Scopus İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/395
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Article Citation - WoS: 54Citation - Scopus: 57Ultralow Bandgap Molecular Semiconductors for Ambient-Stable and Solution-Processable Ambipolar Organic Field-Effect Transistors and Inverters(Royal Soc Chemistry, 2017) Ozdemir, Resul; Choi, Donghee; Ozdemir, Mehmet; Kwon, Guhyun; Kim, Hyekyoung; Sen, Unal; Usta, HakanThe 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 p-electron deficient, ladder-type IFDK/IFDM acceptor cores with bithiophene donor units in D-A-D pi-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 cm(2) V-1 s(-1) and 0.01 cm(2) V-1 s(-1), respectively with I-on/I-off ratios of similar to 10(3)-10(4), and 2OD-TTIFDK-based OFETs exhibit ambipolarity under vacuum with highly balanced (mu(e)/mu(h) similar to 2) electron and hole mobilities of 0.02 cm(2) V-1 s(-1) and 0.01 cm(2) V-1 s(-1), respectively with I-on/I-off ratios of similar to 10(5)-10(6). 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 p-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.Article Citation - WoS: 28Citation - Scopus: 29Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications(Amer Chemical Soc, 2017-05-16) Yilmaz, Mehmet; Erkartal, Mustafa; Ozdemir, Mehmet; Sen, Unal; Usta, Hakan; Demirel, GokhanThe 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 smalt 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-4TEBDY) on flexible regular aluminum foil at a large scale (5 cm X 5 cm) for practical SERS and catalytic applications. To this end, a well-designed-acceptor-donor-atceptor-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 (similar to 50 nm thickness) are achieved when electrospraying solution concentrations of 240 and 253% w/v.(mgimL) 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 X 10(6) 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 X 10(-2) and 9.2 X 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.Article Citation - WoS: 9Citation - Scopus: 10Synthesis of Benzotriazole Functionalized ZIF-8 by Postsynthetic Modification for Enhanced CH4 and CO2 Uptakes(Elsevier, 2022-08) Erkartal, Mustafa; Incekara, Kaan; Sen, UnalIn this work, a series of functionalized ZIF-8 were synthesized via incorporation of benzotriazole ligands into the framework with a post-synthetic method. The crystal structure and porosity were preserved for all functionalized samples. Although a relatively low percentage of ligand exchange (approximately 10-22%) was observed due to steric and kinetic effects, a remarkable improvement was found in CO2 and CH4 uptake capacities due to the incorporation of more polar N sites into the structure and the change in pore size of the frameworks. The resulting ZIF-8-S5 exhibited 45.17(CO2) and 15.08 (CH4) cm(3) g(-1) at 273 K under 1.2 bar, which corresponds to an enhancement of 20 and 35% compared to pristine ZIF-8. Further, all functionalized samples showed the significant improvement of selective CO2 over N-2.Article Citation - WoS: 108Citation - Scopus: 113Proton Conducting Poly(Vinyl Alcohol) (PVA)/Poly (2-Acrylamido Sulfonic Acid) (PAMPS)/Zeolitic Imidazolate Framework (ZIF) Ternary Composite Membrane(Elsevier, 2016-02) Erkartal, Mustafa; Usta, Hakan; Citir, Murat; Sen, UnalThe design, synthesis and characterization of novel proton exchange membranes (PEMs) are of significant scientific and technological importance for the realization of fuel cells, actuators, and sensors. Here, we demonstrate a novel ternary composite membrane consisting of poly(vinyl alcohol) (PVA), poly (2-acrylamido-2-methylpropane sulfonic acid) (PAMPS), zeolitic imidazolate framework-8 (ZIF-8), which is prepared by physical blending and casting methods. To enhance the water management of the membranes, in situ chemical cross-linking is carried out by glutaraldehyde (GA). During the characterization of the new membranes, FT-IR is used for intermolecular and inter-polymer interactions between different components of the membrane, SEM is used to identify morphology, XRD is used to prove the presence of ZIF-8 nanoparticles, and finally TGA is used for thermal stability. The proton conductivity of the membranes is found to increase with temperature and also with the increasing content of PAMPS. The highest proton conductivity under fully hydrated state at 80 degrees C is measured as 0.134 S cm(-1) for PVA: PAMPS: ZIF-8 (55:40:5) composition. In this study, it is clearly shown that ZIF-8 nanoparticles contribute to the proton conductivity by forming hydrogen bonds with the polymer network in the membrane. The water uptake (WU) and ion exchange capacity (IEC) values are 3.28 (gig) and 1.52 meq g(-1), respectively for the same membrane. To the best our knowledge, this study shows one of the first example of a MOFcontaining membrane with truly high proton conductivities, and both values of proton conductivity and electrochemical properties are comparable to those of well-studied membrane, Nation. (C) 2015 Elsevier B.V. All rights reserved.Article Citation - WoS: 54Citation - Scopus: 58Proton Conducting Self-Assembled Metal-Organic Framework/Polyelectrolyte Hollow Hybrid Nanostructures(Amer Chemical Soc, 2016-08-29) Sen, Unal; Erkartal, Mustafa; Kung, Chung-Wei; Ramani, Vijay; Hupp, Joseph T.; Farha, Omar K.Herein, a room temperature chemical process to synthesize functional, hollow nanostructures from zeolitic imidazolate framework-8 (ZIF-8) and poly(vinylphosphonic acid) (PVPA) is reported. Syntheses are initiated by physically blending the components a process that is accompanied first by encapsulation of ZIF-8 crystallites by PVPA and then by fragmentation of the crystallites. The fragmentation process is driven by partial displacement of the methyl-imidazolate ligands of Zn(II) in ZIF-8 by phosphonate groups on PVPA. Differences in rates of diffusion for the components of the reactive mixture yield a Kirkendall-like effect that is expressed as a hollow-particle morphology. The obtained hollow nanostructures feature hybrid shells containing PVPA, ZIF-8, and their cross-reacted products. The hybrid structures display substantial proton conductivities that increase with increasing temperature, even under the anhydrous conditions prevailing at temperatures above the boiling point of water. For example, at T = 413 K the proton conductivity of ZIF-8@PVPA reaches 3.2 (+/- 0.12) x 10(-3) S cm(-1), a value comparatively higher than that for PVPA (or ZIF-8) in isolation. The high value may reflect the availability in the hybrid structures of free (and partially free), amphoteric imidazole species, and their hydrogen-bonding interactions with phosphonate and/or phosphonic acid units. The persistence of ample conductivity at high temperature reflects the elimination of phosphonic acid group dehydration and dimerization-an effect that strikingly degrades the conductivity of pure PVPA under anhydrous conditions.Article Citation - WoS: 70Citation - Scopus: 69Micro-/Nanostructured Highly Crystalline Organic Semiconductor Films for Surface-Enhanced Raman Spectroscopy Applications(Wiley-VCH Verlag GmbH, 2015-08-11) Yilmaz, Mehmet; Ozdemir, Mehmet; Erdogan, Hakan; Tamer, Ugur; Sen, Unal; Facchetti, Antonio; Demirel, GokhanThe utilization of inorganic semiconductors for surface-enhanced Raman spectroscopy (SERS) has attracted enormous interest. However, despite the technological relevance of organic semiconductors for enabling inexpensive, large-area, and flexible devices via solution processing techniques, these p-conjugated systems have never been investigated for SERS applications. Here for the first time, a simple and versatile approach is demonstrated for the fabrication of novel SERS platforms based on micro-/nanostructured 2,7-dioctyl[1]benzothieno[3,2-b][1] benzothiophene (C8-BTBT) thin films via an oblique-angle vapor deposition. The morphology of C8-BTBT thin films is manipulated by varying the deposition angle, thus achieving highly favorable 3D vertically aligned ribbon-like micro-/nanostructures for a 90 degrees deposition angle. By combining C8-BTBT semiconductor films with a nanoscopic thin Au layer, remarkable SERS responses are achieved in terms of enhancement (approximate to 10(8)), stability (>90 d), and reproducibility (RSD < 0.14), indicating the great promise of Au/C8-BTBT films as SERS platforms. Our results demonstrate the first example of an organic semiconductor-based SERS platform with excellent detection characteristics, indicating that p-conjugated organic semiconductors have a great potential for SERS applications.Article Citation - WoS: 8Citation - Scopus: 8Enhancing the Properties of Yttria-Stabilized Zirconia Composites With Zeolitic Imidazolate Framework-Derived Nanocarbons(Amer Chemical Soc, 2023-12-09) Cakan, Niyaz; Issa, Abduselam Abubeker; Alsalman, Hamza; Aliyev, Emin; Duden, Enes Ibrahim; Gurcan Bayrak, Kubra; Sen, UnalCeramic matrix composites (CMCs) reinforced with nanocarbon have attracted significant interest due to their potential to enhance mechanical, thermal, and electrical properties. Although the investigation of carbon-based materials such as graphene and carbon nanotubes as additives for advanced ceramics has been widespread, the utilization of metal-organic framework (MOF)-derived nanocarbons in CMCs remains largely unexplored. We extended our previous proof-of-concept investigations by demonstrating the effectiveness of a different type of MOF-derived carbon as a reinforcing phase in an alternative ceramic matrix. We employed spark plasma sintering (SPS) to consolidate yttria-stabilized zirconia (YSZ) and zeolitic imidazolate framework (ZIF-67) powder blends at 1300 degrees C and a uniaxial pressure of 50 MPa. YSZ serves as the ceramic matrix, whereas ZIF-67 serves as the nanocarbon source. The composite exhibits a highly significant improvement in fracture toughness with an increase of up to 13% compared to that of the YSZ monolith. The formation of ZIF-derived nanocarbon interlayers is responsible for the observed enhancement in ductility, which can be attributed to their ability to facilitate energy dissipation during crack propagation and inhibit grain growth. Furthermore, the room-temperature electrical conductivity of the sintered samples demonstrates a substantial improvement, primarily due to the in situ formation of nanocarbon-based fillers, reaching an impressive 27 S/m with 10 wt % ZIF-67 content. Based on the results, it can be inferred that the incorporation of in situ MOF-derived nanocarbons into CMCs leads to a substantial improvement in both the mechanical and electrical properties.Conference Object Citation - WoS: 15Citation - Scopus: 16Development of Highly Transparent Pd-Coated Ag Nanowire Electrode for Display and Catalysis Applications(Elsevier Science Bv, 2015-09) Canlier, Ali; Ucak, Umit Volkan; Usta, Hakan; Cho, Changsoon; Lee, Jung-Yong; Sen, Unal; Citir, MuratAg nanowire transparent electrode has excellent transmittance (90%) and sheet resistance (20 Omega/sq), yet there are slight drawbacks such as optical haze and chemical instability against aerial oxidation. Chemical stability of Ag nanowires needs to be improved in order for it to be suitable for electrode applications. In our recent article, we demonstrated that coating Ag nanowires with a thin layer of Au through galvanic exchange reactions enhances the chemical stability of Ag nanowire films highly and also helps to obtain lower haze. In this study, coating of a thin Pd layer has been applied successfully onto the surface of Ag nanowires. A mild Pd complex oxidant [Pd(en)(2)](NO3)(2) was prepared in order to oxidize Ag atoms partially on the surface via galvanic displacement. The mild galvanic exchange allowed for a thin layer (1-2 nm) of Pd coating on the Ag nanowires with minimal truncation of the nanowire, where the average length and the diameter were 12.5 mu m and 59 nm, respectively. The Pd-coated Ag nanowires were suspended in methanol and then electrostatically sprayed on flexible polycarbonate substrates. It has been revealed that average total transmittance remain around 95% within visible spectrum region (400-800 nm) whereas sheet resistance rises up to 175 Omega/sq. To the best of our knowledge, for the first time in the literature, Pd coating was employed on Ag nanowires in order to design transparent electrodes for high transparency and strong chemical resistivity against nanowire oxidation. The current Pd-coated Ag nanowires may render an excellent catalyst system for fuel cell applications, as well as in organic synthesis with relatively low costs since our approach enables the fabrication of these nanowires with a very thin layer of Pd. We believe that mesh form of Pd-coated Ag nanowires will coin a new catalyst concept to the related areas since their sheet conductivity is high enough, and also little amount of Pd displays a large surface area as thin layers. (C) 2015 Elsevier B.V. All rights reserved.Article Citation - WoS: 18Citation - Scopus: 18Boosting the Ceramics With in Situ MOF- Derived Nanocarbons(Amer Chemical Soc, 2023-04-23) Duden, Enes Ibrahim; Bayrak, Kubra Gurcan; Balkan, Mert; Cakan, Niyaz; Demiroglu, Arsen; Ayas, Erhan; Sen, Unal; Gurcan Bayrak, KubraMetal-organic framework (MOF)-derived nano-carbons have emerged as promising materials for energy and environmental applications owing to their high surface area, structural and chemical tunability, and hierarchical porosity. Although various carbon-based materials such as graphene and carbon nanotubes have been extensively used as secondary sintering additives to develop advanced ceramics with improved mechanical, thermal, and electrical properties, the potential of MOF-derived nanocarbon-based materials has not been ex-plored. Here, we report the first use of MOF-derived nanocarbons as a reinforcement phase in ceramic composites. To this end, Al2O3 and zeolitic imidazolate framework (ZIF-8) are used as the ceramic matrix and nanocarbon source, respectively. The ceramic composites are produced by densifying Al2O3 and ZIF-8 powder mixtures using spark plasma sintering (SPS) at 1550 degrees C and uniaxial pressure of 50 MPa. The fracture toughness of the composite increases up to 67% in comparison to an alumina monolith as ZIF-derived nanocarbons form interlayers to assist the dissipation of energy during the crack propagation and inhibit grain growth. The room-temperature electrical conductivity of the sintered samples drastically increases with the in situ formed nanocarbon-based fillers, reaching as high as 1410 S/m for 10 wt % ZIF-8 content. These results constitute an excellent initial step toward boosting the mechanical and electrical properties of ceramic matrix composites with in situ MOF-derived nanocarbons.Article Citation - WoS: 45Citation - Scopus: 47Boronic Acid Moiety as Functional Defect in UiO-66 and Its Effect on Hydrogen Uptake Capacity and Selective Co2 Adsorption: a Comparative Study(Amer Chemical Soc, 2017-12-29) Erkartal, Mustafa; Sen, UnalHerein, we use linker fragmentation approach to introduce boronic acid moieties as functional defects into Zr-based metal organic frameworks (MOFs, UiO-66). Our findings show that the amount of permanently incorporated boronic acid containing ligand is directly dependent on the synthesis method. The accessible boronic acid moieties in the pore surfaces significantly improve the hydrogen uptake values, which are 3.10 and 3.44 wt % at 21 bar, 77 K for dimethylformamide (DMF)/H2O and DMF/HCI synthesis methods, respectively. Also, CO2 selectivity of the resulting MOFs over N-2 and CH4 significantly increases due to the quadrupolar interaction between active surfaces and CO2 molecules. To the best of our knowledge, both hydrogen storage and selectivity of CO2 for UiO-66 are the highest reported values in the literature to date. Furthermore, another striking result that emerged from the high-pressure hydrogen uptake isotherms is the direct correlation between the defects and hysteric adsorption behavior, which may result in the shift from rigidity to flexibility of the framework due to the uncoordinated sites.