Scopus İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/395
Browse
9 results
Search Results
Article Citation - WoS: 19Citation - Scopus: 19Understanding and Tailoring Excited State Properties in Solution-Processable Oligo(p-Phenyleneethynylene)s: Highly Fluorescent Hybridized Local and Charge Transfer Character via Experiment and Theory(Amer Chemical Soc, 2021-10-13) Usta, Hakan; Cosut, Bunyemin; Alkan, FahriRod-shaped oligo(p-phenyleneethynylene) (OPE) offers an attractive p-framework for the development of solution-processable highly fluorescent molecules having tunable hybridized local and charge transfer (HLCT) excited states and (reverse) intersystem crossing ((R)ISC) channels. Herein, an HLCT oligo(p-phenyleneethynylene) library was studied for the first time in the literature in detail systematically via experiment and theory. The design, synthesis, and full characterization of a new highly fluorescent (Phi(PL-solution) similar to 1) sky blue emissive 4',4 ''-((2,5-bis((2-ethylhexyl)oxy)-1,4-phenylene)bis(ethyne-2,1-diyl))bis(N,N-diphenyl-[1,1'-bi-phenyl]-4-amine) (2EHO-TPA-PE) was also reported. The new molecule consists of a D'-Ar-pi-D-pi-Ar-D' molecular architecture with an extended pi-spacer and no acceptor unit, and detailed structural, physicochemical, single-crystal, and optoelectronic characterizations were performed. A high solid-state quantum efficiency (Phi(PL-solution) similar to 0.8) was achieved as a result of suppressed exciton-phonon/vibronic couplings (no pi-pi interactions and multiple (14 per dimeric form) strong C-H center dot center dot center dot pi interactions). Strong solution-phase/solid-state dipole-dependent tunable excited state behavior (local excited (LE) -> HLCT -> charge transfer (CT)) and decay dynamics covering a wide spectral region were demonstrated, and the CT state was observed to be highly fluorescent despite extremely large Stokes shift (similar to 130 nm)/fwhm (similar to 125 nm) and significant charge separation (0.75 charge.nm). Employing the Lippert-Mataga model, along with detailed photophysical studies and TDDFT calculations, key relationships between molecular design-electronic structure-exciton characteristics were elucidated with regards to HLCT and hot exciton channel formations. The interstate coupling between CT and LE states and the interplay of this coupling with respect to medium polarity were explored. A key relationship between excited-state symmetry breaking process and the formation of HLCT state was discussed for TPA-ended rod-shaped OPE p-systems. (R)ISC-related delayed fluorescence (tau similar to 2-6 ns) processes were evident following the prompt decays (similar to 0.4-0.9 ns) both in the solution and in the solid-state. As a unique observation, the delayed fluorescence could be tuned and facilitated via small dielectric changes in the medium. Our results and the molecular engineering perspectives presented in this study may provide unique insights into the structural and electronic factors governing tunable excited state and hot-exciton channel formations in OPEs for (un)conventional solution-processed luminescence applications.Article Citation - WoS: 27Citation - Scopus: 29Revisiting the Role of Charge Transfer in the Emission Properties of Carborane-Fluorophore Systems: A TDDFT Investigation(Amer Chemical Soc, 2022-06-05) Tahaoglu, Duygu; Usta, Hakan; Alkan, FahriIn this study, we performed a detailed investigation of the S-1 potential energy surface (PES) of o-carborane-anthracene (o-CB-Ant) with respect to the C-C bond length on o-CB and the dihedral angle between o-CB and Ant moieties. The effects of different substituents (F, Cl, CN, and OH) on carbon- or boron-substituted o-CB, along with a pi-extended acene-based fluorophore, pentacene, on the nature and energetics of S-1 -> S-0 transitions are evaluated. Our results show the presence of a non-emissive S-1 state with an almost pure charge transfer (CT) character for all systems as a result of significant C-C bond elongation (C-C = 2.50-2.56 angstrom) on o-CB. In the case of unsubstituted o-CB-Ant, the adiabatic energy of this CT state corresponds to the global minimum on the S-1 PES, which suggests that the CT state could be involved in emission quenching. Despite large deformations on the o-CB geometry, predicted energy barriers are quite reasonable (0.3-0.4 eV), and the C-C bond elongation can even occur without a noticeable energy penalty for certain conformations. With substitution, it is shown that the dark CT state becomes even more energetically favorable when the substituent shows -M effects (e.g., -CN), whereas substituents showing +M effects (e.g., -OH) can result in an energy increase for the CT state, especially for partially stretched C-C bond lengths. It is also shown that the relative energy of the CT state on the PES depends strongly on the LUMO level of the fluorophore as this state is found to be energetically less favorable compared to other conformations when anthracene is replaced with pi-extended pentacene. To our knowledge, this study shows a unique example of a detailed theoretical analysis on the PES of the S-1 state in o-CB-fluorophore systems with respect to substituents or fluorophore energy levels. Our findings could guide future experimental work in emissive o-CB-fluorophore systems and their sensing/optoelectronic applications.Article Citation - WoS: 13Citation - Scopus: 15Meso-π-extended/Deficient BODIPYs and Low-Band Donor-Acceptor Copolymers for Organic Optoelectronics(Amer Chemical Soc, 2022-02-16) Can, Ayse; Choi, Gi-Seok; Ozdemir, Resul; Park, Soyoon; Park, Jin Su; Lee, Yongchul; Usta, HakanThe realization of pi-deficient acceptors and their donor-acceptor copolymers has become a key research focus for the realization of versatile organic optoelectronic materials and devices. Herein, we demonstrate the theoretical design, synthesis, and physicochemical/optoelectronic characterization of two meso-pi-extended/deficient BODIPY building blocks (2OD-T2BDY and 2OD-TTzBDY) and a library of donor-acceptor copolymers with low band gap (E-g = 1.30-1.35 eV) based on these building blocks. These building blocks, to the best of our knowledge, are the first examples of BODIPYs with meso-pi-extension. A library of BODIPY building blocks with varied meso units/substituents is studied to reveal the meso effects on the semiconducting BODIPY's optoelectronic properties. The building blocks showed favorable pi-acceptor electronic/structural properties with meso-pi-delocalized and stabilized LUMOs (ca. -3.6 eV) and large ground-state dipole moments of 4.9-5.5 D. Consistent with the theoretical/experimental pi-electronic structures, all copolymers functioned as p-type semiconductors in field-effect transistors and as donor materials in the bulk heterojunction organic photovoltaics. Power conversion efficiencies of up to 4.4% with a short-circuit current of 12.07 mA cm(-2) were achieved. This study demonstrates a unique meso-pi-extension strategy to realize BODIPYs with favorable pi-acceptor properties, and our findings could open up future materials design avenues in various organic optoelectronic applications.Article Citation - WoS: 12Citation - Scopus: 14Insights Into Interface Treatments in P-Channel Organic Thin-Film Transistors Based on a Novel Molecular Semiconductor(IEEE-Inst Electrical Electronics Engineers Inc, 2017-05) Liguori, Rosalba; Usta, Hakan; Fusco, Sandra; Facchetti, Antonio; Licciardo, Gian Domenico; Di Benedetto, Luigi; Rubino, AlfredoOrganic thin-film transistors (OTFTs) were fabricated using a novel small molecule, C6-NTTN, as the semiconductor layer in several different architectures. The C6-NTTN layer was deposited via both vacuum evaporation at different substrate temperatures and via solution-processing, which yield maximum hole mobilities of 0.16 and 0.05 cm(2)/V . s, respectively. Surface treatments of the substrate, insulator, and metal contacts used for OTFT fabrication employing polymer films and different self-assembled monolayers were investigated. In particular, in bottom-gate devices, the insulator surface hydrophobicity was optimized by the deposition of poly(methyl methacrylate) or hexamethyldisilazane, while in the top-gate geometry, pentafluorobenzenethiol was efficiently used to modify the substrate surface energy and to change the contact work function. Atomic force microscopy analysis was exploited to understand the relationship between the semiconductor thin-film morphology and the device electrical performance. The results shown here indicate an inverse proportionality between the mobility and the interface trap density, with parameters depending especially on semiconductor-insulator interfacial properties, and a correlation between the threshold voltage and the characteristics of the semiconductor-metal interface.Article Citation - WoS: 5Citation - Scopus: 5Inkjet Printing of Aqueous Silver Inks on Water-Soluble Fabrics for Transient Electronics Applications(Amer Chemical Soc, 2024-07-29) Onses, Zehra Gozutok; Kiremitler, N. Burak; Ozbasaran, Aleyna; Huang, Xian; Onses, Mustafa Serdar; Usta, Hakan; Gozutok Onses, ZehraThere is an urgent need to develop practical routes for manufacturing transient electronic devices to tackle the emerging issue of electronic waste and enable next-generation devices. This study reports additive patterning of conductive layers on industrially available water-soluble nonwoven fabrics composed of poly(vinyl alcohol) (PVA). Aqueous inks composed of reactive silver precursors can be practically patterned over water-soluble fabrics by inkjet printing. The efficient deposition of materials with droplet volumes on the order of picoliters ensures the generation of conductive patterns on a water-soluble fabric using a solution-processable fabrication with aqueous inks. The fabrication of conductive electrodes and transience behavior are studied on PVA fabrics with two different degrees of hydrolysis, providing tunability in the temperature-dependent degradation of the substrate. The application of the printed conductive pads is demonstrated in resistive heaters. The temperature of the fabric can exceed 100 degrees C in less than 15 s at a safe voltage of 3 V. The heater exhibits stable operation under cyclic heating and cooling. The presented approach presents key opportunities in additive patterning of aqueous solutions and colloidal dispersions over water-soluble substrates for transient device applications.Article Citation - WoS: 75Citation - Scopus: 80From 2-Methylimidazole to 1,2,3-Triazole: A Topological Transformation of ZIF-8 and ZIF-67 by Post-Synthetic Modification(Royal Soc Chemistry, 2017) Erkartal, Mustafa; Erkilic, Ufuk; Tam, Benjamin; Usta, Hakan; Yazaydin, Ozgur; Hupp, Joseph T.; Sen, UnalBridging ligand replacement in zeolitic imidazolate frameworks, ZIF-8 and ZIF-67, by 1,2,3-triazole was investigated. A complete substitution of 2-methylimidazole by 1,2,3-triazole resulted in a topological transformation of the parent framework from a sodalite (SOD) network to a diamond (DIA) network.Article Citation - WoS: 20Citation - Scopus: 20Frequency and Electric Field Controllable Photodevice: FYTRONIX Device(Elsevier Science Bv, 2017-08) Tataroglu, A.; Al-Sehemi, Abdullah G.; Ozdemir, Mehmet; Ozdemir, Resul; Usta, Hakan; Al-Ghamdi, Ahmed A.; Yakuphanoglu, F.Al/p-Si/BODIPY/Al diode was fabricated by forming BODIPY organic layer on p-Si having ohmic contact. The electrical and photoresponse properties of the prepared diode were investigated in detail. The current-voltage ( I-V) measurements were performed under dark and various illumination intensities. It is observed that the photocurrent under illumination is higher than the dark current. The transient measurements indicate that the device exhibits both photodiode and photocapacitor behavior. We called this device as FYTRONIX device. The photoresponse behavior of the FYTRONIX device is controlled simultaneously by frequency and electric field. The FYRONIX device can be used as a photoresponse sensor in optoelectronic applications.Article Citation - WoS: 18Citation - Scopus: 20Electrochemical Polymerization of Ambipolar Carbonyl-Functionalized Indenofluorene With Memristive Properties(Elsevier, 2019-08) Figa, Viviana; Usta, Hakan; Macaluso, Roberto; Salzner, Ulrike; Ozdemir, Mehmet; Kulyk, Bohdan; Bruno, MaurizioCarbonyl-functionalized indenofluorene was electropolymerized with a high faradaic efficiency of 85% and the solid state properties of the resulting polymeric thin films were investigated. They displayed modular optical properties depending on their oxidation state. The approach used for inorganic semiconductors was applied to polyindeonofluorene derivative. Mott-Schottky analysis evidenced a switching from p-type to n-type electrical conduction, suggesting an ambipolar behaviour of the polymer. As an application, flexible organic memristors were fabricated and resistive switching properties were observed.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.