Mehmet Ozdemir

Solution-Processable BODIPY-Based Small Molecules for Semiconducting Microfibers in Organic Thin-Film Transistors

Electron-deficient π-conjugated small molecules can function as electron-transporting semiconductors in various optoelectronic applications. Despite their unique structural, optical, and electronic properties, the development of BODIPY-based organic semiconductors has lagged behind that of other π-deficient units. Here, we report the design and synthesis of two novel solution-proccessable BODIPY-based small molecules (BDY-3T-BDY and BDY-4T-BDY) for organic thin-film transistors (OTFTs). The new semiconductors were fully characterized by (1)H/(13)C NMR, mass spectrometry, cyclic voltammetry, UV-vis spectroscopy, photoluminescence, differential scanning calorimetry, and thermogravimetric analysis. The single-crystal X-ray diffraction (XRD) characterization of a key intermediate reveals crucial structural properties. Solution-sheared top-contact/bottom-gate OTFTs exhibited electron mobilities up to 0.01 cm(2)/V·s and current on/off ratios of >10(8). Film microstructural and morphological characterizations indicate the formation of relatively long (∼0.1 mm) and micrometer-sized (1-2 μm) crystalline fibers for BDY-4T-BDY-based films along the shearing direction. Fiber-alignment-induced charge-transport anisotropy (μ∥/μ⊥ ≈ 10) was observed, and higher mobilities were achieved when the microfibers were aligned along the conduction channel, which allows for efficient long-range charge-transport between source and drain electrodes. These OTFT performances are the highest reported to date for a BODIPY-based molecular semiconductor, and demonstrate that BODIPY is a promising building block for enabling solution-processed, electron-transporting semiconductor films.

Nanostructured organic semiconductor films for molecular detection with surface-enhanced Raman spectroscopy.

π-Conjugated organic semiconductors have been explored in several optoelectronic devices, yet their use in molecular detection as surface-enhanced Raman spectroscopy (SERS)-active platforms is unknown. Herein, we demonstrate that SERS-active, superhydrophobic and ivy-like nanostructured films of a molecular semiconductor, α,ω-diperfluorohexylquaterthiophene (DFH-4T), can be easily fabricated by vapour deposition. DFH-4T films without any additional plasmonic layer exhibit unprecedented Raman signal enhancements up to 3.4 × 103 for the probe molecule methylene blue. The combination of quantum mechanical computations, comparative experiments with a fluorocarbon-free α,ω-dihexylquaterthiophene (DH-4T), and thin-film microstructural analysis demonstrates the fundamental roles of the π-conjugated core fluorocarbon substitution and the unique DFH-4T film morphology governing the SERS response. Furthermore, Raman signal enhancements up to ∼1010 and sub-zeptomole (<10-21 mole) analyte detection were accomplished by coating the DFH-4T films with a thin gold layer. Our results offer important guidance for the molecular design of SERS-active organic semiconductors and easily fabricable SERS platforms for ultrasensitive trace analysis.

Design, synthesis, and characterization of α,ω-disubstituted indeno[1,2-b]fluorene-6,12-dione-thiophene molecular semiconductors. Enhancement of ambipolar charge transport through synthetic tailoring of alkyl substituents

A series of indeno[1,2-b]fluorene-6,12-dione-thiophene derivatives with hydrocarbon substituents at α,ω-positions as side groups have been designed and synthesized. The new compounds were fully characterized by 1H/13C NMR, mass spectrometry, cyclic voltammetry, UV-vis absorption spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and melting point measurements. The solid state structure of the indeno[1,2-b]fluorene-6,12-dione acceptor core has been identified based on single-crystal X-ray diffraction (XRD). The structural and electronic properties were also studied using density functional theory calculations, which were found to be in excellent agreement with the experimental findings and provided further insight. The detailed effects of alkyl chain size and orientation on the optoelectronic properties, intermolecular cohesive forces, thin-film microstructures, and charge transport performance of the new semiconductors were investigated. Two of the new solution-processable semiconductors, 2EH-TIFDKT and 2OD-TIFDKT, were deposited as thin-films via solution-shearing, drop-casting, and droplet-pinned crystallization methods, and their morphologies and microstructures were investigated by X-ray diffraction (XRD) and atomic force microscopy (AFM). The solution-processed thin-film transistors based on 2EH-TIFDKT and 2OD-TIFDKT showed ambipolar device operations with electron and hole mobilities as high as 0.12 cm2 V−1 s−1 and 0.02 cm2 V−1 s−1, respectively, with Ion/Ioff ratios of 105 to 106. Here, we demonstrate that rational repositioning of the β-substituents to molecular termini greatly benefits the π-core planarity while maintaining a good solubility, and results in favorable structural and optoelectronic characteristics for more efficient charge-transport in the solid-state. The ambipolar charge carrier mobilities were increased by two–three orders of magnitude in the new indeno[1,2-b]fluorene-6,12-dione-thiophene core on account of the rational side-chain engineering.

Ultralow bandgap molecular semiconductors for ambient-stable and solution-processable ambipolar organic field-effect transistors and inverters

The design and development of novel ambipolar semiconductors is very crucial to advance various optoelectronic technologies including organic complementary (CMOS) integrated circuits. Although numerous high-performance ambipolar polymers have been realized to date, small molecules have been unable to provide high ambipolar performance in combination with ambient-stability and solution-processibility. In this study, by implementing highly π-electron deficient, ladder-type IFDK/IFDM acceptor cores with bithiophene donor units in D–A–D π-architectures, two novel small molecules, 2OD-TTIFDK and 2OD-TTIFDM, were designed, synthesized and characterized in order to achieve ultralow band-gap (1.21–1.65 eV) semiconductors with sufficiently balanced molecular energetics for ambipolarity. The HOMO/LUMO energies of the new semiconductors are found to be −5.47/−3.61 and −5.49/−4.23 eV, respectively. Bottom-gate/top-contact OFETs fabricated via solution-shearing of 2OD-TTIFDM yield perfectly ambient stable ambipolar devices with reasonably balanced electron and hole mobilities of 0.13 cm2 V−1 s−1 and 0.01 cm2 V−1 s−1, respectively with Ion/Ioff ratios of ∼103–104, and 2OD-TTIFDK-based OFETs exhibit ambipolarity under vacuum with highly balanced (μe/μh ∼ 2) electron and hole mobilities of 0.02 cm2 V−1 s−1 and 0.01 cm2 V−1 s−1, respectively with Ion/Ioff ratios of ∼105–106. Furthermore, complementary-like inverter circuits were demonstrated with the current ambipolar semiconductors resulting in high voltage gains of up to 80. Our findings clearly indicate that ambient-stability of ambipolar semiconductors is a function of molecular orbital energetics without being directly related to a bulk π-backbone structure. To the best of our knowledge, considering the processing, charge-transport and inverter characteristics, the current semiconductors stand out among the best performing ambipolar small molecules in the OFET and CMOS-like circuit literature. Our results provide an efficient approach in designing ultralow band-gap ambipolar small molecules with good solution-processibility and ambient-stability for various optoelectronic technologies, including CMOS-like integrated circuits.

A new rod-shaped BODIPY-acetylene molecule for solution-processed semiconducting microribbons in n-channel organic field-effect transistors

BODIPY-based π-conjugated small molecules have been extensively studied in various fields of sensing and biochemical labelling; however, their use in organic optoelectronic applications is very limited. A new solution-processable acceptor–donor–acceptor (A–D–A) type small molecule, BDY-PhAc-BDY, consisting of BODIPY π-acceptors and a rod-shaped 1,4-bis-(thienylethynyl)2,5-dialkoxybenzene π-donor, has been synthesized and fully characterized as a novel n-channel semiconductor in bottom-gate/top-contact organic field-effect transistors (OFETs). The new semiconductor exhibits an electrochemical band gap of 2.12 eV with highly stabilized HOMO/LUMO energy levels of −5.68 eV/−3.56 eV. Single-crystal X-ray diffraction (XRD) analysis of BDY-PhAc-BDY reveals a relatively low “BODIPY-meso-thiophene” dihedral angle (θ = 44.94°), antiparallel π-stacked BODIPY dimers with an interplanar distance of 3.93 A, and strong “C–H⋯π (2.85 A)” interactions. The OFET devices fabricated by solution processing show the formation of highly-crystalline, one-dimensional (1-D) microribbons, which results in clear n-channel semiconductivity with an electron mobility of 0.004 cm2 V−1 s−1 and an on/off current ratio of 105–106. To date, this is the highest reported for BODIPY-based small molecular semiconductors with alkyne linkages. Our results clearly demonstrate that BODIPY is an effective π-acceptor unit for the design of solution-processable, electron-transporting organic semiconductors and easily fabricable 1-D semiconductor micro-/nano-structures for fundamental/applied research in organic optoelectronics.

Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications

The design and development of three-dimensional (3D) nanostructures with high surface-enhanced Raman scattering (SERS) performances have attracted considerable attention in the fields of chemistry, biology, and materials science. Nevertheless, electrospraying of organic small molecules on low-cost flexible substrates has never been studied to realize large-scale SERS-active platforms. Here, we report the facile, efficient, and low-cost fabrication of stable and reproducible Au-coated electrosprayed organic semiconductor films (Au@BDY-4T-BDY) on flexible regular aluminum foil at a large scale (5 cm × 5 cm) for practical SERS and catalytic applications. To this end, a well-designed acceptor-donor-acceptor-type solution-processable molecular semiconductor, BDY-4T-BDY, developed by our group, is used because of its advantageous structural and electrical properties. The morphology of the electrosprayed organic film changes by solution concentration, and two different 3D morphologies with out-of-plane features are obtained. Highly uniform dendritic nanoribbons with sharp needle-like tips and vertically oriented nanoplates (∼50 nm thickness) are achieved when electrospraying solution concentrations of 240 and 253% w/v (mg/mL) are, respectively, used. When these electrosprayed organic films are coated with a nanoscopic thin (30 nm) Au layer, the resulting Au@BDY-4T-BDY platforms demonstrate remarkable SERS enhancement factors up to 1.7 × 106 with excellent Raman signal reproducibility (relative standard deviation ≤ 0.13) for methylene blue over the entire film. Finally, Au@BDY-4T-BDY films showed good catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with rate constants of 1.3 × 10-2 and 9.2 × 10-3 min-1. Our results suggest that electrospraying of rationally designed organic semiconductor molecules on flexible substrates holds great promise to enable low-cost, solution-processed, SERS-active platforms.