Recent Progress in High‐Mobility Organic Transistors: A Reality Check

Over the past three decades, significant research efforts have focused on improving the charge carrier mobility of organic thin‐film transistors (OTFTs). In recent years, a commonly observed nonlinearity in OTFT current–voltage characteristics, known as the “kink” or “double slope,” has led to widespread mobility overestimations, contaminating the relevant literature. Here, published data from the past 30 years is reviewed to uncover the extent of the field‐effect mobility hype and identify the progress that has actually been achieved in the field of OTFTs. Present carrier‐mobility‐related challenges are identified, finding that reliable hole and electron mobility values of 20 and 10 cm² V^?1 s^?1, respectively, have yet to be achieved. Based on the analysis, the literature is then reviewed to summarize the concepts behind the success of high‐performance p‐type polymers, along with the latest understanding of the design criteria that will enable further mobility enhancement in n‐type polymers and small molecules, and the reasons why high carrier mobility values have been consistently produced from small molecule/polymer blend semiconductors. Overall, this review brings together important information that aids reliable OTFT data analysis, while providing guidelines for the development of next‐generation organic semiconductors.     

Halogenated Tetraazapentacenes with Electron Mobility as High as 27.8 cm2 V−1 s−1 in Solution‐Processed n‐Channel Organic Thin‐Film Transistors

Molecular engineering of tetraazapentacene with different numbers of fluorine and chlorine substituents fine‐tunes the frontier molecular orbitals, molecular vibrations, and π–π stacking for n‐type organic semiconductors. Among the six halogenated tetraazapentacenes studied herein, the tetrachloro derivative (4Cl‐TAP) in solution‐processed thin‐film transistors exhibits electron mobility of 14.9 ± 4.9 cm² V^?1 s^?1 with a maximum value of 27.8 cm² V^?1 s^?1, which sets a new record for n‐channel organic field‐effect transistors. Computational studies on the basis of crystal structures shed light on the structure–property relationships for organic semiconductors. First, chlorine substituents slightly decrease the reorganization energy of the tetraazapentacene whereas fluorine substituents increase the reorganization energy as a result of fine‐tuning molecular vibrations. Second, the electron transfer integral is very sensitive to subtle changes in the 2D π‐stacking with brickwork arrangement. The unprecedentedly high electron mobility of 4Cl‐TAP is attributed to the reduced reorganization energy and enhanced electron transfer integral as a result of modification of tetraazapentacene with four chlorine substituents.     

Dielectric‐Screening Reduction‐Induced Large Transport Gap in Suspended Sub‐10 nm Graphene Nanoribbon Functional Devices

The predicted quasiparticle energy gap of more than 1 eV in sub‐6 nm graphene nanoribbons (GNRs) is elusive, as it is strongly suppressed by the substrate dielectric screening. The number of techniques that can produce suspended high‐quality and electrically contacted GNRs is small. The helium ion beam milling technique is capable of achieving sub‐5 nm patterning; however, the functional device fabrication and the electrical characteristics are not yet reported. Here, the electrical transport measurement of suspended ≈6 nm wide mono‐ and bilayer GNR functional devices is reported, which are obtained through sub‐nanometer resolution helium ion beam milling with controlled total helium ion budget. The transport gap opening of 0.16–0.8 eV is observed at room temperature. The measured transport gap of the different edge orientated GNRs is in good agreement with first‐principles simulation results. The enhanced electron–electron interaction and reduced dielectric screening in the suspended quasi‐1D GNRs and anti‐ferromagnetic coupling between opposite edges in the zigzag GNRs substantiate the observed large transport gap.     

Quinoline‐Flanked Diketopyrrolopyrrole Copolymers Breaking through Electron Mobility over 6 cm2 V−1 s−1 in Flexible Thin Film Devices

Herein, the design and synthesis of novel π‐extended quinoline‐flanked diketopyrrolopyrrole (DPP) [abbreviated as QDPP] motifs and corresponding copolymers named PQDPP‐T and PQDPP‐2FT for high performing n‐type organic field‐effect transistors (OFETs) in flexible organic thin film devices are reported. Serving as DPP‐flankers in backbones, quinoline is found to effectively tune copolymer optoelectric properties. Compared with TDPP and pyridine‐flanked DPP (PyDPP) analogs, widened bandgaps and strengthened electron deficiency are achieved. Moreover, both hole and electron mobility are improved two orders of magnitude compared to those of PyDPP analogs ( PPyDPP‐T and PPyDPP‐2FT ). Notably, featuring an all‐acceptor‐incorporated backbone, PQDPP‐2FT exhibits electron mobility of 6.04 cm² V^?1 s^?1, among the highest value in OFETs fabricated on flexible substrates to date. Moreover, due to the widened bandgap and strengthened electron deficiency of PQDPP, n‐channel on/off ratio over 10⁵ with suppressed hole transport is first realized in the ambipolar DPP‐based copolymers.