Covalent Bond Torsion-Enabled Unique Crystal-Phase Transformation of an Organic Semiconductor for Multicolor Light-Emitting Transistors.

High-mobility and color-tunable highly emissive organic semiconductors (OSCs) are highly promising for various optoelectronic device applications and novel structure-property relationship investigations. However, such OSCs have never been reported because of the great trade-off between mobility, emission color, and emission efficiency. Here, we report a novel strategy of molecular conformation-induced unique crystalline polymorphism to realize the high mobility and color-tunable high emission in a novel OSC, 2,7-di(anthracen-2-yl) naphthalene (2,7-DAN). Interestingly, 2,7-DAN has unique crystalline polymorphism, which has an almost identical packing motif but slightly different molecular conformation enabled by the small bond rotation angle variation between anthracene and naphthalene units. More remarkably, the subtle covalent bond rotation angle change leads to a big change in color emission (from blue to green) but does not significantly modify the mobility and emission efficiency. The carrier mobility of 2,7-DAN crystals can reach up to a reliable 17 cm2 V-1 s-1, which is rare for the reported high-mobility OSCs. Based on the unique phenomenon, high-performance light-emitting transistors with blue to green emission are simultaneously demonstrated in an OSC crystal. These results open a new way for designing emerging multifunctional organic semiconductors toward next-generation advanced molecular (atomic)-scale optoelectronics devices.

[1]  Huanli Dong,et al.  Organic Polarized Light‐Emitting Transistors , 2023, Advanced materials.

[2]  Liwei Liu,et al.  Synchronous Light Harvesting and Energy Storing Organic Cathode Material 1,4-Dihydroxyanthraquinone for Lithium-Ion Batteries , 2023, Chemical Engineering Journal.

[3]  H. Sirringhaus,et al.  SmartMat: Smart materials to Smart world , 2020, SmartMat.

[4]  Huanli Dong,et al.  High‐Efficiency Single‐Component Organic Light‐Emitting Transistors , 2019, Advanced materials.

[5]  Yi Jiang,et al.  Low‐Threshold Organic Semiconductor Lasers with the Aid of Phosphorescent Ir(III) Complexes as Triplet Sensitizers , 2019, Advanced Functional Materials.

[6]  Yang Han,et al.  Recent Progress in High‐Mobility Organic Transistors: A Reality Check , 2018, Advanced materials.

[7]  S. Hecht,et al.  Collective molecular switching in hybrid superlattices for light-modulated two-dimensional electronics , 2018, Nature Communications.

[8]  Yu Huang,et al.  Approaching the Schottky–Mott limit in van der Waals metal–semiconductor junctions , 2018, Nature.

[9]  Qi Wu,et al.  Enhancing Ultralong Organic Phosphorescence by Effective π‐Type Halogen Bonding , 2018 .

[10]  Huanli Dong,et al.  Aromatic Extension at 2,6-Positions of Anthracene toward an Elegant Strategy for Organic Semiconductors with Efficient Charge Transport and Strong Solid State Emission. , 2017, Journal of the American Chemical Society.

[11]  B. Ong,et al.  Enhancing Crystalline Structural Orders of Polymer Semiconductors for Efficient Charge Transport via Polymer‐Matrix‐Mediated Molecular Self‐Assembly , 2016, Advanced materials.

[12]  Deqing Zhang,et al.  Molecular Materials That Can Both Emit Light and Conduct Charges: Strategies and Perspectives. , 2016, Chemistry.

[13]  A. Heeger,et al.  High mobility emissive organic semiconductor , 2015, Nature Communications.

[14]  Hyun Ho Choi,et al.  A Pseudo‐Regular Alternating Conjugated Copolymer Using an Asymmetric Monomer: A High‐Mobility Organic Transistor in Nonchlorinated Solvents , 2015, Advanced materials.

[15]  Zhenan Bao,et al.  Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method , 2014, Nature Communications.

[16]  T. Shin,et al.  Boosting the ambipolar performance of solution-processable polymer semiconductors via hybrid side-chain engineering. , 2013, Journal of the American Chemical Society.

[17]  Zhenghong Lu,et al.  Metal/Metal‐Oxide Interfaces: How Metal Contacts Affect the Work Function and Band Structure of MoO3 , 2013 .

[18]  F. Rosei,et al.  Maximizing field-effect mobility and solid-state luminescence in organic semiconductors. , 2012, Angewandte Chemie.

[19]  Tian Lu,et al.  Multiwfn: A multifunctional wavefunction analyzer , 2012, J. Comput. Chem..

[20]  M. Caironi,et al.  Charge injection engineering of ambipolar field-effect transistors for high-performance organic complementary circuits. , 2011, ACS applied materials & interfaces.

[21]  J. Moon,et al.  High-Detectivity Polymer Photodetectors with Spectral Response from 300 nm to 1450 nm , 2009, Science.

[22]  Ashwini Nangia,et al.  Conformational polymorphism in organic crystals. , 2008, Accounts of chemical research.

[23]  F. Cicoira,et al.  Organic Light Emitting Field Effect Transistors: Advances and Perspectives , 2007 .

[24]  S. W. Thomas,et al.  Chemical sensors based on amplifying fluorescent conjugated polymers. , 2007, Chemical reviews.

[25]  H. Sirringhaus,et al.  Efficient Top‐Gate, Ambipolar, Light‐Emitting Field‐Effect Transistors Based on a Green‐Light‐Emitting Polyfluorene , 2006 .

[26]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[27]  E. W. Meijer,et al.  About Supramolecular Assemblies of π-Conjugated Systems , 2005 .

[28]  Hyun Ho Choi,et al.  Critical assessment of charge mobility extraction in FETs. , 2017, Nature materials.