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This study focuses on the fabrication of nanocomposite thermoelectric devices by blending either a naphthalene-diimide (NDI)-based conjugated polymer (NDI-T1 or NDI-T2), or an isoindigo (IID)-based conjugated polymer (IID-T2), with single-walled carbon nanotubes (SWCNTs). This is followed by sequential process doping method with the small molecule 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) to provide the nanocomposite with n-type thermoelectric properties. Experiments in which the concentrations of the N-DMBI dopant are varied demonstrate the successful conversion of all three polymer/SWCNT nanocomposites from p-type to n-type behavior. Comprehensive spectroscopic, microstructural, and morphological analyses of the pristine polymers and the various N-DMBI-doped polymer/SWCNT nanocomposites are performed in order to gain insights into the effects of various interactions between the polymers and SWCNTs on the doping outcomes. Among the obtained nanocomposites, the NDI-T1/SWCNT exhibits the highest n-type Seebeck coefficient and power factor of -57.7 µV K-1 and 240.6 µW m-1 K-2 , respectively. However, because the undoped NDI-T2/SWCNT exhibits a slightly higher p-type performance, an integral p-n thermoelectric generator is fabricated using the doped and undoped NDI-T2/SWCNT nanocomposite. This device is shown to provide an output power of 27.2 nW at a temperature difference of 20 K.
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Stretchable conjugated polymers with conjugation break spacers (CBSs) synthesized via random terpolymerization have gained considerable attention because of their efficacy in modulating mobility and stretchability. This study incorporates a series of dianhydrohexitol diastereomers of isosorbide (ISB) and isomannide (IMN) units into the diketopyrrolopyrrole-based backbone as CBSs. It is found that the distorted CBS (IMN) improves the mobility-stretchability properties of the polymer with a highly coplanar backbone, whereas the extended CBS (ISB) enhances those of the polymer with a noncoplanar backbone. Additionally, the different configurations of ISB and IMN sufficiently affect the solid-state packing, aggregation capabilities, crystallographic parameters, and mobility-stretchability properties of the polymer. The IMN-based polymers exhibit the highest mobility of 1.69 cm2 V-1 s-1 and crystallinity retentions of (85.7, 78.6)% under 20% and 60% strains, outperforming their ISB-based or unmodified counterparts. The improvement is correlated with a robust aggregation capability. Furthermore, the CBS content affects aggregation behavior, notably affecting mobility. This result indicates that incorporating CBSs into the polymer can enhance backbone flexibility via movement and rotation of the CBS without affecting the crystalline regions.
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Polímeros , Pirróis , Polímeros/química , Polímeros/síntese química , Pirróis/química , Estereoisomerismo , Estrutura Molecular , Polimerização , Cetonas/químicaRESUMO
Conjugated polymers are of great interest owing to their potential in stretchable electronics to function under complex deformation conditions. To improve the performance of conjugated polymers, various structural designs have been proposed and these conjugated polymers are specially applied in exotic optoelectronics. In this work, a series of all-conjugated block copolymers (PII2T-b-PNDI2T) comprising poly(isoindigo-bithiophene) (PII2T) and poly(naphthalenediimide-bithiophene) (PNDI2T) are developed with varied compositions and applied to electret-free phototransistor memory. Accordingly, these memory devices present p-type transport capability and electrical-ON/photo-OFF memory behavior. The efficacy of the all-conjugated block copolymer design in improving the memory-photoresponse properties in phototransistor memory is revealed. By optimizing the composition of the block copolymer, the corresponding device achieves a wide memory window of 36 V and a high memory ratio of 7 × 104 . Collectively, the results of this study indicate a new concept for designing electret-free phototransistor memory by using all-conjugated block copolymer heterojunctions to mitigate the phase separation of conjugated polymer blends. Meanwhile, the intrinsic optoelectronic properties of the constituent conjugated polymers can be well-maintained by using an all-conjugated block copolymer design.
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Eletricidade , Eletrônica , Polímeros/químicaRESUMO
Chain-end-functionalized poly(3-hexylthiophene)s (P3HTs) with benzyl alcohol (âPhCH2 OH), phenol (âPhOH), and benzoic acid (âPhCOOH) groups are directly synthesized based on the Negishi catalyst-transfer polycondensation method utilizing the zincate complex of t Bu4 ZnLi2 . In this system, neither protection nor deprotection steps are required, and also providing a living polymerization system to control the molecular weight while maintaining a low molar mass dispersity (ÐM ) of the obtained P3HT derivatives. Indeed, the chain-end-functionalized P3HTs can be synthesized along with controlled number-average molecular weights (Mn = 5100-20 000), low ÐM (1.06-1.14), and high chain-end functionality (Fn = 46-86%). The Fn values for the alcohol and phenol groups are found to be high (86% for âPhCH2 OH and 71% for âPhOH based on 1 H NMR, respectively), as also confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. The easily synthesizable chain-end-functionalized P3HTs will be applicable for the facile synthesis of block and branched polymers containing P3HT as well as its related semiconducting polymer segments.
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Compostos Organometálicos/química , Tiofenos/síntese química , Zinco/química , Ácido Benzoico/química , Álcool Benzílico/química , Catálise , Estrutura Molecular , Fenóis/química , Polimerização , Tiofenos/químicaRESUMO
Various molecular weight π-conjugated donor-acceptor polymers based on thiadiazole and thiophene units are investigated with respect to nanoscale film morphology and digital memory performance. Interestingly, all polymers reveal excellent n-type digital permanent memory characteristics, which are governed by the combination of Ohmic and trap-limited space charge limited conductions via a hopping process using thiadiazole and thiophene units as charge traps and stepping stones. The digital memory performance is significantly influenced by the film morphology details that vary with the polymer molecular weight as well as the film thickness. A higher population of face-on structure formation, as well as higher molecular weight, provides a wider film thickness window of digital memory operation. Overall, π-conjugated PBTDzTV polymers are suitable for the production of high-performance, programmable n-type permanent memory devices with very low power consumption.
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Nanopartículas/química , Polímeros/química , Tiadiazóis/química , Tiofenos/química , Estrutura Molecular , Peso MolecularRESUMO
An efficient and scalable strategy to prepare libraries of discrete conjugated oligomers (D = 1.0) using the combination of controlled polymerization and automated flash chromatography is reported. From this two-step process, a series of discrete conjugated materials from dimers to tetradecamers could be isolated in high yield with excellent structural control. Facile and scalable access to monodisperse libraries of different conjugated oligomers opens pathways to designer mixtures with precise composition and monomer sequence, allowing exquisite control over their physical, optical, and electronic properties.
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Well-defined poly(2,5-dihexyloxyphenylene-1,4-diyl) (PPP) is successfully synthesized by the Negishi catalyst-transfer polycondensation (NCTP) using dilithium tetra(tert-butyl)zincate (t Bu4 ZnLi2 ). The obtained PPP possesses the number-averaged molecular weight (Mn ) values in the range of 2100-22 000 and the molar-mass dispersity (ÐM ) values in the range of 1.09-1.23. In addition, block copolymers containing PPP and poly(3-hexylthiophene) (P3HT) segments (PPP-b-P3HT) are synthesized to confirm the feasibility of chain extension between the different monomers based on NCTP.
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Polímeros/síntese química , Zinco/química , Catálise , Peso Molecular , Tiofenos/químicaRESUMO
The development of intrinsically stretchable n-type semiconducting polymers has garnered much interest in recent years. In this study, three biobased dianhydrohexitol epimers of isosorbide (ISB), isomannide (IMN), and isoidide (IID), derived from cellulose, were incorporated into the backbone of a naphthalenediimide (NDI)-based n-type semiconducting polymer as conjugation break spacers (CBSs). Accordingly, three polymers were synthesized through the Migita-Kosugi-Stille coupling polymerization with NDI, bithiophene, and CBSs, and the mobility-stretchability properties of these polymers were investigated and compared with those of their analogues with conventional alkyl-based CBSs. Experimental results showed that the different configurations of these epimers in CBSs sufficiently modulate the melt entropies, surface aggregation, crystallographic parameters, chain entanglements, and mobility-stretchability properties. Comparable ductility and edge-on preferred stacking were observed in polymers with endo- or exo-configurations in IMN- and IID-based polymers. By contrast, ISB with endo-/exo-configurations exhibits an excellent chain-realigning capability, a reduced crack density, and a proceeding bimodal orientation under tensile strain. Therefore, the ISB-based polymer exhibits high orthogonal electron mobility retention of (53 and 56)% at 100% strain. This study is one of the few examples where biobased moieties are incorporated into semiconducting polymers as stress-relaxation units. Additionally, this is the first study to report on the effect of stereoisomerism of epimers on the morphology and mobility-stretchability properties of semiconducting polymers.
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The vision-inspired artificial neural network based on optical synapses has drawn a tremendous amount of attention for emulating biological senses. Although photoexcitation-induced synaptic functionalities have been widely studied, optical habituation via the photoinhibitory pathway is yet to be demonstrated for sophisticated biomimetic visual adaptive systems. Here, the first optical neuromorphic block copolymer (BCP) phototransistor is demonstrated as an all-optical operation responding to various wavelengths, fulfilling photoassisted dynamic learning/forgetting cycles via optical potentiation without gate bias. The polyfluorene BCPs were precisely designed to enable wavelength-adaptive responses, benefiting from interfacial semiconductor/electret morphology and the crystallinity/electron affinity of the BCPs. Notably, this is the first work to simultaneously exhibit fully light-controlled short- and long-term memory based on organic material systems. The device presents a high current contrast above 100-fold and long-term retention over 104 s. As a proof-of-concept for neural networks, a 6 × 6 array of photosynapses performed outstanding visual pattern learning/forgetting with high accuracy. This study exploits the design strategy of a conjugated BCP electret to unleash the full potential of wavelength-adaptive visual neuroplasticity transitions. It provides an effective architecture for designing high-performance and high-storage capacity required applications in next-generation neuromorphic systems.
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Semiaromatic polyamides were directly synthesized by bulk polycondensation of aliphatic dicarboxylic acids (with 5, 6, 7, and 10 carbon numbers) and aromatic diamines (4,4'-oxydianiline and 4,4'-diaminodiphenylmethane) under natural pressure. In addition, copolyamides were successfully obtained by the copolymerization of aliphatic dicarboxylic acids, aromatic diamines, and biobased amino acid, 4-aminohydrocinnamic acid. The obtained polyamides had relatively high inherent viscosity values of 0.35-0.76 dL/g. The obtained polyamides exhibited good thermal stability with T d5% in the range of 316-416 °C, even when incorporated with aliphatic methylene units. In particular, some copolyamides (2AO, 2PO, and 2GM) had high T g values of 150, 158, and 156 °C and relatively low T m values of 277, 288, and 234 °C, respectively, which may be preferable thermal properties for melt-drawing processes.
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The development of single-component organic solar cells (SCOSCs) using only one photoactive component with a chemically bonded D/A structure has attracted increasing research attention in recent years. At represent, most relevant studies focus on comparing the performance difference between a donor-acceptor (D-A) conjugated block copolymer (CBC) and the commensurate blending systems based on the same donor and acceptor segments, and still there are no reports on the impact of the segment ratio for a certain D-A CBC on the resultant photovoltaic performance. In this study, we synthesized a D-A all-conjugated polymers based on an n-type PNDI2T block and a p-type PBDB-T donor block but with three different segment ratios (P1-P3) and demonstrate the significance of the D/A segment ratio on photovoltaic performance. Our results reveal that the n-type PNDI2T block plays a more critical role in the inter/intra-chain charge transfer. P1 with a higher content of PNDI2T delivers superior exciton dissociation and charge transfer behavior than P2 and P3, benefitting from its more balanced hole/electron mobility. In addition, a higher packing regularity associated with a more dominant face-on orientation is also observed for P1. As a result, SCOSC based on P1 exhibits the highest PCE among the synthesized CBCs. It also possesses a minimal energy loss due to the better suppressed non-radiative recombination loss. This work provides the first discussion of the impact of the segment ratio for a D-A all-conjugated block copolymer and signifies the critical role of the n-type segment in designing high-performance single-component CBCs.
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Neuromorphic computation possesses the advantages of self-learning, highly parallel computation, and low energy consumption, and is of great promise to overcome the bottleneck of von Neumann computation. In this work, a series of poly(3-hexylthiophene) (P3HT)-based block copolymers (BCPs) with different coil segments, including polystyrene, poly(2-vinylpyridine) (P2VP), poly(2-vinylnaphthalene), and poly(butyl acrylate), are utilized in photosynaptic transistor to emulate paired-pulse facilitation, spike time/rate-dependent plasticity, short/long-term neuroplasticity, and learning-forgetting-relearning processes. P3HT serves as a carrier transport channel and a photogate, while the insulating coils with electrophilic groups are for charge trapping and preservation. Three main factors are unveiled to govern the properties of these P3HT-based BCPs: i) rigidity of the insulating coil, ii) energy levels between the constituent polymers, and iii) electrophilicity of the insulating coil. Accordingly, P3HT-b-P2VP-based photosynaptic transistor with a sought-after BCP combination demonstrates long-term memory behavior with current contrast up to 105 , short-term memory behavior with high paired-pulse facilitation ratio of 1.38, and an ultralow energy consumption of 0.56 fJ at an operating voltage of -0.0003 V. As far as it is known, this is the first work to utilize conjugated BCPs in an electret-free photosynaptic transistor showing great potential to the artificial intelligence technology.
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Regioregular polythiophenes have been widely used in organic electronic applications due to their solution processability with chemical modification through side chain engineering, as well as their microstructural organization and good hole transport properties. Here, we introduce alkylthio side chains, (poly[(3-alkylthio)thiophene]s; P3ATTs), with strong noncovalent sulfur molecular interactions, to main chain thienyl backbones. These P3ATTs were compared with alkyl-substituted polythiophene (poly(3-alkylthiophene); P3AT) variants such that the effects of straight (hexyl and decyl) and branched (2-ethylhexyl) side chains (with and without S atoms) on their thin-film morphologies and crystalline states could be investigated. P3ATTs with linear alkylthio side chains (P3HTT, hexylthio; P3DTT, decylthio) did not attain the expected higher organic field-effect transistor (OFET) mobilities with respect to P3HT (hexyl) and P3DT (decyl) mainly due to their lower regioregularity (76-78%), although P3ATTs exhibit an enhanced tendency for aggregation and compact molecular packing, as indicated by the red-shifting of the absorption spectra and the shortening of the π-π stacking distance, respectively. Moreover, the loss of regioregularity issue can be solved by introducing more soluble 2-ethylhexylthio branched side chains to form poly[3-(2-ethylhexylthio)thiophene] (P3EHTT), which provides enhanced crystallinity and efficient charge mobility (increased by up to a factor of 3) with respect to the poly(2-ethylhexylthiophene) (P3EHT) without S atoms in the side moieties. This study demonstrates that the presence of side chain alkylthio structural motifs with nonbonded interactions in polythiophene semiconductors has a beneficial impact on the molecular conformation, morphologies, structural packing, and charge transport in OFET devices.
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As a key component in stretchable electronics, semiconducting polymers have been widely studied. However, it remains challenging to achieve stretchable semiconducting polymers with high mobility and mechanical reversibility against repeated mechanical stress. Here, we report a simple and universal strategy to realize intrinsically stretchable semiconducting polymers with controlled multi-scale ordering to address this challenge. Specifically, incorporating two types of randomly distributed co-monomer units reduces overall crystallinity and longer-range orders while maintaining short-range ordered aggregates. The resulting polymers maintain high mobility while having much improved stretchability and mechanical reversibility compared with the regular polymer structure with only one type of co-monomer units. Interestingly, the crystalline microstructures are mostly retained even under strain, which may contribute to the improved robustness of our stretchable semiconductors. The proposed molecular design concept is observed to improve the mechanical properties of various p- and n-type conjugated polymers, thus showing the general applicability of our approach. Finally, fully stretchable transistors fabricated with our newly designed stretchable semiconductors exhibit the highest and most stable mobility retention capability under repeated strains of 1,000 cycles. Our general molecular engineering strategy offers a rapid way to develop high mobility stretchable semiconducting polymers.
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A linear polymer, hyperbranched polymers with various degrees of branching, and 100% hyperbranched polymers were successfully synthesized by self-polycondensation of 2,2,2-trifluoro-1-[4-(4-phenoxyphenoxy)phenyl]ethanone by using different amounts of trifluoromethanesulfonic acid from the same AB(2) monomer.
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This paper reviews the precise synthesis of many-armed and multi-compositional star-branched polymers, exact graft (co)polymers, and structurally well-defined dendrimer-like star-branched polymers, which are synthetically difficult, by a commonly-featured iterative methodology combining living anionic polymerization with branched reactions to design branched polymers. The methodology basically involves only two synthetic steps; (a) preparation of a polymeric building block corresponding to each branched polymer and (b) connection of the resulting building unit to another unit. The synthetic steps were repeated in a stepwise fashion several times to successively synthesize a series of well-defined target branched polymers.
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Understanding the relationship between the molecular structure and morphological behaviors of well-defined semiconducting polymers is essential for developing novel conjugated building blocks and determining the origin of the functional characteristics of semiconducting polymers. Here, we provide insights into the significant temperature-dependent morphological transitions of novel well-defined polythiophene derivatives with m-alkoxy-substituted fluoro-aryl side units: poly(3-(4-fluoro-3-(hexyloxy)phenyl)thiophene) (PHFPT) and poly(3-(4-fluoro-3-(dodecyloxy)phenyl)thiophene) (PDFPT). We found that these unique morphological transitions depend on the alkyl chain length of the substituted fluoro-aryl side units. In PHFPT with short alkyl chains, the thermal treatment promotes a crowded interdigitated packing structure, resulting in narrow lamellar spacings in its crystalline structure. In contrast, the long alkyl chain of PDFPT acts as a physical spacer and disturbs the crowded interdigitation. In addition, the thermal treatment induces the backbone planarization and an ordered packing morphology in PDFPT. These demonstrations provide a critical milestone for the phase transitions of semiconducting polymers with conjugated side units.
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High-refractive-index (high-n) polymers with a high optical transparency and low birefringence (Δn) have been desired in progressive optoelectronic devices. However, the trade-off between high-n and low-Δn remains a challenge at present. Here, the development of a novel array of high-n, high-sulfur-containing, highly transparent, colorless poly(phenylene sulfide) (PPS) polymers bearing triazine units in the main chains is reported. Six new triazine monomers T1-T6 with various pendant groups via different linkers (-O- and -NH-) could be prepared for developing PPSs with high-n and low Δn values. These PPSs (P1-P6) were obtained by the polycondensation of T1-T6 with commercial aromatic dithiol, 4,4'-thiobisbenzenethiol, respectively, which showed very high-n values (n av: 1.6902-1.7169 at 633 nm), high optical transparency (T % > 90% @ 400 nm), and low birefringence (Δn = 0.0015-0.0042). All the PPSs displayed high n ∞ values (1.6340-1.6654), providing valuable information for the development of high-n triazine-based PPS materials for application not only in the visible region but also in the near-infrared region.
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The development of a π-conjugated polymer with hydrogen-bonding moieties has aroused great attention because of the improved molecular stacking and the hydrogen-bonding network. In this study, PDPPTVT (diketopyrrolopyrrole-thiophenevinylenethiophene) and PDPPSe (diketopyrrolopyrrole-selenophene) alkylated with a carbosilane (SiC8) side chain and poly(acryl amide) (PAM)-incorporated alkyl side chain were prepared, and their structure-performance and structure-stretchability correlation were evaluated. By incorporating the DPPTVT backbone and 0, 5, 10, or 20% PAM-incorporated alkyl side chain, the µh value could reach 2.0, 0.97, 0.74, and 0.42 cm2 V-1 s-1, respectively (P1 to P4). The polymer with the PDPPSe backbone and 5% PAM-incorporated alkyl side-chain (P5) exhibited the maximum µh value of 0.96 cm2 V-1 s-1. By extending the PAM moiety from the backbone with alkyl spacers, the solid-state packing and edge-on orientation can be properly maintained. Surprisingly, the PAM-incorporated alkyl side-chain can provide a hydrogen-bonding network serving as sacrificial bonding to mechanical deformation. Therefore, the relevant changes in the crystallographic parameters including the crystalline size and the in-plane π-π stacking distance with a 100% external strain were less than 4 and 0.8%, respectively, from P1 to P3. Therefore, P3 achieved an excellent stretchability while maintaining its molecular orientation and charge-transporting performance. Even with 100% external strain, P3 still provided an orthogonal µh over 0.1 cm2 V-1 s-1. Moreover, by substituting the TVT moiety with the Se moiety, the ductility of the backbone can be further increased when the elastic modulus decreases from 0.80 to 0.36 GPa for P2 to P5. The achieved high µh retention is over 20% after 500 stretching-releasing cycles with a 60% external strain perpendicular to the channel direction for the polymer composed of PDPPSe and 5% PAM content. The results manifest that our newly designed DPP with the PAM-incorporated alkyl side chain provides a promising approach to promote the intrinsic stretchability of the π-conjugated polymers.
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Poly(3-hexylthiophene) (P3HT)-segment-based block copolymers have been reported to deliver an effective compatibilizer function in the P3HT:PC61BM bulk-heterojunction (BHJ) system to simultaneously improve performance and stability. However, as limited by the deficient optophysic properties of the P3HT:PC61BM system, the resultant power conversion efficiency (PCE) of compatibilizer-mediated devices is low despite the optimized chemical structures of the P3HT-segment-based block copolymers. To better shed light on such a compatibilizer effect, the compatibilizer function of the P3HT-segment-based block copolymers is herein investigated in the emerging non-fullerene acceptor (NFA)-based BHJ systems. A P3HT analogue, poly[(4,4'-bis(2-butyloctoxycarbonyl-[2,2'-bithiophene]-5,5-diyl)-alt-(2,2'-bithiophene-5,5'-diyl))] (PDCBT), is used as the polymer donor since it shares the same backbone as P3HT to afford good compatibility with the P3HT-segment-based block copolymers and it has been proven to deliver a higher PCE than P3HT in the NFA BHJ systems. The P3HT-segment-based block copolymers (P1-P4) are manifested to offer similar compatibilizer functions for the PDCBT-based NFA BHJ systems, and the importance of their structural design is also revealed. As a result, addition of P4 delivers the largest enhancement in PCE: from 5.30 to 7.11% for the PDCBT:ITIC blend and from 6.21 to 8.04% for the PDCBT:IT-M blend. Moreover, it can also enhance the device's thermal stability, which can maintain 77% of the initial PCE after annealing at 85 °C for 120 h (for the PDCBT:ITIC blend), outperforming the pristine binary device (66% preservation). More importantly, the entire compatibilizer-mediated device exhibits an improved Voc. Such reduced potential loss can be attributed to the improved interfacial compatibility between the photoactive components, the most important function of a compatibilizer.