Polymer Semiconductors: Synthesis, Processing, and Applications.

Polymer semiconductors composed of a carbon-based π conjugated backbone have been studied for several decades as active layers of multifarious organic electronic devices. They combine the advantages of the electrical conductivity of metals and semiconductors and the mechanical behavior of plastics, which are going to become one of the futures of modulable electronic materials. The performance of conjugated materials depends both on their chemical structures and the multilevel microstructures in solid states. Despite the great efforts that have been made, they are still far from producing a clear picture among intrinsic molecular structures, microstructures, and device performances. This review summarizes the development of polymer semiconductors in recent decades from the aspects of material design and the related synthetic strategies, multilevel microstructures, processing technologies, and functional applications. The multilevel microstructures of polymer semiconductors are especially emphasized, which plays a decisive role in determining the device performance. The discussion shows the panorama of polymer semiconductors research and sets up a bridge across chemical structures, microstructures, and finally devices performances. Finally, this review discusses the grand challenges and future opportunities for the research and development of polymer semiconductors.

Determining the Number of Graphene Nanoribbons in Dual-Gate Field-Effect Transistors.

Bottom-up synthesized graphene nanoribbons (GNRs) are increasingly attracting interest due to their atomically controlled structure and customizable physical properties. In recent years, a range of GNR-based field-effect transistors (FETs) has been fabricated, with several demonstrating quantum-dot (QD) behavior at cryogenic temperatures. However, understanding the relationship between the cryogenic charge-transport characteristics and the number of the GNRs in the device is challenging, as the length and location of the GNRs in the junction are not precisely controlled. Here, we present a methodology based on a dual-gate FET that allows us to identify different scenarios, such as single GNRs, double or multiple GNRs in parallel, and a single GNR interacting with charge traps. Our dual-gate FET architecture therefore offers a quantitative approach for comprehending charge transport in atomically precise GNRs.

BN-Isosteres of Nonacene with Antiaromatic B2 C4 and N2 C4 Heterocycles: Synthesis and Strong Luminescence.

Embedding both boron and nitrogen into the backbone of acenes to generate their isoelectronic structures has significantly enriched the acene chemistry to offer appealing properties. However, only small BN-heteroacenes have been extensively investigated, with BN-heptacenes as the hitherto longest homologue. Herein, we report the synthesis of three new nonacene BN-isosteres via incorporating a pair of antiaromatic B2 C4 and N2 C4 heterocycles, representing a new length record for BN-heteroacenes. The distance between the B2 C4 and N2 C4 rings affects the contribution of the charge-separated resonance forms, leading to tunable antiaromaticity of the two heterocycles. The adjusted local antiaromaticity manifests substantial influence on the molecular orbital arrangement, and consequently, the radiative transition rate of BN-3 is greatly enhanced compared with BN-1 and BN-2, realizing a high fluorescence quantum yield of 92 %. This work provides a novel design concept of large acene BN-isosteres and reveals the importance of BN/CC isosterism on their luminescent properties.

NIR-Absorbing B,N-Heteroarene as Photosensitizer for High-Performance NIR-to-Blue Triplet-Triplet Annihilation Upconversion.

Triplet-triplet annihilation upconversion (TTA-UC) with near-infrared (NIR) photosensitizers is highly desirable for a variety of emerging applications. However, the development of NIR-to-blue TTA-UC with a large anti-Stokes shift is extremely challenging because of the energy loss during the intersystem crossing (ISC). Here, we develop the first NIR-absorbing B,N-heteroarene-based sensitizer (BNS) with multi-resonance thermally activated delayed fluorescence (MR-TADF) characters to achieve efficient NIR-to-blue TTA-UC. The small energy gap between the singlet and triplet excited states (0.14 eV) of BNS suppresses the ISC energy loss, and its long-delayed fluorescence lifetime (115 µs) contributes to efficient triplet energy transfer. As a result, the largest anti-Stokes shift (1.03 eV) among all heavy-atom-free NIR-activatable TTA-UC systems is obtained with a high TTA-UC quantum yield of 2.9 % (upper limit 50 %).

Unravelling the Superiority of Nonbenzenoid Acepleiadylene as a Building Block for Organic Semiconducting Materials.

Acepleiadylene (APD), a nonbenzenoid isomer of pyrene, exhibits a unique charge-separated character with a large molecular dipole and a small optical gap. However, APD has never been explored in optoelectronic materials to take advantage of these appealing properties. Here, we employ APD as a building block in organic semiconducting materials for the first time, and unravel the superiority of nonbenzenoid APD in electronic applications. We have synthesized an APD derivative (APD-IID) with APD as the terminal donor moieties and isoindigo (IID) as the acceptor core. Theoretical and experimental investigations reveal that APD-IID has an obvious charge-separated structure and enhanced intermolecular interactions as compared with its pyrene-based isomers. As a result, APD-IID displays significantly higher hole mobilities than those of the pyrene-based counterparts. These results imply the advantages of employing APD in semiconducting materials and great potential of nonbenzenoid polycyclic arenes for optoelectronic applications.

Synthesis of Highly Luminescent Chiral Nanographene.

Chiral nanographenes with both high fluorescence quantum yields (ΦF ) and large dissymmetry factors (glum ) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement of glum , whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with high ΦF by helical π-extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record high ΦF of 93 % among the reported chiral nanographenes and excellent CPL brightness (BCPL ) of 32 M-1 cm-1 .

Growth Optimization and Device Integration of Narrow-Bandgap Graphene Nanoribbons.

The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultrahigh vacuum conditions from Br- and I-substituted precursors. It is shown that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed the integration of 5-AGNRs into devices and the realization of the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

Controlling the Emissive, Chiroptical, and Electrochemical Properties of Double [7] Helicenes through Embedded Aromatic Rings.

We present here the synthesis and in-depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole-fused double helicene with the previously reported all-carbon and thiadiazole-fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from <1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole-fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin-related applications.

Pushing the Length Limit of Dihydrodiboraacenes: Synthesis and Characterizations of Boron-Embedded Heptacene and Nonacene.

Boron-embedded heteroacenes (boraacenes) have attracted enormous interest in organic chemistry and materials science. However, extending the skeleton of boraacenes to higher acenes (N≥6) is synthetically challenging because of their limited stability under ambient conditions. Herein, we report the synthesis of boron-embedded heptacene (DBH) and nonacene (DBN) as the hitherto longest boraacenes. The former is highly stable (even after 240 h in tetrahydrofuran), while the latter is air-sensitive with the half-life (t1/2 ) of 11.8 min. The structures of both compounds are verified by single-crystal X-ray diffraction, revealing a linear backbone with an antiaromatic C4 B2 core. Photophysical characterizations associated with theoretical calculations indicate that both compounds exhibit highly efficient anti-Kasha emissions. Remarkably, the air-stable DBH manifests an ultrahigh photoluminescence quantum yield (PLQY) of 98±2 % and can be chemically reduced to its radical anion and dianion states, implying the value of boron-doped higher acenes as novel functional materials.

Heteroatom-Edged [4]Triangulene: Facile Synthesis and Two-Dimensional On-Surface Self-Assemblies.

Triangulenes have attracted enormous interest in organic chemistry and materials science, but suffer from their high instability towards oxygen. Embedding heteroatoms into triangulenes provides a new class of ambient stable materials for various applications. However, [3]heterotriangulenes have dominated the chemistry of heteroatom-doped triangulenes, while their higher homologues have been rarely explored. In this work, we synthesize a new [4]heterotriangulene with three oxygen-boron-oxygen (OBO) segments incorporated into the zigzag edges. The planar geometry of the OBO-doped [4]triangulene is demonstrated by single-crystal X-ray diffraction. Self-assembly on metal surfaces reveals substrate-dependent nanostructures, leading to different long-range ordered 2D patterns on Ag and Cu substrates with negligible defects.

A Deep-Learning Framework for the Automated Recognition of Molecules in Scanning-Probe-Microscopy Images.

Computer vision as a subcategory of deep learning tackles complex vision tasks by dealing with data of images. Molecular images with exceptionally high resolution have been achieved thanks to the development of techniques like scanning probe microscopy (SPM). However, extracting useful information from SPM image data requires careful analysis which heavily relies on human supervision. In this work, we develop a deep learning framework using an advanced computer vision algorithm, Mask R-CNN, to address the challenge of molecule detection, classification and instance segmentation in binary molecular nanostructures. We employ the framework to determine two triangular-shaped molecules of similar STM appearance. Our framework could accurately differentiate two molecules and label their positions. We foresee that the application of computer vision in SPM images will become an indispensable part in the field, accelerating data mining and the discovery of new materials.

BN-Anthracene for High-Mobility Organic Optoelectronic Materials through Periphery Engineering.

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B-N bonds (BN-PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high-mobility organic semiconductors based on existing BN-PAHs through a "periphery engineering" strategy. Tetraphenyl- and diphenyl-substituted BN-anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized. DPBNA exhibits the highest hole mobility of 1.3 cm2  V-1 s-1 in organic field-effect transistors, significantly outperforming TPBNA and all the reported BN-PAHs. Remarkably, this is the first BN-PAH with mobility over 1 cm2  V-1 s-1 , which is a benchmark value for practical applications as compared with amorphous silicon. Furthermore, high-performance phototransistors based on DPBNA are also demonstrated, implying the high potential of BN-PAHs for optoelectronic applications when the "periphery engineering" strategy is implemented.

Revisiting Acepleiadylene: Two-Step Synthesis and π-Extension toward Nonbenzenoid Nanographene.

Acepleiadylene (APD), a nonbenzenoid nonalternant isomer of pyrene, exhibits different electronic properties from pyrene, but has been rarely studied since its first synthesis in 1956, probably due to the difficulties in synthesis and further derivatization. In this work, we revisited this long-known compound and developed a new two-step synthetic route to efficiently access APD on the gram scale. Theoretical and experimental characterizations elucidated the unique properties of APD as compared with its benzenoid isomer pyrene, particularly revealing its dipolar structure with a narrow optical gap. The functionalization of APD was demonstrated for the first time, providing doubly brominated APD as a key precursor for further π-extension. As a proof of concept, a π-extended APD and a cyclotrimer nanographene (C48H24) were constructed, opening up new avenues to nonbenzenoid nanographenes with low HOMO-LUMO gaps.

B,N-Embedded Double Hetero[7]helicenes with Strong Chiroptical Responses in the Visible Light Region.

The development of helicene molecules with significant chiroptical responses covering a broad range of the visible spectrum is highly desirable for chiral optoelectronic applications; however, their absorption dissymmetry factors (gabs) have been mostly lower than 0.01. In this work, we report unprecedented B,N-embedded double hetero[7]helicenes with nonbonded B and N atoms, which exhibit excellent chiroptical properties, such as strong chiroptical activities from 300 to 700 nm, record high gabs up to 0.033 in the visible spectral range, and tunable circularly polarized luminescence (CPL) from red to near-infrared regions (600-800 nm) with high photoluminescence quantum yields (PLQYs) up to 100%. As revealed by theoretical analyses, the high gabs values are related to the separate molecular orbital distributions owing to the incorporation of nonbonded B and N atoms. The new type of B,N-embedded double heterohelicenes opens up an appealing avenue to the future exploitation of high-performance chiroptical materials.

Parent B2 N2 -Perylenes with Different BN Orientations.

Introducing BN units into polycyclic aromatic hydrocarbons expands the chemical space of conjugated materials with novel properties. However, it is challenging to achieve accurate synthesis of BN-PAHs with specific BN positions and orientations. Here, three new parent B2 N2 -perylenes with different BN orientations are synthesized with BN-naphthalene as the building block, providing systematic insight into the effects of BN incorporation with different orientations on the structure, (anti)aromaticity, crystal packing and photophysical properties. The intermolecular dipole-dipole interaction shortens the π-π stacking distance. The crystal structure, (anti)aromaticity, and photophysical properties vary with the change of BN orientation. The revealed BN doping effects may provide a guideline for the synthesis of BN-PAHs with specific stacking structures, and the synthetic strategy employed here can be extended toward the synthesis of larger BN-embedded PAHs with adjustable BN patterns.

Correlating Charge Transport Properties of Conjugated Polymers in Solution Aggregates and Thin-Film Aggregates.

The role of solution aggregates on the charge transport process of conjugated polymers in electronic devices has gained increasing attention; however, the correlation of the charge carrier mobilities between the solution aggregates and the solid-state films remains elusive. Herein, three polymers, FBDOPV-2T, FBDOPV-2F2T, and FBDOPV-4F2T, are designed and synthesized with distinct aggregation behavior in solution. By combining contact-free ultrafast terahertz (THz) spectroscopy and field-effect transistor measurements, we track the charge carrier mobility of the aggregates of these polymers from the solution to the thin-film state. Remarkably, the mobility of these three polymers is found to follow nearly the same trend (FBDOPV-2T>FBDOPV-2F2T≫FBDOPV-4F2T) in both solutions and thin-film states. The quantitative mobility correlation indicates that the charge transport properties of solution aggregates play a critical role in determining the thin-film charge transport properties and final device performance. Our results highlight the importance of investigating and controlling solution aggregation structures towards efficient organic electronic devices.

Bottom-Up, On-Surface-Synthesized Armchair Graphene Nanoribbons for Ultra-High-Power Micro-Supercapacitors.

Bottom-up-synthesized graphene nanoribbons (GNRs) with excellent electronic properties are promising materials for energy storage systems. Herein, we report bottom-up-synthesized GNR films employed as electrode materials for micro-supercapacitors (MSCs). The micro-device delivers an excellent volumetric capacitance and an ultra-high power density. The electrochemical performance of MSCs could be correlated with the charge carrier mobility within the differently employed GNRs, as determined by pump-probe terahertz spectroscopy studies.

Heteroatom-Doped Nanographenes with Structural Precision.

Nanographenes, which are defined as nanoscale (1-100 nm) graphene cutouts, include quasi-one-dimensional graphene nanoribbons (GNRs) and quasi-zero-dimensional graphene quantum dots (GQDs). Polycyclic aromatic hydrocarbons (PAHs) larger than 1 nm can be viewed as GQDs with atomically precise molecular structures and can thus be termed nanographene molecules. As a result of quantum confinement, nanographenes are promising for next-generation semiconductor applications with finite band gaps, a significant advantage compared with gapless two-dimensional graphene. Similar to the atomic doping strategy in inorganic semiconductors, incorporation of heteroatoms into nanographenes is a viable way to tune their optical, electronic, catalytic, and magnetic properties. Such properties are highly dependent not only on the molecular size and edge structure but also on the heteroatom type, doping position, and concentration. Therefore, reliable synthetic methods are required to precisely control these structural features. In this regard, bottom-up organic synthesis provides an indispensable way to achieve structurally well-defined heteroatom-doped nanographenes. Polycyclic heteroaromatic compounds have attracted great attention of organic chemists for decades. Research in this direction has been further promoted by modern interest in supramolecular chemistry and organic electronics. The rise of graphene in the 21st century has endowed large polycyclic heteroaromatic compounds with a new role as model systems for heteroatom-doped graphene. Heteroatom-doped nanographene molecules are in their own right promising materials for photonic, optoelectronic, and spintronic applications because of the extended π conjugation. Despite the significant advances in polycyclic heteroaromatic compounds, heteroatom-doped nanographene molecules with sizes of over 1 nm and their relevant GNRs are still scarce. In this Account, we describe the synthesis and properties of large heteroatom-doped nanographenes, mainly summarizing relevant advances in our group in the past decade. We first present several examples of heteroatom doping based on the prototypical nanographene molecule, i.e., hexa-peri-hexabenzocoronene (HBC), including nitrogen-doped HBC analogues by formal replacement of benzene with other heterocycles (e.g., aromatic pyrimidine and pyrrole and antiaromatic pyrazine) and sulfur-doped nanographene molecules via thiophene annulation. We then introduce heteroatom-doped zigzag edges and a variety of zigzag-edged nanographene molecules incorporating nitrogen, boron, and oxygen atoms. We finally summarize heteroatom-doped GNRs based on the success in the molecular cases. We hope that this Account will further stimulate the synthesis and applications of heteroatom-doped nanographenes with a combined effort from different disciplines.

Compressing Double [7]Helicene by Successive Charging with Electrons.

Chemical reduction of a benzo-fused double [7]helicene (1) with two alkali metals, K and Rb, provided access to three different reduced states of 1. The doubly-reduced helicene 12- has been characterized by single-crystal X-ray diffraction as a solvent-separated ion triplet with two potassium counterions. The triply- and tetra-reduced helicenes, 13- and 14- , have been crystallized together in an equimolar ratio and both form the contact-ion complexes with two Rb+ ions each, leaving three remaining Rb+ ions wrapped by crown ether and THF molecules. As structural consequence of the stepwise reduction of 1, the central axis of helicene becomes more compressed upon electron addition (1.42 Šin 14- vs. 2.09 Šin 1). This is accompanied by an extra core twist, as the peripheral dihedral angle increases from 16.5° in 1 to 20.7° in 14- . Theoretical calculations provided the pattern of negative charge build-up and distribution over the contorted helicene framework upon each electron addition, and the results are consistent with the X-ray crystallographic and NMR spectroscopic data.

π-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon.

A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm-1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices.