Systematic Investigation of Side‐Chain Branching Position Effect on Electron Carrier Mobility in Conjugated Polymers

Recently, polymer field‐effect transistors have gone through rapid development. Nevertheless, charge transport mechanism and structure‐property relationship are less understood. Here we use strong electron‐deficient benzodifurandione‐based poly(p‐phenylene vinylene) ( BDPPV ) as polymer backbone and develop six BDPPV ‐based polymers ( BDPPV‐C1 to C6 ) with various side‐chain branching positions to systematically study the side‐chain effect on device performance. All the polymers exhibited ambient‐stable n‐type transporting behaviors with the highest electron mobility of up to 1.40 cm² V^?1 s^?1. The film morphologies and microstructures of all the six polymers were systematically investigated. Our results demonstrate that the interchain π–π stacking distance decreases as moving the branching position away from polymer backbones, and an unprecedentedly close π–π stacking distance down to 3.38 Å is obtained for BDPPV‐C4 to C6 . Nonetheless, closer π–π stacking distance does not always correlate with higher electron mobility. Polymer crystallinity, thin film disorder, and polymer packing conformation, which all influenced by side‐chain branching position, are proved to show significant influence on device performance. Our study not only reveals that π–π stacking distance is not the decisive factor on carrier mobility in conjugated polymers but also demonstrates that side‐chain branching position engineering is a powerful strategy to modulate and balance these factors in conjugated polymers.     

Effect of Spacer Length of Siloxane‐Terminated Side Chains on Charge Transport in Isoindigo‐Based Polymer Semiconductor Thin Films

A series of isoindigo‐based conjugated polymers (PII2F‐C_mSi, m = 3–11) with alkyl siloxane‐terminated side chains are prepared, in which the branching point is systematically “moved away” from the conjugated backbone by one carbon atom. To investigate the structure–property relationship, the polymer thin film is subsequently tested in top‐contact field‐effect transistors, and further characterized by both grazing incidence X‐ray diffraction and atomic force microscopy. Hole mobilities over 1 cm² V^?1 s^?1 is exhibited for all soluble PII2F‐C_mSi (m = 5–11) polymers, which is 10 times higher than the reference polymer with same polymer backbone. PII2F‐C₉Si shows the highest mobility of 4.8 cm² V^?1 s^?1, even though PII2F‐C₁₁Si exhibits the smallest π–π stacking distance at 3.379 Å. In specific, when the branching point is at, or beyond, the third carbon atoms, the contribution to charge transport arising from π–π stacking distance shortening becomes less significant. Other factors, such as thin‐film microstructure, crystallinity, domain size, become more important in affecting the resulting device's charge transport.     

Phthalocyanine‐Based 2D Conjugated Metal‐Organic Framework Nanosheets for High‐Performance Micro‐Supercapacitors

2D conjugated metal‐organic frameworks (2D c‐MOFs) are emerging as a novel class of conductive redox‐active materials for electrochemical energy storage. However, developing 2D c‐MOFs as flexible thin‐film electrodes have been largely limited, due to the lack of capability of solution‐processing and integration into nanodevices arising from the rigid powder samples by solvothermal synthesis. Here, the synthesis of phthalocyanine‐based 2D c‐MOF (Ni₂[CuPc(NH)₈]) nanosheets through ball milling mechanical exfoliation method are reported. The nanosheets feature with average lateral size of ≈160 nm and mean thickness of ≈7 nm (≈10 layers), and exhibit high crystallinity and chemical stability as well as a p‐type semiconducting behavior with mobility of ≈1.5 cm² V^?1 s^?1 at room temperature. Benefiting from the ultrathin feature, the nanosheets allow high utilization of active sites and facile solution‐processability. Thus, micro‐supercapacitor (MSC) devices are fabricated mixing Ni₂[CuPc(NH)₈] nanosheets with exfoliated graphene, which display outstanding cycling stability and a high areal capacitance up to 18.9 mF cm^?2; the performance surpasses most of the reported conducting polymers‐based and 2D materials‐based MSCs.     

Structural and Electronic Properties of the First Monolayers of Spin‐Cast Poly(fluorene)‐Based Conjugated‐ Polymer Films

This study is an extended investigation on the formation of the first few monolayers of conjugated poly(fluorene)‐based polymer films prepared from solution on defined polar and nonpolar surfaces. In particular, a symmetrical A–B–A triblock copolymer consisting of poly(2‐alkylaniline) as A blocks and poly(9,9‐dialkylfluorene) as B blocks and a poly(9,9‐dialkylfluorene) homopolymer is used for this study. The dependence on drying conditions by means of solvent selection, the influence of a subsequent heat treatment, and the influence of the substrate polarity are investigated for ultrathin films as well as the transition from the first monolayers to the bulk polymer. The study is performed with optical absorption and photoluminescence spectroscopy, and atomic force microscopy to obtain complementary information of optical properties and morphological details. We find that ultrathin films (ca. 1–2 nm) prepared on mica from various solvents form highly defined, flat monolayers at the interface without lateral regularities indicating a dipole–dipole interaction between conjugated‐polymer segments and mica surface dipoles. This is further confirmed by bathochromic photoluminescence shifts observed for the ultrathin layers compared to the bulk polymer. Complementary experiments on nonpolar surfaces, highly oriented pyrolytic graphite (HOPG), show a total absence of defined flat films supporting the assumption of a dipole–dipole assisted formation on mica. For increased film thickness on mica (5 nm and more) the homopolymer does not form any regular structures or ordered layers on top of the monolayer. In contrast, the triblock copolymer, shorter in length, revealed a tendency to form a less‐defined layer‐type growth (3–3.5 nm thick) above the monolayer that was of higher order for higher‐boiling‐point solvents, indicating that the polymers are found in a different conformation. Moreover, one finds that some solvents that show partial immiscibility with the polymer strongly alter the formation of the film. The observations made for the two different types of polymers allow for an assignment of film‐formation driving forces to individual polymer segments and allow for the formulation of a growth model that explains the observed results and indicates the importance of appropriate substrate selection for organic electronic/optoelectronic devices.     

Angular‐Shaped 4,9‐Dialkyl α‐ and β‐Naphthodithiophene‐Based Donor–Acceptor Copolymers: Investigation of Isomeric Structural Effects on Molecular Properties and Performance of Field‐Effect Transistors and Photovoltaics

Two angular‐shaped 4,9‐didodecyl α‐aNDT and 4,9‐didodecyl β‐aNDT isomeric structures have been regiospecifically designed and synthesized. The distannylated α‐aNDT and β‐aNDT monomers are copolymerized with the Br‐DTNT monomer by the Stille coupling to furnish two isomeric copolymers, PαNDTDTNT and PβNDTDTNT, respectively. The geometric shape and coplanarity of the isomeric α‐aNDT and β‐aNDT segments in the polymers play a decisive role in determining their macroscopic device performance. Theoretical calculations show that PαNDTDTNT possesses more linear polymeric backbone and higher coplanarity than PβNDTDTNT. The less curved conjugated main chain facilitates stronger intermolecular π–π interactions, resulting in more redshifted absorption spectra of PαNDTDTNT in both solution and thin film compared to the PβNDTDTNT counterpart. 2D wide‐angle X‐ray diffraction analysis reveals that PαNDTDTNT has more ordered π‐stacking and lamellar stacking than PβNDTDTNT as a result of the lesser curvature of the PαNDTDTNT backbone. Consistently, PαNDTDTNT exhibits a greater field effect transistor hole mobility of 0.214 cm² V^?1 s^?1 than PβNDTDTNT with a mobility of 0.038 cm² V^?1 s^?1. More significantly, the solar cell device incorporating the PαNDTDTNT:PC₇₁BM blend delivers a superior power conversion efficiency (PCE) of 8.01% that outperforms the PβNDTDTNT:PC₇₁BM‐based device with a moderate PCE of 3.6%.     

D‐A1‐D‐A2 Backbone Strategy for Benzobisthiadiazole Based n‐Channel Organic Transistors: Clarifying the Selenium‐Substitution Effect on the Molecular Packing and Charge Transport Properties in Electron‐Deficient Polymers

Unipolar n‐type semiconducting polymers based on the benzobisthiadiazole (BBT) unit and its heteroatom‐substituted derivatives are for the first time synthesized by the D‐A₁‐D‐A₂ polymer‐backbone design strategy. Selenium (Se) substitution is a very effective molecular design, but it has been seldom studied in n‐type polymers. In this study, within the similar conjugated framework, the Se substitution effects on the optical, electrochemical, solid‐state polymer packing, electron mobility, and air‐stability of the target unipolar n‐type polymers are unraveled. Replacing the sulfur (S) atom in the thiadiazole heterocycles with the Se atom leads to narrower bandgaps and deeper lowest unoccupied molecular orbital (LUMO) levels of the n‐type polymers. Furthermore, the Se‐substituted polymer (pSeN‐NDI) shows shorter lamellar packing distances and stronger edge‐on π–π stacking interactions than its S‐counterpart (pSN‐NDI), as observed by the two‐dimensional grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) patterns. With the deeper LUMO level and thin‐film microstructures suitable for transistors, pSeN‐NDI exhibits four‐fold higher electron mobilities (μ_e) than pSN‐NDI. However, the other Se‐containing polymer, pSeS‐NDI, forms rather amorphous film structures, which is caused by its limited thermal stability and decomposition during the thermal annealing processes, thus giving rise to a lower μ_e than its S‐counterpart (pBBT‐NDI). Most importantly, pBBT‐NDI demonstrates an electron mobility of 0.039 cm² V^?1 s^?1, which is noticeable among the unipolar n‐type polymers based on the BBT and its analogs.     

Spontaneous Phase Separation of Poly(3‐hexylthiophene)s with Different Regioregularity for a Stretchable Semiconducting Film

Highly regioregular (RR) poly(3‐hexylthiophene)s PHTs are known to exhibit excellent electrical properties in comparison to chemically identical but regiorandom (rr) PHTs. In this study, distinct RR (97% and 55%)‐graded PHTs are subjected to solution blending to spontaneously separate the high‐RR PHT chains from the low‐RR PHT media and develop highly conjugated nanodomains in both solution and film. In the spun‐cast blend films, the rr PHT matrix imparts sufficient deformability of the channel layer required for stretchable organic thin‐film transistors (OTFTs), compared to neat RR PHTs and blends with a deformable polymer. OTFTs including RR PHT/rr PHT blend films show excellent hole mobility (µ) values up to 0.13 cm² V^?1 s^?1, surpassing that of the best RR PHT films (0.026 cm² V^?1 s^?1) fabricated by ultrasound solution pretreatment. Furthermore, a 50% stretched RR PHT/rr PHT film maintains ≈55% of its µ value at no strain, while RR PHT films show a sudden decrease in µ even at 10% stretch. The simple blending approach imparts deformability to π‐conjugated polymer films for application in stretchable OTFTs.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

Short‐Wavelength Lasing‐Spasing and Random Spasing with Deeply Subwavelength Thin‐Film Gain Media

Lasing‐spasers are subwavelength‐sized metal/dielectric structures that emit light via stimulated emission of surface plasmons. Here, it is demonstrated that silver nanoparticles combined with deeply subwavelength, blue‐emitting conjugated polymer thin films can function as room‐temperature lasing‐spasers and random spasers with quality factors up to 250. In contrast to other thin‐film‐based spaser and plasmonic random laser studies, which have used gain films ranging from ≈200 nm to 500 nm in thickness and which monitor emission guided to the sample edges, in this study, the thickness of the thin‐film gain medium ranges from 30 nm to 70 nm and emission is collected normal to the plane of the film. This eliminates effects that arise from optical trapping of scattered emission within the gain medium that is typically associated with plasmonic random lasing. The use of the conjugated polymer thin‐film gain medium allows higher chromophore densities compared to organic dye‐doped layers, which enables spasing using deeply subwavelength gain layers. Samples implementing gold nanoparticles and the conjugated polymer gain medium do not exhibit stimulated emission, demonstrating that it is the spectral overlap between the silver nanoparticle's surface plasmon resonance and the gain medium's emission that is necessary for observation of stimulated emission from this material system.     

On the Relation between Morphology and FET Mobility of Poly(3‐alkylthiophene)s at the Polymer/SiO2 and Polymer/Air Interface

The influence of the interface of the dielectric SiO₂ on the performance of bottom‐contact, bottom‐gate poly(3‐alkylthiophene) (P3AT) field‐effect transistors (FETs) is investigated. In particular, the operation of transistors where the active polythiophene layer is directly spin‐coated from chlorobenzene (CB) onto the bare SiO₂ dielectric is compared to those where the active layer is first spin‐coated then laminated via a wet transfer process such that the film/air interface of this film contacts the SiO₂ surface. While an apparent alkyl side‐chain length dependent mobility is observed for films directly spin‐coated onto the SiO₂ dielectric (with mobilities of ≈10^?3 cm² V^?1 s^?1 or less) for laminated films mobilities of 0.14 ± 0.03 cm² V^?1 s^?1 independent of alkyl chain length are recorded. Surface‐sensitive near edge X‐ray absorption fine structure (NEXAFS) spectroscopy measurements indicate a strong out‐of‐plane orientation of the polymer backbone at the original air/film interface while much lower average tilt angles of the polymer backbone are observed at the SiO₂/film interface. A comparison with NEXAFS on crystalline P3AT nanofibers, as well as molecular mechanics and electronic structure calculations on ideal P3AT crystals suggest a close to crystalline polymer organization at the P3AT/air interface of films from CB. These results emphasize the negative influence of wrongly oriented polymer on charge carrier mobility and highlight the potential of the polymer/air interface in achieving excellent “out‐of‐plane” orientation and high FET mobilities.     

Selective Dispersion of Large‐Diameter Semiconducting Carbon Nanotubes by Functionalized Conjugated Dendritic Oligothiophenes for Use in Printed Thin Film Transistors

Selective dispersion of semiconducting single walled carbon nanotubes (s‐SWCNTs) by conjugated polymer wrapping is recognized as the most promising scalable method for s‐SWCNT separation. Despite a number of linear conjugated polymers being reported for use in s‐SWCNT separation, these linear polymers suffer batch‐to‐batch variation for their undefined molecular structure. Here, it is reported that conjugated dendritic oligothiophenes with multiple diketopyrrolopyrrole groups at the periphery have the capability of selectively dispersing large diameter s‐SWCNTs with high dispersion efficiency and certain chiral selectivity. Printed top‐gated thin film transistors using the dendrimer sorted s‐SWCNTs show high charge carrier mobility of up to 57 cm² V^?1 s^?1 and on/off ratios of ≈10⁶ with high reproducibility, which is ascribed to the defined and monodispersed molecular structure of dendrimers. Moreover, owing to the multiple peripheral anchoring groups of these dendritic molecules, these dendrimer‐s‐SWCNT dispersions display excellent stability. The current work proves that dendritic molecules are excellent dispersion reagents for s‐SWCNT separation.     

ε‐Branched Flexible Side Chain Substituted Diketopyrrolopyrrole‐Containing Polymers Designed for High Hole and Electron Mobilities

Based on the integrated consideration and engineering of both conjugated backbones and flexible side chains, solution‐processable polymeric semiconductors consisting of a diketopyrrolopyrrole (DPP) backbone and a finely modulated branching side chain (ε‐branched chain) are reported. The subtle change in the branching point from the backbone alters the π?π stacking and the lamellar distances between polymer backbones, which has a significant influence on the charge‐transport properties and in turn the performances of field‐effect transistors (FETs). In addition to their excellent electron mobilities (up to 2.25 cm² V^?1 s^?1), ultra‐high hole mobilities (up to 12.25 cm² V^?1 s^?1) with an on/off ratio (I_on/I_off) of at least 10⁶ are achieved in the FETs fabricated using the polymers. The developed polymers exhibit extraordinarily high electrical performance with both hole and electron mobilities superior to that of unipolar amorphous silicon.     

Kinetically Controlled Crystallization in Conjugated Polymer Films for High‐Performance Organic Field‐Effect Transistors

Ordering of semiconducting polymers in thin films from the nano to microscale is strongly correlated with charge transport properties as well as organic field‐effect transistor performance. This paper reports a method to control nano to microscale ordering of poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)) thin films by precisely regulating the solidification rate from the metastable state just before crystallization. The proposed simple but effective approach, kinetically controlled crystallization, achieves optimized P(NDI2OD‐T2) films with large polymer domains, long range ordered fibrillar structures, and molecular orientation preferable for electron transport leading to dramatic morphological changes in both polymer domain sizes at the micrometer scale and molecular packing structures at nanoscales. Structural changes significantly increase electron mobilities up to 3.43 ± 0.39 cm² V^?1 s^?1 with high reliability, almost two orders of enhancement compared with devices from naturally dried films. Small contact resistance is also obtained for electron injection (0.13 MΩ cm), low activation energy (62.51 meV), and narrow density of states distribution for electron transport in optimized thin films. It is believed that this study offers important insight into the crystallization of conjugated polymers that can be broadly applied to optimize the morphology of semiconducting polymer films for solution processed organic electronic devices.     

Simultaneous Enhancement in Electrical Conductivity and Thermopower of n‐Type NiETT/PVDF Composite Films by Annealing

Nickel ethenetetrathiolate (NiETT) polymers are promising n‐type thermoelectric (TE) materials, but their insolubility requires the use of an inert polymer matrix to form films, which is detrimental to the TE performance. In this work, the use of thermal annealing as a post‐treatment process simultaneously enhances the electrical conductivity from 6 ± 2 to 23 ± 3 S cm^?1 and thermopower from ?28 ± 3 to ?74 ± 4 µV K^?1 for NiETT/PVDF composite films. Spectroscopic characterization reveals that the underlying mechanism involves removal of residual solvent and volatile impurities (carbonyl sulfide and water) in the NiETT polymer backbone. Additionally, microscopic characterization reveals morphological changes caused by a densification of the film that improves chain packing. These effects result in a 25 × improvement in power factor from 0.5 to 12.5 µW m^?1 K^?2 for NiETT/PVDF films and provide insight into the composition of these coordination polymers that maintain their stability under ambient conditions.     

Combinatorial Study of Temperature‐Dependent Nanostructure and Electrical Conduction of Polymer Semiconductors: Even Bimodal Orientation Can Enhance 3D Charge Transport

Temperature‐dependent (80–350 K) charge transport in polymer semiconductor thin films is studied in parallel with in situ X‐ray structural characterization at equivalent temperatures. The study is conducted on a pair of isoindigo‐based polymers containing the same π‐conjugated backbone with different side chains: one with siloxane‐terminated side chains (PII2T‐Si) and the other with branched alkyl‐terminated side chains (PII2T‐Ref). The different chemical moiety in the side chain results in a completely different film morphology. PII2T‐Si films show domains of both edge‐on and face‐on orientations (bimodal orientation) while PII2T‐Ref films show domains of edge‐on orientation (unimodal orientation). Electrical transport properties of this pair of polymers are also distinctive, especially at high temperatures (>230 K). Smaller activation energy (E _A) and larger pre‐exponential factor (μ ₀) in the mobility‐temperature Arrhenius relation are obtained for PII2T‐Si films when compared to those for PII2T‐Ref films. The results indicate that the more effective transport pathway is formed for PII2T‐Si films than for the other, despite the bimodally oriented film structure. The closer π–π packing distance, the longer coherence length of the molecular ordering, and the smaller disorder of the transport energy states for PII2T‐Si films altogether support the conduction to occur more effectively through a system with both edge‐on and face on orientations of the conjugated molecules. Reminding the 3D nature of conduction in polymer semiconductor, our results suggest that the engineering rules for advanced polymer semiconductors should not simply focus on obtaining films with conjugated backbone in edge‐on orientation only. Instead, the engineering should also encounter the contribution of the inevitable off‐directional transport process to attain effective transport from polymer thin films.     

Shift of the Branching Point of the Side‐Chain in Naphthalenediimide (NDI)‐Based Polymer for Enhanced Electron Mobility and All‐Polymer Solar Cell Performance

The branching point of the side‐chain of naphthalenediimide (NDI)‐based conjugated polymers is systematically controlled by incorporating four different side‐chains, i.e., 2‐hexyloctyl (P(NDI1‐T)), 3‐hexylnonyl (P(NDI2‐T)), 4‐hexyldecyl (P(NDI3‐T)), and 5‐hexylundecyl (P(NDI4‐T)). When the branching point is located farther away from the conjugated backbones, steric hindrance around the backbone is relaxed and the intermolecular interactions between the polymer chains become stronger, which promotes the formation of crystalline structures in thin film state. In particular, thermally annealed films of P(NDI3‐T) and P(NDI4‐T), which have branching points far away from the backbone, possess more‐developed bimodal structure along both the face‐on and edge‐on orientations. Consequently, the field‐effect electron mobilities of P(NDIm‐T) polymers are monotonically increased from 0.03 cm² V⁻¹ s⁻¹ in P(NDI1‐T) to 0.22 cm² V⁻¹ s⁻¹ in P(NDI4‐T), accompanied by reduced activation energy and contact resistance of the thin films. In addition, when the series of P(NDIm‐T) polymers is applied in all‐polymer solar cells (all‐PSCs) as electron acceptor, remarkably high‐power conversion efficiency of 7.1% is achieved along with enhanced current density in P(NDI3‐T)‐based all‐PSCs, which is mainly attributed to red‐shifted light absorption and enhanced electron‐transporting ability.     

Energy Level Bending in Ultrathin Polymer Layers Obtained through Langmuir–Shäfer Deposition

The semiconductor–electrode interface impacts the function and the performance of (opto)electronic devices. For printed organic electronics the electrode surface is not atomically clean leading to weakly interacting interfaces. As a result, solution‐processed organic ultrathin films on electrodes typically form islands due to dewetting. It has therefore been utterly difficult to achieve homogenous ultrathin conjugated polymer films. This has made the investigation of the correct energetics of the conjugated polymer–electrode interface impossible. Also, this has hampered the development of devices including ultrathin conjugated polymer layers. Here, Langmuir–Shäfer‐manufactured homogenous mono‐ and multilayers of semiconducting polymers on metal electrodes are reported and the energy level bending using photoelectron spectroscopy is tracked. The amorphous films display an abrupt energy level bending that does not extend beyond the first monolayer. These findings provide new insights of the energetics of the polymer–electrode interface and opens up for new high‐performing devices based on ultrathin semiconducting polymers.     

Anisotropy of Charge Transport in a Uniaxially Aligned and Chain‐Extended,High‐Mobility,Conjugated Polymer Semiconductor

Charge transport in the ribbon phase of poly(2,5‐bis(3‐alkylthiophen‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT)—one of the most highly ordered, chain‐extended crystalline microstructures available in a conjugated polymer semiconductor—is studied. Ribbon‐phase PBTTT has previously been found not to exhibit high carrier mobilities, but it is shown here that field‐effect mobilities depend strongly on the device architecture and active interface. When devices are constructed such that the ribbon‐phase films are in contact with either a polymer gate dielectric or an SiO₂ gate dielectric modified by a hydrophobic, self‐assembled monolayer, high mobilities of up to 0.4 cm² V^?1 s^?1 can be achieved, which is comparable to those observed previously in terrace‐phase PBTTT. In uniaxially aligned, zone‐cast films of ribbon‐phase PBTTT the mobility anisotropy is measured for transport both parallel and perpendicular to the polymer chain direction. The mobility anisotropy is relatively small, with the mobility along the polymer chain direction being higher by a factor of 3–5, consistent with the grain size encountered in the two transport directions.     

Effect of Alkyl Chain Branching Point on 3D Crystallinity in High N‐Type Mobility Indolonaphthyridine Polymers

Herein, this study investigates the impact of branching‐point‐extended alkyl chains on the charge transport properties of three ultrahigh n‐type mobility conjugated polymers. Using grazing incidence wide‐angle X‐ray scattering, analysis of the crystallinity of the series shows that while π–π interactions are increased for all three polymers as expected, the impact of the side‐chain engineering on polymer backbone crystallinity is unique to each polymer and correlates to the observed changes in charge transport. With the three polymers exhibiting n‐type mobilities between 0.63 and 1.04 cm² V^?1 s^?1, these results ratify that the indolonaphthyridine building block has an unprecedented intrinsic ability to furnish high‐performance n‐type organic semiconductors.     

Layer‐by‐Layer Conjugated Extension of a Semiconducting Polymer for High‐Performance Organic Field‐Effect Transistor

A donor–acceptor (D–A) semiconducting copolymer, PDPP‐TVT‐29, comprising a diketopyrrolopyrrole (DPP) derivative with long, linear, space‐separated alkyl side‐chains and thiophene vinylene thiophene (TVT) for organic field‐effect transistors (OFETs) can form highly π‐conjugated structures with an edge‐on molecular orientation in an as‐spun film. In particular, the layer‐like conjugated film morphologies can be developed via short‐term thermal annealing above 150 °C for 10 min. The strong intermolecular interaction, originating from the fused DPP and D–A interaction, leads to the spontaneous self‐assembly of polymer chains within close proximity (with π‐overlap distance of 3.55 Å) and forms unexpectedly long‐range π‐conjugation, which is favorable for both intra‐ and intermolecular charge transport. Unlike intergranular nanorods in the as‐spun film, well‐conjugated layers in the 200 °C‐annealed film can yield more efficient charge‐transport pathways. The granular morphology of the as‐spun PDPP‐TVT‐29 film produces a field‐effect mobility (μ _FET) of 1.39 cm² V^?1 s^?1 in an OFET based on a polymer‐treated SiO₂ dielectric, while the 27‐Å‐step layered morphology in the 200 °C‐annealed films shows high μ _FET values of up to 3.7 cm² V^?1 s^?1.