PubMed İndeksli Yayınlar Koleksiyonu

Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/397

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Achieving Extreme Solubility and Green Solvent-Processed Organic Field-Effect Transistors: A Viable Asymmetric Functionalization of [1]Benzothieno[3,2-B][1]Benzothiophenes
(American Chemical Society, 2025) Yıldız, T.A.; Deneme, İ.; Usta, H.; 01. Abdullah Gül University; 10. Rektörlük; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 02. Mühendislik Fakültesi
Novel structural engineering strategies for solubilizing high-mobility semiconductors are critical, which enables green solvent processing for eco-friendly, sustainable device fabrication, and unique molecular properties. Here, we introduce a viable asymmetric functionalization approach, synthesizing monocarbonyl [1]benzothieno[3,2-b][1]benzothiophene molecules on a gram scale in two transition-metal-free steps. An unprecedented solubility of up to 176.0 mg·mL–1(at room temperature) is achieved, which is the highest reported to date for a high-performance organic semiconductor. The single-crystal structural analysis reveals a herringbone motif with multiple edge-to-face interactions and nonclassical hydrogen bonds involving the carbonyl unit. The asymmetric backbones adopt an antiparallel arrangement, enabling face-to-face π-π interactions. The mono(alkyl-aryl)carbonyl-BTBT compound, m-C6PhCO-BTBT enables formulations in varied green solvents, including acetone and ethanol, all achieving p-channel top-contact/bottom-gate OFETs in ambient conditions. Charge carrier mobilities of up to 1.87 cm2/V·s (μeff≈ 0.4 cm2/V·s; Ion/Ioff≈ 107–108) were achieved. To the best of our knowledge, this is one of the highest OFET performances achieved using a green solvent. Hansen solubility parameters (HSP) analysis, combined with Scatchard–Hildebrand regular solution theory and single-crystal packing analysis, elucidates this exceptional solubility and reveals unique relationships between molecular structure, interaction energy densities, cohesive energetics, and solute–solvent distances (Ra). An optimal solute–green solvent interaction distance in HSP space proves critical for green solvent-processed thin-film properties. This asymmetric functionalization approach, with demonstrated unique solubility insights, provides a foundation for designing green solvent-processable π-conjugated systems, potentially advancing innovation in sustainable (opto)electronics and bioelectronics. © 2025 Elsevier B.V., All rights reserved.
Citation - WoS: 43
Citation - Scopus: 44
Boronic 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, 2018) Erkartal, Mustafa; Sen, Unal; 01. Abdullah Gül University
Herein, 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.
Citation - WoS: 52
Citation - Scopus: 54
Cadmium-Free and Efficient Type-II InP/ZnO Quantum Dots and Their Application for Leds
(Amer Chemical Soc, 2021) Eren, Guncem Ozgun; Sadeghi, Sadra; Jalali, Houman Bahmani; Ritter, Maximilian; Han, Mertcan; Baylam, Isinsu; Nizamoglu, Sedat; 01. Abdullah Gül University
It is a generally accepted perspective that type-II nanocrystal quantum dots (QDs) have low quantum yield due to the separation of the electron and hole wavefunctions. Recently, high quantum yield levels were reported for cadmium-based typeII QDs. Hence, the quest for finding non-toxic and efficient type-II QDs is continuing. Herein, we demonstrate environmentally benign type-II InP/ZnO/ZnS core/shell/shell QDs that reach a high quantum yield of similar to 91%. For this, ZnO layer was grown on core InP QDs by thermal decomposition, which was followed by a ZnS layer via successive ionic layer adsorption. The small-angle Xray scattering shows that spherical InP core and InP/ZnO core/ shell QDs turn into elliptical particles with the growth of the ZnS shell. To conserve the quantum efficiency of QDs in device architectures, InP/ZnO/ZnS QDs were integrated in the liquid state on blue light-emitting diodes (LEDs) as down-converters that led to an external quantum efficiency of 9.4% and a power conversion efficiency of 6.8%, respectively, which is the most efficient QD-LED using type-II QDs. This study pointed out that cadmium-free type-II QDs can reach high efficiency levels, which can stimulate novel forms of devices and nanomaterials for bioimaging, display, and lighting.
Citation - WoS: 7
Citation - Scopus: 7
Enhancing the Properties of Yttria-Stabilized Zirconia Composites With Zeolitic Imidazolate Framework-Derived Nanocarbons
(Amer Chemical Soc, 2023) Cakan, Niyaz; Issa, Abduselam Abubeker; Alsalman, Hamza; Aliyev, Emin; Duden, Enes Ibrahim; Gurcan Bayrak, Kubra; Sen, Unal; 01. Abdullah Gül University
Ceramic 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.
Citation - WoS: 62
Citation - Scopus: 62
Highly Efficient Deep-Blue Electroluminescence Based on a Solution-Processable A-Π Oligo(p-Phenyleneethynylene) Small Molecule
(Amer Chemical Soc, 2019) Usta, Hakan; Alimli, Dilek; Ozdemir, Resul; Dabak, Salih; Zorlu, Yunus; Alkan, Fahri; Can, Ayse; 01. Abdullah Gül University; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 02. Mühendislik Fakültesi
The 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.
Citation - WoS: 66
Citation - Scopus: 72
Highly Transparent Au-Coated Ag Nanowire Transparent Electrode With Reduction in Haze
(Amer Chemical Soc, 2014) Kim, Taegeon; Canlier, Ali; Cho, Changsoon; Rozyyev, Vepa; Lee, Jung-Yong; Han, Seung Min; 01. Abdullah Gül University
Ag nanowire transparent electrode has excellent transmittance and sheet resistance, yet its optical haze still needs to be improved in order for it to be suitable for display applications. Ag nanowires are known to have high haze because of the geometry of the nanowire and the high light scattering characteristic of the Ag. In this study, a Au-coated Ag nanowire structure was proposed to reduce the haze, where a thin layer of Au was coated on the surface of the Ag nanowires using a mild [Au(en)(2)]Cl-3 galvanic displacement reaction. The mild galvanic exchange allowed for a thin layer of Au coating on the Ag nanowires with minimal truncation of the nanowire, where the average length and the diameter were 13.0 mu m and 60 nm, respectively. The Au-coated Ag nanowires were suspended in methanol and then electrostatically sprayed on a flexible polycarbonate substrate that revealed a clear reduction in haze with a 2-4% increase in total transmittance, sheet resistance ranges of 80-90%, and 8.8-36.8 Ohm/sq. Finite difference time domain simulations were conducted for Au-coated Ag nanowires that indicated a significant reduction in the average scattering from 1 to 0.69 fo Au layer thicknesses of 0-10 nm.
Labyrinthine Microstructures with a High Dipole Moment Boron Complex for Molecular Physically Unclonable Functions
(Amer Chemical Soc, 2025) Yildiz, Tevhide Ayca; Kiremitler, N. Burak; Kayaci, Nilgun; Kalay, Mustafa; Ozcan, Emrah; Deneme, Ibrahim; Usta, Hakan; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 01. Abdullah Gül University; 02. Mühendislik Fakültesi; 10. Rektörlük
The design and development of novel molecular-physically unclonable functions (PUFs) with advanced encoding characteristics and ease of fabrication have recently attracted attention in cryptography, secure authentication, and anticounterfeiting. Here, we report the development of a new high dipole-moment small molecule, InIm-BF2, a difluoroborate complex of an indolyl-imine ligand, and the fabrication of unique labyrinthine patterns through a facile two-step thin film process under ambient conditions. The new molecule has a dipolar, coplanar pi-backbone and arranges in the solid state with antisymmetric cofacial pi-stackings (3.86 & Aring;). These properties, along with short C-Hpi contacts (2.74-2.88 & Aring;) and nonclassical C-HF hydrogen bonds (2.47-2.51 & Aring;) (23.4% and 11.5% of the Hirshfeld surfaces, respectively), drive the formation of amorphous molecular PUF patterns with disordered, short-range interactions. Spin-coating followed by thermal annealing at a moderate temperature produces nanoscopic molecular thin films with intricate labyrinthine patterns. These patterns, characterized by interconnected, irregularly shaped, micron-sized (approximate to 50-100 mu m) features, exhibit excellent PUF characteristics, verified through advanced image analysis and computational algorithms. Unlike randomly positioned isolated features in classical binarized keys, the interconnected labyrinthine patterns possess rich entropy and complex features, directly authenticated via deep-learning methodologies. Our work not only demonstrates a facile, promising approach to fabricating unique high-entropy PUF patterns but also provides critical insights into designing advanced molecular materials for next-generation security applications.
Citation - WoS: 54
Citation - Scopus: 58
Proton Conducting Self-Assembled Metal-Organic Framework/Polyelectrolyte Hollow Hybrid Nanostructures
(Amer Chemical Soc, 2016) Sen, Unal; Erkartal, Mustafa; Kung, Chung-Wei; Ramani, Vijay; Hupp, Joseph T.; Farha, Omar K.; 01. Abdullah Gül University
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.
Citation - WoS: 63
Citation - Scopus: 74
Solution-Processable Bodipy-Based Small Molecules for Semiconducting Microfibers in Organic Thin-Film Transistors
(Amer Chemical Soc, 2016) Ozdemir, Mehmet; Choi, Donghee; Kwon, Guhyun; Zorlu, Yunus; Cosut, Bunyemin; Kim, Hyekyoung; Usta, Hakan; 01. Abdullah Gül University; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 02. Mühendislik Fakültesi
Electron-deficient pi-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 pi-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 H-1/C-13 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 center dot s and current on/off ratios of >10(8). Film microstructural and morphological characterizations indicate the formation of relatively long (similar to 0.1 mm) and micrometer-sized (1-2 mu m) crystalline fibers for BDY-4T-BDY-based films along the shearing direction. Fiber-alignment-induced charge-transport anisotropy (mu?/mu approximate to 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.
Citation - WoS: 10
Citation - Scopus: 11
Solution-Processable Indenofluorenes on Polymer Brush Interlayer: Remarkable N-Channel Field-Effect Transistor Characteristics Under Ambient Conditions
(Amer Chemical Soc, 2023) Can, Ayse; Deneme, Ibrahim; Demirel, Gokhan; Usta, Hakan; 01. Abdullah Gül University; 10. Rektörlük; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 02. Mühendislik Fakültesi
The development of solution-processable n-type molecularsemiconductorsthat exhibit high electron mobility (& mu;(e) & GE;0.5 cm(2)/(V & BULL;s)) under ambient conditions, along withhigh current modulation (I (on)/I (off) & GE; 10(6)-10(7)) andnear-zero turn on voltage (V (on)) characteristics,has lagged behind that of other semiconductors in organic field-effecttransistors (OFETs). Here, we report the design, synthesis, physicochemicaland optoelectronic characterizations, and OFET performances of a libraryof solution-processable, low-LUMO (-4.20 eV) 2,2 & PRIME;-(2,8-bis(3-alkylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile small molecules, & beta;,& beta;& PRIME;-C (n) -TIFDMTs, having varied alkyl chain lengths (n = 8, 12, 16). An intriguing correlation is identifiedbetween the solid-isotropic liquid transition enthalpies andthe solubilities, indicating that cohesive energetics, which are tunedby alkyl chains, play a pivotal role in determining solubility. Thesemiconductors were spin-coated under ambient conditions on denselypacked (grafting densities of 0.19-0.45 chains/nm(2)) ultrathin (& SIM;3.6-6.6 nm) polystyrene-brush surfaces.It is demonstrated that, on this polymer interlayer, thermally induceddispersive interactions occurring over a large number of methyleneunits between flexible alkyl chains (i.e., zipper effect) are criticalto achieve a favorable thin-film crystallization with a proper microstructureand morphology for efficient charge transport. While C-8 and C-16 chains show a minimal zipper effect upon thermalannealing, C-12 chains undergo an extended interdigitationinvolving & SIM;6 methylene units. This results in the formationof large crystallites having lamellar stacking ((100) coherence length & SIM;30 nm) in the out-of-plane direction and highly favorablein-plane & pi;-interactions in a slipped-stacked arrangement. Uninterruptedmicrostructural integrity (i.e., no face-on (010)-oriented crystallites)was found to be critical to achieving high mobilities. The excellentcrystallinity of the C-12-substituted semiconductor thinfilm was also evident in the observed crystal lattice vibrations (phonons)at 58 cm(-1) in low-frequency Raman scattering. Two-dimensionalmicrometer-sized (& SIM;1-3 & mu;m), sharp-edged plate-likegrains lying parallel with the substrate plane were observed. OFETsfabricated by the current small molecules showed excellent n-channelbehavior in ambient with & mu;(e) values reaching & SIM;0.9cm(2)/(V & BULL;s), I (on)/I (off) & SIM; 10(7)-10(8), and V (on) & AP; 0 V. Our study notonly demonstrates one of the highest performing n-channel OFET devicesreported under ambient conditions via solution processing but alsoelucidates significant relationships among chemical structures, molecularproperties, self-assembly from solution into a thin film, and semiconductingthin-film properties. The design rationales presented herein may openup new avenues for the development of high-electron-mobility novelelectron-deficient indenofluorene and short-axis substituted donor-acceptor & pi;-architectures via alkyl chain engineering and interface engineering.
Citation - WoS: 27
Citation - Scopus: 28
Three-Dimensional Au-Coated Electrosprayed Nanostructured BODIPY Films on Aluminum Foil as Surface-Enhanced Raman Scattering Platforms and Their Catalytic Applications
(Amer Chemical Soc, 2017) Yilmaz, Mehmet; Erkartal, Mustafa; Ozdemir, Mehmet; Sen, Unal; Usta, Hakan; Demirel, Gokhan; 01. Abdullah Gül University; 02.07. Malzeme Bilimi ve Nanoteknoloji Mühendisliği; 02. Mühendislik Fakültesi; 02.01. Mühendislik Bilimleri
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 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.

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