WoS İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/394
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Article Citation - WoS: 124Citation - Scopus: 127Molecular Engineering of Organic Semiconductors Enables Noble Metal-Comparable SERS Enhancement and Sensitivity(Nature Publishing Group, 2019-12-03) Demirel, Gokhan; Gieseking, Rebecca L. M.; Ozdemir, Resul; Kahmann, Simon; Loi, Maria A.; Schatz, George C.; Usta, HakanNanostructured molecular semiconductor films are promising Surface-Enhanced Raman Spectroscopy (SERS) platforms for both fundamental and technological research. Here, we report that a nanostructured film of the small molecule DFP-4T, consisting of a fully pi-conjugated diperfluorophenyl-substituted quaterthiophene structure, demonstrates a very large Raman enhancement factor (>10(5)) and a low limit of detection (10(-9) M) for the methylene blue probe molecule. This data is comparable to those reported for the best inorganic semiconductor- and even intrinsic plasmonic metal-based SERS platforms. Photoluminescence spectroscopy and computational analysis suggest that both charge-transfer energy and effective molecular interactions, leading to a small but non-zero oscillator strength in the charge-transfer state between the organic semiconductor film and the analyte molecule, are required to achieve large SERS enhancement factors and high molecular sensitivities in these systems. Our results provide not only a considerable experimental advancement in organic SERS figure-of-merits but also a guidance for the molecular design of more sensitive SERS systems.Article Citation - WoS: 63Citation - Scopus: 63Highly Efficient Deep-Blue Electroluminescence Based on a Solution-Processable A-Π Oligo(p-Phenyleneethynylene) Small Molecule(Amer Chemical Soc, 2019-10-14) Usta, Hakan; Alimli, Dilek; Ozdemir, Resul; Dabak, Salih; Zorlu, Yunus; Alkan, Fahri; Can, AyseThe development of solution-processable fluorescent small molecules with highly efficient deep-blue electroluminescence is of growing interest for organic light-emitting diode (OLED) applications. However, high-performance deep-blue fluorescent emitters with external quantum efficiencies (EQEs) over 5% are still scarce in OLEDs. Herein, a novel highly soluble oligo(p-phenyleneethynylene)-based small molecule, 1,4-bis((2-cyanophenyl)ethynyl)-2,5-bis(2-ethylhexyloxy)benzene (2EHO-CNPE), is designed, synthesized, and fully characterized as a wide band gap (2.98 eV) and highly fluorescent (Phi(PL) = 0.90 (solution) and 0.51 (solid-state)) deep-blue emitter. The new molecule is functionalized with cyano (-CN)/2-ethylhexyloxy (-OCH2CH(C2H5)C4H9) electron-withdrawing/-donating substituents, and ethynylene is used as a pi-spacer to form an acceptor (A)-pi-donor (D)-pi-acceptor (A) molecular architecture with hybridized local and charge transfer (HLCT) excited states. Physicochemical and optoelectronic characterizations of the new emitter were performed in detail, and the single-crystal structure was determined. The new molecule adopts a nearly coplanar pi-conjugated framework packed via intermolecular "C-H center dot center dot center dot pi" and "C-H center dot center dot center dot N" hydrogen bonding interactions without any pi-pi stacking. The OLED device based on 2EHO-CNPE shows an EQE(max) of 7.06% (EQE = 6.30% at 200 cd/m(2)) and a maximum current efficiency (CEmax) of 5.91 cd/A (CE = 5.34 cd/A at 200 cd/m(2)) with a deep-blue emission at CIE of (0.15, 0.09). The electroluminescence performances achieved here are among the highest reported to date for a solution-processed deep-blue fluorescent small molecule, and, to the best of our knowledge, it is the first time that a deep-blue OLED is reported based on the oligo(p-phenyleneethynylene) pi-framework. TDDFT calculations point to facile reverse intersystem crossing (RISC) processes in 2EHO-CNPE from high-lying triplet states to the first singlet excited state (T-2/T-3 -> S-1) (hot-exciton channels) that enable a high radiative exciton yield (eta(r) similar to 69%) breaking the theoretical limit of 25% in conventional fluorescent OLEDs. These results demonstrate that properly designed fluorescent oligo(p-phenyleneethynylenes) can be a key player in high-performance deep-blue OLEDs.Article Citation - WoS: 110Citation - Scopus: 116Bodipy-Based Semiconducting Materials for Organic Bulk Heterojunction Photovoltaics and Thin-Film Transistors(Wiley-VCH Verlag GmbH, 2018-12-13) Ho, Dongil; Ozdemir, Resul; Kim, Hyungsug; Earmme, Taeshik; Usta, Hakan; Kim, ChoongikThe rapid emergence of organic (opto)electronics as a promising alternative to conventional (opto)electronics has been achieved through the design and development of novel pi-conjugated systems. Among various semiconducting structural platforms, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) pi-systems have recently attracted attention for use in organic thin-films transistors (OTFTs) and organic photovoltaics (OPVs). This Review article provides an overview of the developments in the past 10 years on the structural design and synthesis of BODIPY-based organic semiconductors and their application in OTFT/OPV devices. The findings summarized and discussed here include the most recent breakthroughs in BODIPYs with record-high charge carrier mobilities and power conversion efficiencies (PCEs). The most up-to-date design rationales and discussions providing a strong understanding of structure-property-function relationships in BODIPY-based semiconductors are presented. Thus, this review is expected to inspire new research for future materials developments/applications in this family of molecules.Article Citation - WoS: 19Citation - Scopus: 20A Solution-Processable Meso-Phenyl N-Channel Semiconductor With Enhanced Fluorescence Emission(Wiley-VCH Verlag GmbH, 2019-06-26) Ozcan, Emrah; Ozdemir, Mehmet; Ho, Dongil; Zorlu, Yunus; Ozdemir, Resul; Kim, Choongik; Cosut, BunyeminThe cover feature shows the delicate balance between locally excited (LE) and twisted intramolecular charge-transfer (TICT) states, which could be controlled by solvent polarity and nano-aggregation, of a meso-phenyl-BODIPY-based fluorescent semiconductor. The dihedral angle between the meso-aromatic unit and BODIPY pi-core was found to be the key factor in this balance. This is the first report of highly emissive characteristics for an A-D-A type BODIPY-based n-channel semiconductor. Details are given in the Full Paper by B. Cosut, H. Usta, C. Kim, and co-workers (DOI: 10.1002/cplu.201900317).Article Citation - WoS: 29Citation - Scopus: 30A Solution-Processable Liquid-Crystalline Semiconductor for Low-Temperature Air-Stable N-Channel Field-Effect Transistors(Wiley-VCH Verlag GmbH, 2017-02-22) Ozdemir, Resul; Choi, Donghee; Ozdemir, Mehmet; Kim, Hyekyoung; Kostakoglu, Sinem Tuncel; Erkartal, Mustafa; Usta, HakanA new solution-processable and air-stable liquid-crystalline nchannel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl) thiophen-2-yl) indeno[1,2-b] fluorene-6,12-diylidene) dimalononitrile, alpha,omega-2OD-TIFDMT) with donor-acceptor-donor (D-AD) pi conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (approximate to 0.5-1 mu m) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 degrees C) top-contact/bottom-gate OFETs have provided good electron obility values as high as 0.11 cm(2) (Vs)(-1) and high I-on/I-off ratios of 10(7) to 10(8) with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100 V) when compared with the b-substituted parent semiconductor, beta-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen- 2-yl) indeno[1,2-b] fluorene-6,12-diylidene) dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D pi-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that alpha,omega-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.
