solar cells (PSCs), control of the interfacial tension between the electron donor and the electron acceptor is critically important in order to increase miscibility and achieve optimized BHJ morphology for producing efficient exciton dissociation and charge transport. Herein, we report the synthesis of a series of indene-C60 bis-adducts (ICBA) derivatives by modifying their end-groups with fluorine (FICBA), methoxy (MICBA) and bromine (BICBA) functional units. We systematically studied the effects of their structural changes on the blend morphology with poly(3-hexylthiophene) (P3HT) and their performance in the PSCs. The end-group modification of ICBA derivatives induced a dramatic change in their interfacial tensions with P3HT (i.e., from 4.9 to 8.3mN m−1), resulting in large variations in the power conversion efficiency (PCE) of the PSCs, ranging from 2.9 to 5.2%.

A new series of conjugated random terpolymers (PDPP2T-Se-Th) was synthesized from an electron-deficient diketopyrrolopyrrole (DPP)-based unit in conjugation with two electron-rich selenophene (Se) and thiophene (Th) species, with a view to inducing different crystalline behaviors of the polymers. The crystallinity of the polymers can be systematically controlled by tuning the ratio between Se and Th; an increase in Se content induced a remarkable increase in the melting and crystallization temperatures as well as the crystallinity of the PDPP2T-Se-Th terpolymers. These changes in the crystalline properties of polymers had a dramatic effect on the performances of organic field-effect transistors (OFETs) and polymer solar cells (PSCs). However, their effect on each type of devices was very different. The charge carrier mobilities of the PDPP2T-Se-Th terpolymers in OFET devices increased remarkably as the Se content increased in the polymers, showing that PDPP2T-Se100 with Se/Th ratio = 100/0 had very high h...

A novel framework of azide containing photo-crosslinkable, conducting copolymer, that is, poly(azido-styrene)-random-poly(triphenylamine) (X-PTPA), is reported as a hole-transporting material for efficient solution-processed, multi-layer, organic light emitting diodes (OLEDs). A facile and energy-efficient crosslinking process is demonstrated with UV irradiation (254 nm, 2 mW/cm2) at a short exposure time (5 min). By careful design of X-PTPA, in which 5 mol% of the photo-crosslinkable poly(azido-styrene) is copolymerized with hole-transporting poly(triphenylamine) (X-PTPA-5), the adverse effect of the crosslinking of azide moieties is prevented to maximize the performances of X-PTPA-5. Since the photo-crosslinking chemistry of azide molecules does not involve any photo-initiators, superior hole-transporting ability is achieved, producing efficient devices. To evaluate the performances of X-PTPA-5 as a hole-transporting/electron-blocking layer, Ir(ppy)3-based, solution-processable OLEDs are fabricated. The results show high EQE (11.8%), luminous efficiency (43.7 cd/A), and power efficiency (10.4 lm/W), which represent about twofold enhancement over the control device without X-PTPA-5 film. Furthermore, micro-patterned OLEDs with the photo-crosslinkable X-PTPA-5 can be fabricated through standard photolithography. The versatility of this approach is also demonstrated by introducing the same azide moiety into other hole-transporting materials such as poly(carbazole) (X-PBC).

While most high-efficiency polymer solar cells (PSCs) are made of bulk heterojunction (BHJ) blends of conjugated polymers and fullerene derivatives, they have a significant morphological instability issue against mechanical and thermal stress. Herein, we developed an architecturally engineered compatibilizer, poly(3-hexylthiophene)-graft-poly(2-vinylpyridine) (P3HT-g-P2VP), that effectively modifies the sharp interface of a BHJ layer composed of a P3HT donor and various fullerene acceptors, resulting in a dramatic enhancement of mechanical and thermal stabilities. We directly measured the mechanical properties of active layer thin films without a supporting substrate by floating a thin film on water, and the enhancement of mechanical stability without loss of the electronic functions of PSCs was successfully demonstrated. Supramolecular interactions between the P2VP of the P3HT-g-P2VP polymers and the fullerenes generated their universal use as compatibilizers regardless of the type of fullerene acceptors, including mono- and bis-adduct fullerenes, while maintaining their high device efficiency. Most importantly, the P3HT-g-P2VP copolymer had better compatibilizing efficiency than linear type P3HT-b-P2VP with much enhanced mechanical and thermal stabilities. The graft architecture promotes preferential segregation at the interface, resulting in broader interfacial width and lower interfacial tension as supported by molecular dynamics simulations.

A new series of donor–acceptor (D–A) conjugated random terpolymers (PBDTT–DPP–TPD) were synthesized from electron-rich thienyl-substituted benzo[1,2-b:4,5-b′]dithiophene (BDTT), in conjugation with two electron-deficient units, pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) and thieno[3,4-c]pyrrole-4,6-dione (TPD), of different electron-withdrawing strengths. The optical properties of these random terpolymers can be easily controlled by tuning the ratio between DPP and TPD; an increase in TPD induced increased absorption between 400 and 650 nm and a lower highest occupied molecular orbital energy level, while higher DPP contents resulted in stronger absorption between 600 and 900 nm. The best power conversion efficiency (PCE) of 6.33% was obtained from PBDTT–DPP75–TPD25 with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) due to the improved light absorption and thus a short-circuit current density (JSC) higher than 16 mA/cm2. Interestingly, the trend observed in the PCE values differed from that of optical be...

Two semiconducting conjugated polymers were synthesized via Stille polymerization. The structures combined unsubstituted or (triisopropylsilyl)ethynyl (TIPS)-substituted 2,6-bis(trimethylstannyl)benzo[1,2-b:4.5-b']dithiophene (BDT) as a donor unit and benzotriazole with a symmetrically branched alkyl side chain (DTBTz) as an acceptor unit. We investigated the effects of the different BDT moieties on the optical, electrochemical, and photovoltaic properties of the polymers and the film crystallinities and carrier mobilities. The optical-band-gap energies were measured to be 1.97 and 1.95 eV for PBDT-DTBTz and PTIPSBDT-DTBTz, respectively. Bulk heterojunction photovoltaic devices were fabricated and power conversion efficiencies of 5.5% and 2.9% were found for the PTIPSBDT-DTBTz- and PBDT-DTBTz-based devices, respectively. This difference was explained by the more optimal morphology and higher carrier mobility in the PTIPSBDT-DTBTz-based devices. This work demonstrates that, under the appropriate processing conditions, TIPS groups can change the molecular ordering and lower the highest occupied molecular orbital level, providing the potential for improved solar cell performance.

Fullerene tris-adducts have the potential of achieving high open-circuit voltages (V(OC)) in bulk heterojunction (BHJ) polymer solar cells (PSCs), because their lowest unoccupied molecular orbital (LUMO) level is higher than those of fullerene mono- and bis-adducts. However, no successful examples of the use of fullerene tris-adducts as electron acceptors have been reported. Herein, we developed a ternary-blend approach for the use of fullerene tris-adducts to fully exploit the merit of their high LUMO level. The compound o-xylenyl C60 tris-adduct (OXCTA) was used as a ternary acceptor in the model system of poly(3-hexylthiophene) (P3HT) as the electron donor and the two soluble fullerene acceptors of OXCTA and fullerene monoadduct (o-xylenyl C60 monoadduct (OXCMA), phenyl C61-butyric acid methyl ester (PCBM), or indene-C60 monoadduct (ICMA)). To explore the effect of OXCTA in ternary-blend PSC devices, the photovoltaic behavior of the device was investigated in terms of the weight fraction of OXCTA (W(OXCTA)). When W(OXCTA) is small (0.3), OXCTA can generate a synergistic bridging effect between P3HT and the fullerene monoadduct, leading to simultaneous enhancement in both V(OC) and short-circuit current (J(SC)). For example, the ternary PSC devices of P3HT:(OXCMA:OXCTA) with W(OXCTA) of 0.1 and 0.3 exhibited power-conversion efficiencies (PCEs) of 3.91% and 3.96%, respectively, which were significantly higher than the 3.61% provided by the P3HT:OXCMA device. Interestingly, for W(OXCTA)0.7, both V(OC) and PCE of the ternary-blend PSCs exhibited nonlinear compositional dependence on W(OXCTA). We noted that the nonlinear compositional trend of P3HT:(OXCMA:OXCTA) was significantly different from that of P3HT:(OXCMA:o-xylenyl C60 bis-adduct (OXCBA)) ternary-blend PSC devices. The fundamental reasons for the differences between the photovoltaic trends of the two different ternary-blend systems were investigated systemically by comparing their optical, electrical, and morphological properties.

Polymer solar cells (PSCs) consisting of fullerene bis-adduct and poly(3-hexylthiophene) (P3HT) blends have shown higher efficiencies than P3HT:phenyl C(61)-butyric acid methyl ester (PCBM) devices, because of the high-lying lowest unoccupied molecular orbital (LUMO) level of the fullerene bis-adducts. In contrast, the use of fullerene bis-adducts in donor-acceptor (DA) copolymer systems typically causes a decrease in the device's performance due to the decreased short-circuit current (J(SC)) and the fill factor (FF). However, the reason for such poor performance in DA copolymer:fullerene bis-adduct blends is not fully understood. In this work, bulk-heterojunction (BHJ)-type PSCs composed of three different electron donors with four different electron acceptors were chosen and compared. The three electron donors were (1) poly[(4,8-bis-(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(5-octylthieno[3,4-c]pyrrole-4,6-dione)-1,3-diyl] (PBDTTPD), (2) poly[(4,8-bis-(2-ethylhexyloxy)benzo[1,2-b:4,5-b']dithiophene)-2,6-diyl-alt-(4-(2-ethylhexanoyl)-thieno[3,4-b]thiophene)-2,6-diyl] (PBDTTT-C), and (3) P3HT polymers. The four electron acceptors were (1) PCBM, (2) indene-C(60) monoadduct (ICMA), (3) indene-C(60) bis-adduct (ICBA), and (4) indene-C(60) tris-adduct (ICTA). To understand the difference in the performance of BHJ-type PSCs for the three different polymers in terms of the choice of fullerene acceptor, the structural, optical, and electrical properties of the blends were measured by the external quantum efficiency (EQE), photoluminescence, grazing incidence X-ray scattering, and transient absorption spectroscopy. We observed that while the molecular packing and optical properties cannot be the main reasons for the dramatic decrease in the PCE of the DA copolymers and ICBA, the value of the driving force for charge transfer (ΔG(CT)) is a key parameter for determining the change in J(SC) and device efficiency in the DA copolymer- and P3HT-based PSCs in terms of fullerene acceptor. The low EQE and J(SC) in PBDTTPD and PBDTTT-C blended with ICBA and ICTA were attributed to an insufficient ΔG(CT) due to the higher LUMO levels of the fullerene multiadducts. Quantitative information on the efficiency of the charge transfer was obtained by comparing the polaron yield, lifetime, and exciton dissociation probability in the DA copolymer:fullerene acceptor films.

Systematic control of the chemical structure of conjugated polymers is critically important to elucidate the relationship between the conjugated polymer structures and properties and to optimize their performance in bulk heterojunction (BHJ) polymer solar cell (PSC) devices. Herein, we synthesized three new copolymers, i.e., P0, P1, and P2; these copolymers contain the same benzodithiophene donor unit but have different acceptor units with different numbers of nitrogen atoms in the range of 0–2. The effects of the introduced nitrogen atoms on the structural, optical, electrical, and photovoltaic properties of the conjugated polymers were investigated; the structural properties of the polymers, in particular, were studied using both experimental (grazing-incidence X-ray scattering (GIXS) measurements) and computational methods (molecular simulation). As the number of introduced nitrogen atoms increased, the planarity of the main chain conformation increased in the order of P0 < P1 < P2. Additionally, the P...

Structural control of solubilizing side groups in fullerene-based electron acceptors is critically important to optimize their performance in bulk heterojunction (BHJ)-type polymer solar cell (PSC) devices. The structural changes of fullerene derivatives affect not only their optical and electrochemical properties but also their solubility and miscibility with electron donor polymers. Herein, we synthesized a series of o-xylenyl C60 bis-adduct (OXCBA) derivatives with different solubilizing side groups to systematically investigate the effects of fullerene derivative structures on the photovoltaic properties of PSCs. The xylenyl side groups on the OXCBA were modified to produce several different OXCBA derivatives in which the xylenyl groups were functionalized with fluorine (FXCBA), nitro (NXCBA), methoxy and bromine (BMXCBA), and phenyl groups (ACBA). End group modifications of OXCBA dramatically affect photovoltaic performance in blend films with poly(3-hexylthiophene) (P3HT), resulting in power convers...

The ability to tune the lowest unoccupied molecular orbital (LUMO)/highest occupied molecular orbital (HOMO) levels of fullerene derivatives used as electron acceptors is crucial in controlling the optical/electrochemical properties of these materials and the open circuit voltage (V(oc)) of solar cells. Here, we report a series of indene fullerene multiadducts (ICMA, ICBA, and ICTA) in which different numbers of indene solubilizing groups are attached to the fullerene molecule. The addition of indene units to fullerene raised its LUMO and HOMO levels, resulting in higher V(oc) values in the photovoltaic device. Bulk-heterojunction (BHJ) solar cells fabricated from poly(3-hexylthiophene) (P3HT) and a series of fullerene multiadducts-ICMA, ICBA, and ICTA showed V(oc) values of 0.65, 0.83, and 0.92 V, respectively. Despite demonstrating the highest V(oc) value, the P3HT:ICTA device exhibited lower efficiency (1.56%) than the P3HT:ICBA device (5.26%) because of its lower fill factor and current. This result could be explained by the lower light absorption and electron mobility of the P3HT:ICTA device, suggesting that there is an optimal number of the solubilizing group that can be added to the fullerene molecule. The effects of the addition of solubilizing groups on the optoelectrical properties of fullerene derivatives were carefully investigated to elucidate the molecular structure-device function relationship.

Conjugated polymers, in general, are unstable when exposed to air, solvent, or thermal treatment, and these challenges limit their practical applications. Therefore, it is of great importance to develop new materials or methodologies that can enable organic electronics with air stability, solvent resistance, and thermal stability. Herein, we have developed a simple but powerful approach to achieve solvent-resistant and thermally stable organic electronic devices with a remarkably improved air stability, by introducing an azide cross-linkable group into a conjugated polymer. To demonstrate this concept, we have synthesized polythiophene with azide groups attached to end of the alkyl chain (P3HT-azide). Photo-cross-linking of P3HT-azide copolymers dramatically improves the solvent resistance of the active layer without disrupting the molecular ordering and charge transport. This is the first demonstration of solvent-resistant organic transistors. Furthermore, the bulk-heterojunction organic photovoltaics (B...

The ability to control the lowest unoccupied molecular orbital (LUMO) level of an electron-accepting material is a critical parameter for producing highly efficient polymer solar cells (PSCs). Soluble bis-adducts of C60 have great potential for improving the VOC in PSCs because of their high LUMO level. In this work, we have developed a novel o-xylenyl C60 bis-adduct (OXCBA) via a [4 + 2] cycloaddition between C60 and an irreversible diene intermediate from α,α′-dibromo-o-xylene. OXCBA was successfully applied as the electron acceptor with poly(3-hexylthiophene) (P3HT) in a PSC, showing a high efficiency of 5.31% with VOC of 0.83 V. This composite showed a nearly 50% enhancement in efficiency compared to the P3HT:PCBM control device (3.68% with VOC of 0.59 V). Furthermore, tuning the molar ratio between C60 and the α,α′-dibromo-o-xylene group from 1:1 to 1:3 in the reaction scheme enables facile control over the number of o-xylenyl solubilizing groups ultimately tethered to the fullerene, thus producing o...

A new series of polysilafluorene-type low-bandgap polymers containing 3,6-dialkyloxy-9,9-dialkylsilafluorene and 4,7-di-2-thienyl-2,1,3-benzothiadiazole units has been synthesized. UV/vis absorption spectroscopy and grazing incident X-ray diffraction results showed that the alkoxy moiety on the silafluorene unit broadens the absorption band of the polymers because of its electron-donating property, enabling more efficient harvesting of photons from the solar spectrum. Furthermore, the silicon atoms of the polymers lead to a highly ordered structure, which is essential for high charge-carrier mobility. In addition, high molecular weight polymers can be prepared by using long octyloxy/hexyl solubilizing groups. The blend of new poly[2,7-(3,6-dioctyloxy-9,9-dihexylsilafluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (P4H) and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) exhibited a power-conversion efficiency of 4.05% with an open-circuit voltage of 0.67 V, a short-circuit current den...

We have investigated the effects of a directly nanopatterned active layer on the electrical and optical properties of inverted polymer solar cells (i-PSCs). The capillary force in confined molds plays a critical role in polymer crystallization and phase separation of the film. The nanoimprinting process induced improved crystallization and multidimensional chain alignment of polymers for more effective charge transfer and a fine phase-separation between polymers and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) to favor exciton dissociation and increase the generation rate of charge transfer excitons. Consequently, the power conversion efficiency with a periodic nanostructure was enhanced from 7.40% to 8.50% and 7.17% to 9.15% in PTB7 and PTB7-Th based i-PSCs, respectively.

All-polymer solar cells have shown great potential as flexible and portable power generators. These devices should offer good mechanical endurance with high power-conversion efficiency for viability in commercial applications. In this work, we develop highly efficient and mechanically robust all-polymer solar cells that are based on the PBDTTTPD polymer donor and the P(NDI2HD-T) polymer acceptor. These systems exhibit high power-conversion efficiency of 6.64%. Also, the proposed all-polymer solar cells have even better performance than the control polymer-fullerene devices with phenyl-C61-butyric acid methyl ester (PCBM) as the electron acceptor (6.12%). More importantly, our all-polymer solar cells exhibit dramatically enhanced strength and flexibility compared with polymer/PCBM devices, with 60- and 470-fold improvements in elongation at break and toughness, respectively. The superior mechanical properties of all-polymer solar cells afford greater tolerance to severe deformations than conventional polymer-fullerene solar cells, making them much better candidates for applications in flexible and portable devices., All-polymer solar cells have advantages over fullerene-based solar cells due to improved stability and tunable chemical and electronic properties. Here, Kim et al. develop highly efficient and robust solar cells based on PBDTTTPD and P(NDI2HD-T), highlighting their potential in flexible and portable electronics.

The effectiveness of side-chain engineering is demonstrated to produce highly efficient all-polymer solar cells (efficiency of 5.96%) using a series of naphthalene diimide-based polymer acceptors with controlled side chains. The dramatic changes in the polymer packing, blend morphology, and electron mobility of all-polymer solar cells elucidate clear trends in the photovoltaic performances.

A series of aryl-substituted fullerene derivatives were prepared in which the aromatic moiety of [6,6]-phenyl C61-butyric acid methyl ester (PC61BM) was modified by replacing the monocyclic phenyl ring with bicyclic naphthalene (NC61BM), tricyclic anthracene (AC61BM), and tetracyclic pyrene (PyC61BM). The PC61BM derivatives were synthesized from C60 using tosylhydrazone and were tested as electron acceptors in poly(3-hexylthiophene) (P3HT)-based organic photovoltaic cells (OPVs). The lowest unoccupied molecular orbital (LUMO) energy level of NC61BM (-3.68 eV) was found to be slightly higher than those of PC61BM (-3.70 eV), AC61BM (-3.75 eV), and PyC61BM (-3.72 eV). The electron mobility values obtained for the P3HT:PC61BM, P3HT:NC61BM, P3HT:AC61BM, and P3HT:PyC61BM blend films were 2.39 × 10(-4), 2.27 × 10(-4), 1.75 × 10(-4), and 2.13 × 10(-4) cm(2) V(-1) s(-1), respectively. P3HT-based bulk-heterojunction (BHJ) solar cells were fabricated using NC61BM, AC61BM, and PyC61BM as electron acceptors, and their performances were compared with that of the device fabricated using PC61BM. The highest power conversion efficiencies (PCEs) observed for devices fabricated with PC61BM, NC61BM, AC61BM, and PyC61BM were 3.80, 4.09, 1.14, and 1.95%, respectively, suggesting NC61BM as a promising electron acceptor for OPVs.

In this paper, we report and discuss our successful synthesis of monodispersed, polystyrene-coated gold core-shell nanoparticles (Au@PS NPs) for use in highly efficient, air-stable, organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs). These core-shell NPs retain the dual functions of (1) the plasmonic effect of the Au core and (2) the stability and solvent resistance of the cross-linked PS shell. The monodispersed Au@PS NPs were incorporated into a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film that was located between the ITO substrate and the emitting layer (or active layer) in the devices. The incorporation of the Au@PS NPs provided remarkable improvements in the performances of both OLEDs and OPVs, which benefitted from the plasmonic effect of the Au@PS NPs. The OLED device with the Au@PS NPs achieved an enhancement of the current efficiency that was 42% greater than that of the control device. In addition, the power conversion efficiency was increased from 7.6% to 8.4% in PTB7:PC71BM-based OPVs when the Au@PS NPs were embedded. Direct evidence of the plasmonic effect on optical enhancement of the device was provided by near-field scanning optical microscopy measurements. More importantly, the Au@PS NPs induced a remarkable and simultaneous improvement in the stabilities of the OLED and OPV devices by reducing the acidic and hygroscopic properties of the PEDOT:PSS layer.

The randomly nanotextured back electrode provides a simple and efficient route for enhancing photocurrent in polymer solar cells (PSCs) by light trapping, which can increase light absorption within a finite thickness of the active layer. In this study, we incorporated mono-disperse 60 nm polystyrene nanoparticles (PS NPs) into a 50 nm thick poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) anode buffer layer (ABL) to create a randomly nanotextured back electrode with 10 nm height variations in inverted-type PSCs. The roughened interface between the PS NP-PEDOT:PSS ABL and the Ag electrode scatters light in the visible range, leading to efficient light trapping within the device and enhanced light absorption in the active layer. Inverted PSCs with randomly nanotextured electrodes (φ(NP) = 0.31) showed short-circuit current density (J(SC)) and power conversion efficiency (PCE) values that were 15% higher than those of control devices with flat electrodes. External quantum efficiency, reflectance, and optical light scattering as a function of ϕ(NP) were examined to determine the origin of the enhancement in J(SC) and PCE.

Nanometer-sized monodisperse polystyrene nanospheres (PS NS) were designed as an opal template for the formation of three-dimensionally continuous poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films. The resultant films were successfully applied as the anode buffer layer (ABL) to produce highly efficient polymer solar cells (PSCs) with enhanced stability. The conductivity of the PS NS-PEDOT:PSS films was maintained up to ø(PS) = 0.75-0.80, indicating that the formation of continuous PEDOT:PSS films using PS NS templates was successful. To demonstrate the applicability of the PS NS-PEDOT:PSS film for organic electronics, the PS NS-PEDOT:PSS films were used as ABLs in two different PSCs: P3HT:PCBM and P3HT:OXCBA. The photovoltaic performances of both PSCs were maintained up to ø(PS) = 0.8. In particular, the power conversion efficiency of the P3HT:OXCBA PSC with a PS NS-PEDOT:PSS ABL (ø(PS) = 0.8) was greater than 5% and the air stability of the device was significantly enhanced.

An elastomeric poly(dimethylsiloxane) (PDMS) block engraved with periodically arrayed nanopillars serves as a transferable light-trapping stamp for encapsulated organic thin-film solar cells. Diffracted light rays from the stamp interfere with one another and self-focus onto the active layer of the solar cell, generating enhanced absorption, as indicated in the current density-voltage measurements.

We demonstrate that TiO(x) nanocomposite films fabricated using electrostatic layer-by-layer (LbL) assembly improve the power conversion efficiency of photovoltaic cells compared to conventional TiO(x) films fabricated via the sol-gel process. For this study, titanium precursor/poly(allylamine hydrochloride) (PAH) multilayer films were first deposited onto indium tin oxide-coated glass to produce TiO(x) nanocomposites (TiO(x)NC). The specific effect of the LbL processed TiO(x) on photovoltaic performance was investigated using the planar bilayer TiO(x)NC and highly regioregular poly(3-hexylthiophene) (P3HT) solar cells, and the P3HT/LbL TiO(x)NC solar cells showed a dramatic increase in power efficiency, particularly in terms of the short current density and fill factor. The improved efficiency of this device is mainly due to the difference in the chemical composition of the LbL TiO(x)NC films, including the much higher Ti(3+)/Ti(4+) ratio and the highly reactive facets of crystals as demonstrated by XPS and XRD measurement, thus enhancing the electron transfer between electron donors and acceptors. In addition, the grazing incidence wide-angle X-ray scattering (GIWAXS) study revealed the presence of more highly oriented P3HT stacks parallel to the substrate on the LbL TiO(x)NC film compared to those on the sol-gel TiO(x) films, possibly influencing the hole mobility of P3HT and the energy transfer near and at the interface between the P3HT and TiO(x) layers. The results of this study demonstrate that this approach is a promising one for the design of hybrid solar cells with improved efficiency.

Intermolecular interactions have a critical role in determining the molecular packing and orientation of conjugated polymers and organic molecules, leading to significant changes in their electrical and optical properties. Herein, we investigated the effects of intermolecular interactions of electron-donating small molecules on their structural, optical, and electrical properties, as well as on their performance in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). A series of dithienosilole-based small molecule donors were synthesized by introducing different terminal groups of ester and amide groups combined with three different versions of alkyl side chains. In comparison to dithienosilole-based small molecules with ester terminal groups, those with amide terminal groups exhibit strong intermolecular interaction by hydrogen bonding in a non-destructive manner. In addition, in order to control the intermolecular distance during assembly and thus fine-tune the interaction between the small molecule donors, three different alkyl side chains (i.e., n-octyl, n-decyl, and 2-ethylhexyl chains) were introduced into both small molecules with amide and ester terminal groups. The molecular packing and orientation of the small molecule donors were dramatically changed upon modifying the terminal groups and the alkyl side chains, as evidenced by grazing incidence X-ray scattering (GIXS) measurements. This feature significantly affected the electrical properties of the small molecules in OFETs. The trends in the activation energies for charge transport and the hole mobilities in OFETs were consistent with the molecular ordering and orientation propensity. In addition, the nano-scale morphology of small molecules blended with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was also influenced by the intermolecular interaction of small molecule donors. Power conversion efficiencies of more than 4.3% in OPVs were obtained from dithienosilole-based small molecules with ester terminal groups and linear side chains due to the optimized intermolecular interaction and morphology of the active layer.