Conjugated Polymer Chains Research Articles

Dynamics of Hot Exciton Relaxation in Conjugated Polymer Chain

Hot excitons are formed after photoexcitation of conjugated polymer chains. Hot excitons relax and convert into cold excitons with the aid of vibrational modes. In this study, the dynamics of such conversion is studied within the strong coupling regime. It has been found that the magnitudes of electronic coupling integrals for hot exciton relaxation are mostly due to exchange interactions between the interacting units. During relaxation, hot excitons oscillate back and forth between two different sites until they lose their extra energy. The time step for each oscillation has been found as small as 0.3 fs. It has also been found that photoexcited states in conjugated polymer chains do not necessarily localize at their initial location formed. Monte-Carlo simulations show that hot excitons can sustain their coherent motion along the conjugated backbone to some extent before total relaxation.

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Activation Energies of Diffusion for Relaxed Singlet and Triplet Excitons over Conjugated Polymer Chains

Optimizing Spin-Coat Speed for Fabrication of P3HT: PCBM Solar Cells

The effect of spin speed on the orientation of the conjugated polymer chains becomes a matter of concern while fabricating bulk heterojunction devices such as solar cells. The stability and performance strongly depend on the intertwining of the two molecules that form the bulk heterojunctions. In the case of P3HT: PCBM, it is the long chains of P3HT that encompasses the PCBM molecules. This work investigates the fabricating conditions of Poly (3-hexylthiophene) (P3HT) on the glass substrates in terms of spin coating speeds to obtain favourable geometry of P3HT. For this purpose, three different samples were prepared, keeping spin rate as 6850, 8150 and 9700 rpm, respectively. It was observed that at high spin rates, a large centrifugal force acts upon polymer chains, unfolding them into highly oriented structures. These P3HT chains are free from twists, kinks and are not intermingled. The results of the present work advocate fabricating P3HT: PCBM films at spin speeds less than 6850 rpm.

Effects of Soliton Creation on Transient Transport through a Polymer Chain.

By using a nonadiabatic molecular dynamics method combined with the hierarchical equations of motion, we have investigated the nonequilibrium transient transport through a conjugated polymer chain. The polymer chain is described by the Su-Schrieffer-Heeger model, and its two ends are coupled with metal electrodes of different chemical potentials. In order to present the evolutions of the electronic injection and transport in the real-time domain, we have mainly discussed the dynamic relaxation processes of the excited states and transient transport currents. It is found that due to the existence of electron-phonon couplings in the conjugated polymers, creation of solitons not only affects the time of the system achieving the steady state but also leads to periodical oscillations of the steady-state transport currents with time in our simulations. Furthermore, with increasing applied bias voltage, the steady-state transport electronic current increases, which proved that the creation of the solitons can assist the electronic transport. These results have shown that the creation of the excited states is important in understanding the transport properties in organic nanostructures.

Nonadiabatic molecular dynamics under adiabatic representation

<sec>In this paper, we develop a nonadiabatic molecular dynamics method based on Su-Schriffer-Heeger (SSH) Hamiltonian, and this method is widely used to study the photoexcitation dynamics and polaron motion in conjugated polymers. However, in this method, the time-dependent Schrödinger equation has so far been solved in a diabatic representation, also known as site representation. In order to provide a deeper insight into the nonadiabatic molecular dynamics method, we solve the time-dependent Schrödinger equation in an adiabatic representation. The new method can directly provide the important information about the strength of nonadiabatic couplings between different molecular orbitals in the excited-state relaxation process, helping us to predict the electron and energy transfer within or between polymer chains.</sec><sec>Solving the time-dependent Schrödinger equation in an adiabatic representation is much more complicated, it is mainly because we need to calculate the nonadiabatic couplings between different molecular orbitals. In this paper, the detailed formula derivation and actual calculation process of the nonadiabatic molecular dynamics method in an adiabatic representation are given. Using this new method, we simulate three photoexcitation processes in a conjugated polymer chain, HOMO→LUMO, HOMO–1→LUMO+1 and HOMO–2→LUMO+2. We analyze in detail the time evolutions of lattice configuration for these three photoexcitation processes, and compare these results with those obtained by diabatic representation (site representation) showing that the results obtained from these two representations are consistent with each other.</sec>

Effect of solvent quality and sidechain architecture on conjugated polymer chain conformation in solution.

Conjugated polymers (CPs) are solution-processible for various electronic applications, where solution aggregation and dynamics could impact the morphology in the solid state. Various solvents and solvent mixtures have been used to dissolve and process CPs, but few studies have quantified the effect of solvent quality on the solution behavior of CPs. Herein, we performed static light scattering and small-angle X-ray scattering combined with molecular dynamics (MD) simulation to investigate CP solution behaviors with solvents of varying quality, including poly(3-alkylthiophene) (P3ATs) with various sidechain lengths from -C4H9 to -C12H25, poly[bis(3-dodecyl-2-thienyl)-2,2'-dithiophene-5,5'-diyl] (PQT-12) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-12). We found that chlorobenzene is a better solvent than toluene for various CPs, which was evident from the positive second virial coefficient A2 ranging from 0.3 to 4.7 × 10-3 cm3 mol g-2 towards P3ATs. For P3ATs in non-polar solvents, longer sidechains promote more positive A2, indicating a better polymer-solvent interaction, wherein A2 for toluene increases from -5.9 to 1.4 × 10-3 cm3 mol g-2, and in CB, A2 ranges from 1.0 to 4.7 × 10-3 cm3 mol g-2 when sidechain length increases from -C6H13 to -C12H25. Moreover, PQT-12 and PBTTT-12 have strong aggregation tendencies in all solutions, with an apparent positive A2 (∼0.5 × 10-3 cm3 mol g-2) due to multi-chain aggregates and peculiar chain folding. These solvent-dependent aggregation behaviors can be well correlated to spectroscopy measurement results. Our coarse-grained MD simulation results further suggested that CPs with long, dense, and branched sidechains can achieve enhanced polymer-solvent interaction, and thus enable overall better solution dispersion. This work provides quantitative insights into the solution behavior of conjugated polymers that can guide both the design and process of CPs toward next-generation organic electronics.

Stretchable Semiconducting Polymers with Hydrogen-Bonding-Capable Conjugation Breakers: Synthesis and Application in Organic Thin-Film Transistors.

Diketopyrrolopyrrole (DPP)-based conjugated copolymers are important organic semiconductors for applications in high-efficiency organic thin-film transistors (OTFTs). However, the direct application of these polymers with rigid backbones in stretchable devices has limitations. In this study, we designed and synthesized three kinds of DPPBT-based copolymers, DPPBT-A1, DPPBT-A3, and DPPBT-A5, which have amide-coupled alkylene conjugation breakers capable of hydrogen bonding. Linkers with different segment lengths were copolymerized with DPP and bithiophene (BT) backbone units. A DPP-based copolymer with alternating BT moieties, DPPBT, was synthesized as a reference fully conjugated copolymer. The synthesized polymers with freely rotational backbone linkers have sufficient flexibility to develop ordered phase domains, even in thin films, in comparison to the reference copolymer. However, the introduction of the conjugation breakers, which disconnect the intramolecular π-π overlapping, tends to decrease the hole mobility (μ) from 0.76 to 0.20 cm2 V-1 s-1 in the corresponding OTFT devices. The TFT fabricated using DPPBT-A3 showed a mobility of 0.50 cm2 V-1 s-1, and the mobility value did not show a significant change even when elongated by more than 50%. Therefore, the molecular design strategy of introducing amide-coupled alkylene conjugation breakers into conjugated polymer chains can contribute significantly to the development of high-mobility stretchable conjugated polymers in future.

Stochastic Electrical Detection of Single Ion-Gated Semiconducting Polymers.

Semiconducting polymer chains constitute the building blocks for a wide range of electronic materials and devices. However, most of their electrical characteristics at the single-molecule level have received little attention. Elucidating these properties can help understanding performance limits and enable new applications. Here, coupled ionic-electronic charge transport is exploited to measure the quasi-1D electrical current through long single conjugated polymer chains as they form transient contacts with electrodes separated by ≈10nm. Fluctuations between internal conformations of the individual polymers are resolved as abrupt, multilevel switches in the electrical current. This behavior is consistent with the theoretical simulations based on the worm-like-chain (WLC) model for semiflexible polymers. In addition to probing the intrinsic properties of single semiconducting polymer chains, the results provide an unprecedented window into the dynamics of random-coil polymers and enable the use of semiconducting polymers as electrical labels for single-molecule (bio)sensing assays.

Triggering the Donor-Acceptor Phase Segregation with Solid Additives Enables 16.5% Efficiency in All-Polymer Solar Cells.

All-polymer solar cells have attracted considerable research interest due to their superior morphological stabilities, stretchability, and mechanical durability. However, the morphology optimization of the all-polymer bulk heterojunctions remains challenging due to the two long conjugated polymer chains, limiting its power conversion efficiency. Herein, we focus on the donor-acceptor phase segregation of an all-polymer active layer composed of PM6/PY-IT, a state-of-the-art all-polymer combination, by the introduction of volatile solid additives. Especially with 1,3-dibromo-5-chlorobenzene (DBCl) as the processing additive, we could effectively tune the miscibility between PM6 and PY-IT and thus optimize the phase segregation of the polymer donor and acceptor. Due to the synergetic effects on the favorable phase segregation and desired donor-acceptor distribution, the DBCl-treated devices feature the evident improvement of charge transport and collection, accompanied by the suppressed trap-assisted charge recombination. We consequently achieved a champion device efficiency of 16.5% (16.4% averaged), which is a 13% improvement compared with the control device without DBCl (14.6%). Our results highlight the importance of altering the miscibility of the polymer donor-acceptor pairs for practical applications of high-performance all-polymer solar cells.

A Quasi-2D Polypyrrole Film with Band-Like Transport Behavior and High Charge-Carrier Mobility.

Quasi-2D (q2D) conjugated polymers (CPs) are polymers that consist of linear CP chains assembled through non-covalent interactions to form a layered structure. In this work, the synthesis of a novel crystalline q2D polypyrrole (q2DPPy) film at the air/H2 SO4 (95%) interface is reported. The unique interfacial environment facilitates chain extension, prevents disorder, and results in a crystalline, layered assembly of protonated quinoidal chains with a fully extended conformation in its crystalline domains. This unique structure features highly delocalized π-electron systems within the extended chains, which is responsible for the low effective mass and narrow electronic bandgap. Thus, the temperature-dependent charge-transport properties of q2DPPy are investigated using the van der Pauw (vdP) method and terahertz time-domain spectroscopy (THz-TDS). The vdP method reveals that the q2DPPy film exhibits a semiconducting behavior with a thermally activated hopping mechanism in long-range transport between the electrodes. Conversely, THz-TDS reveals a band-like transport, indicating intrinsic charge transport up to a record short-range high THz mobility of ≈107.1 cm2 V-1 s-1 .

Molecular Dynamics Simulations for Rationalizing Polymer Bioconjugation Strategies: Challenges, Recent Developments, and Future Opportunities.

The covalent modification of proteins with polymers is a well-established method for improving the pharmacokinetic properties of therapeutically valuable biologics. The conjugated polymer chains of the resulting hybrid represent highly flexible macromolecular structures. As the dynamics of such systems remain rather elusive for established experimental techniques from the field of protein structure elucidation, molecular dynamics simulations have proven as a valuable tool for studying such conjugates at an atomistic level, thereby complementing experimental studies. With a focus on new developments, this review aims to provide researchers from the polymer bioconjugation field with a concise and up to date overview of such approaches. After introducing basic principles of molecular dynamics simulations, as well as methods for and potential pitfalls in modeling bioconjugates, the review illustrates how these computational techniques have contributed to the understanding of bioconjugates and bioconjugation strategies in the recent past and how they may lead to a more rational design of novel bioconjugates in the future.

Helical polymers for dissymmetric circularly polarized light imaging.

Control of the spin angular momentum (SAM) carried in a photon provides a technologically attractive element for next-generation quantum networks and spintronics1-5. However, the weak optical activity and inhomogeneity of thin films from chiral molecular crystals result in high noise and uncertainty in SAM detection. Brittleness of thin molecular crystals represents a further problem for device integration and practical realization of chiroptical quantum devices6-10. Despite considerable successes with highly dissymmetric optical materials based on chiral nanostructures11-13, the problem of integration of nanochiral materials with optical device platforms remains acute14-16. Here we report a simple yet powerful method to fabricate chiroptical flexible layers via supramolecular helical ordering of conjugated polymer chains. Their multiscale chirality and optical activity can be varied across the broad spectral range by chiral templating with volatile enantiomers. After template removal, chromophores remain stacked in one-dimensional helical nanofibrils producing a homogeneous chiroptical layer with drastically enhanced polarization-dependent absorbance, leading to well-resolved detection and visualization of SAM. This study provides a direct path to scalable realization of on-chip detection of the spin degree of freedom of photons necessary for encoded quantum information processing and high-resolution polarization imaging.

Simultaneous Force and Fluorescence Spectroscopy on Single Chains of Polyfluorene: Effect of Intra-Chain Aggregate Coupling

Conjugated polymer chains in compact conformations or in films exhibit spectral features that can be attributed to interactions between individual conjugated segments of the chain, including formation of aggregates or excimers. Here, we use atomic force microscopy (AFM) on single chains of the conjugated polymer polyfluorene (PFO) to control the intersegment interactions by mechanically unfolding the chain. Simultaneously with the force spectroscopy we monitor fluorescence from the single PFO chains using a fluorescence microscope. We found that mechanical stretching of the chain causes disappearance of the green emission band. This observation provides evidence that the green emission originates from an intrachain aggregated state on the self-folded chain, which is decoupled by the stretching. In addition, the stretching upon laser irradiation leads to the appearance of additional features in the force spectra, small force peaks in the initial stages of the unfolding. These features are attributed to a combination of excitonic and van der Waals coupling of a ground-state intrachain aggregate.

Enhanced luminescence sensing performance and increased intrachain order in blended films of P3HT and cellulose nanocrystals

Blended films comprising poly(butyl acrylate) (PBA)-grafted cellulose nanocrystals (CNCs) and poly(3-hexylthiophene) (P3HT), exhibited more intense photoluminescence (PL) and longer PL emission lifetimes compared to pristine P3HT films. Optical absorption and photoluminescence spectra indicated reduced torsional disorder i.e. enhanced backbone planarity in the P3HT@CNC blended composites compared to the bare P3HT. Such molecule-level geometrical modification resulted in both smaller interchain and higher intrachain exciton bandwidth in the blended composites compared to the bare P3HT, because of reduced interchain interactions and enhanced intrachain order. These results indicate a potential switch of the aggregation behavior from dominant H-aggregates to J-aggregates, supported by Raman spectroscopy. The reorganization of micromolecular structure and concomitant macroscopic aggregation of the conjugated polymer chains resulted in a longer conjugation length for the P3HT@CNC blended composites compared to the bare P3HT. Additionally, this nanoscale morphological change produced a reduction in the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap of the blends, evidenced from optical absorption spectra. Classical molecular dynamics simulation studies predicted the probability of enhanced planarity in the polymer backbone following interactions with CNC surfaces. Theoretical results from density functional theory calculations corroborate the experimentally observed reduction of optical bandgap in the blends compared to bare P3HT. The blended composite outperformed the bare P3HT in nitro-group PL sensing tests with a pronounced difference in the reaction kinetics. While the PL quenching dynamics for bare P3HT followed Stern–Volmer kinetics, the P3HT@CNC blended composite exhibited a drastic deviation from the same. This work shows the potential of a functionalized rod-like biopolymer in tuning the optoelectronic properties of a technologically important polymeric organic semiconductor through control of the nanoscale morphology.

Photo‐Patternable Stretchable Semi‐Interpenetrating Polymer Semiconductor Network Using Thiol–Ene Chemistry for Field‐Effect Transistors

AbstractStretchable polymer semiconductors are an essential component for skin‐inspired electronics. However, the lack of scalable patterning capability of stretchable polymer semiconductors limits the development of stretchable electronics. To address this issue, photo‐curable stretchable polymer blends consisting of a high‐mobility donor–acceptor conjugated polymer and an elastic rubber through thiol–ene chemistry are developed. The thiol–ene reaction can selectively cross‐link the rubber with alkene or vinyl groups without damaging the electronic properties of the conjugated polymer. The conjugated polymer chains embedded in the elastic polymer matrix induce a semi‐interpenetrating polymer network (SIPN). The thiol–ene‐cross‐linked network provides great solvent resistance and enhances stretchability for the embedded conjugated polymer. The well‐defined patterned film with a feature size of ≈10 µm can be obtained using UV light at 365 nm through conventional photolithography processes. Furthermore, the SIPN‐based transistors show increased mobilities from 0.61 to 1.18 cm2 V−1 s−1 when applying the strain from 0% to 100%. Moreover, the hole mobility can still maintain at 0.87 cm2 V−1 s−1 after 1000 strain‐and‐release cycles at the strain of 25%. This study sheds light on the molecular design of photo‐curable polymer semiconductors for the mass production of stretchable circuits.

Molecular single crystals induce chain alignment in a semiconducting polymer

The blending of π-conjugated molecules with polymeric semiconductors into a composite system is an effective strategy to promote charge carrier mobility because of the transmission path by the conductive polymers through electrical bridge connection of the small organic molecule crystalline domain. In this work, pentacene single crystal was prepared to induce the conjugated polymer chain alignment of polymeric semiconductor PDPP2T-TT-OD to form the semiconducting composite, which led to enhanced field-effect mobility of the organic thin-film transistor (OTFT) by improving the crystallinity due to nucleation and growth phase separation. Besides, with the addition of anti-solvents, the crystallization of the blend film was further improved, 27 times higher than that of a pure polymer semiconductor–based OTFT. That was because the pentacene nuclei induced polymer crystallization through π-π interactions and the addition of anti-solvent promoted the aggregation of polymer chains in solution, enabling the molecular chains packed more closely in solid films. Therefore, the chain arrangement of polymers induced via small molecular single crystals provides a new idea to improve mobility in composite semiconductor thin films for the construction of novel organic optoelectronic devices.

Balanced Coexistence of Reversible and Irreversible Covalent Bonds in a Conductive Triple Polymeric Network Enables Stretchable Hydrogels with High Toughness and Adhesiveness.

The application of soft hydrogels to stretchable devices has attracted increasing attention in deformable bioelectronics owing to their unique characteristic, "modulus matching between materials and organs". Despite considerable progress, their low toughness, low conductivity, and absence of tissue adhesiveness remain substantial challenges associated with unstable skin-interfacing, where body movements undesirably disturb electrical signal acquisitions. Herein, we report a material design of a highly tough strain-dissipative and skin-adhesive conducting hydrogel fabricated through a facile one-step sol-gel transition and its application to an interactive human-machine interface. The hydrogel comprises a triple polymeric network where irreversible amide linkage of polyacrylamide with alginate and dynamic covalent bonds entailing conjugated polymer chains of poly(3,4-ethylenedioxythiophene)-co-(3-thienylboronic acid) are simultaneously capable of high stretchability (1300% strain), efficient strain dissipation (36,209 J/m2), low electrical resistance (590 Ω), and even robust skin adhesiveness (35.0 ± 5.6 kPa). Based on such decent characteristics, the hydrogel was utilized as a multifunctional layer for successfully performing either electrophysiological cardiac/muscular on-skin sensors or an interactive stretchable human-machine interface.

Interactive Aqueous Ink from Core‐Shell Liquid Metal and PEDOT:PSS

AbstractLiquid metals (LMs) and conjugated polymers are both critically important materials in modern technologies including soft robotics, printable circuits, and stretchable electronics. Although broadly applied, the joint use of LMs and conjugated polymers are rarely explored due to the notoriously interfacial challenges of the high surface tension of LMs and the unfavorable rigid backbones of conjugated polymer chains. This work successfully introduced conjugated polymers (poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate, (PEDOT:PSS)) into the system of liquid metals to provide a highly stable, aqueous, and electrically conductive ink (LM‐PEDOT:PSS inks, LMPInks) for flexible electronics. The PSS segments act as a strong ionic bridge to effectively stabilize core‐shell structure of the PEDOT and LMs in the homogenous ink. Different from previous insulated LM‐inks, LMPInk is aqueous and more importantly, electrically conductive without posttreatments due to the intrinsically conductive PEDOT:PSS. Interestingly, with low content of LM particles (<2 wt%), the printed circuits inherit the valuable transparency of PEDOT:PSS (transmission >92% in visible region), which has never been observed in LM‐based organic systems. Furthermore, such LMPInks show distinguished electrical robustness, which can automatically recover their initial electrical conductivity even after severe physical damage. With the above phenomenal advantages, various flexible circuits on different substrates are successfully provided.

Fluorene based electrochromic conjugated polymers: A review

This review briefly describes electrochromic conductive polymers containing fluorene in the main chain or as a subunit/core. According to the arrangement of the fluorene unit and its chemical location on the chain, polyfluorene family was expressed in three classes; fluorene EC homopolymers, copolymers and functional EC polymers. With its sometimes surprising properties and countless advantages, fluorene monomer has many contributions to the electrochromic conductive polymer chain. Although there are many fluorene derived polymers in the literature that have been functionalized and/or used in various applications, this review only found it appropriate to focus on conductive electrochromic polymers with possessing fluorene chemical units. For this purpose, it has been tried to review and comment on fluorene polymers by comparing their chemical, electrochemical and optical properties in a logical framework. One of the biggest problems of electrochromic conductive polymer researchers is to analyze how the redox and electrochromic properties of polymers, which consist of a functional group, change according to the position on the conjugated polymer chain. For this reason, it is thought that the contribution and guideness of this study to the literature will be considerable.

Crystal Structures of Lignocellulosic Furfuryl Biobased Polydiacetylenes with Hydrogen-Bond Networks: Influencing the Direction of Solid-State Polymerization through Modification of the Spacer Length.

We present the topochemical polymerization of two lignocellulosic biobased diacetylenes (DAs) that only differ by an alkyl spacer length of 1 methylene (n = 1) or 3 methylene units (n = 3) between the diyne and carbamate functionalities. Their crystalline molecular organizations have the distinctive feature of being suitable for polymerization in two potential directions, either parallel or skewed to the hydrogen-bonded (HB) network. However, single-crystal structures of the final polydiacetylenes (PDAs) demonstrate that the resulting orientation of the conjugated backbones is different for these two derivatives, which lead to HB supramolecular polymer networks (2D nanosheets) for n = 1 and to independent linear PDA chains with intramolecular HBs for n = 3. Thus, spacer length modification can be considered a new strategy to influence the molecular orientation of conjugated polymer chains, which is crucial for developing the next generation of materials with optimal mechanical and optoelectronic properties. Calculations were performed on model oligodiacetylenes to evaluate the cooperativity effect of HBs in the different crystalline supramolecular packing motifs and the energy profile related to the torsion of the conjugated backbone of a PDA chain (i.e., its ability to adopt planar or helical conformations).