WoS İndeksli Yayınlar Koleksiyonu
Permanent URI for this collectionhttps://hdl.handle.net/20.500.12573/394
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Article Citation - WoS: 8Citation - Scopus: 8Writing Chemical Patterns Using Electrospun Fibers as Nanoscale Inkpots for Directed Assembly of Colloidal Nanocrystals(Royal Soc Chemistry, 2020) Kiremitler, N. Burak; Torun, Ilker; Altintas, Yemliha; Patarroyo, Javier; Demir, Hilmi Volkan; Puntes, Victor F.; Onses, M. SerdarApplications that range from electronics to biotechnology will greatly benefit from low-cost, scalable and multiplex fabrication of spatially defined arrays of colloidal inorganic nanocrystals. In this work, we present a novel additive patterning approach based on the use of electrospun nanofibers (NFs) as inkpots for end-functional polymers. The localized grafting of end-functional polymers from spatially defined nanofibers results in covalently bound chemical patterns. The main factors that determine the width of the nanopatterns are the diameter of the NF and the extent of spreading during the thermal annealing process. Lowering the surface energy of the substrates via silanization and a proper choice of the grafting conditions enable the fabrication of nanoscale patterns over centimeter length scales. The fabricated patterns of end-grafted polymers serve as the templates for spatially defined assembly of colloidal metal and metal oxide nanocrystals of varying sizes (15 to 100 nm), shapes (spherical, cube, rod), and compositions (Au, Ag, Pt, TiO2), as well as semiconductor quantum dots, including the assembly of semiconductor nanoplatelets.Article Citation - WoS: 15Citation - Scopus: 14Understanding Plasmon Coupling in Nanoparticle Dimers Using Molecular Orbitals and Configuration Interaction(Royal Soc Chemistry, 2019) Alkan, Fahri; Aikens, Christine M.We perform a theoretical investigation of the electronic structure and optical properties of atomic nanowire and nanorod dimers using DFT and TDDFT. In both systems at separation distances larger than 0.75 nm, optical spectra show a single feature that resembles the bonding dipole plasmon (BDP) mode. A configuration interaction (CI) analysis shows that the BDP mode arises from constructive coupling of transitions, whereas the destructive coupling does not produce significant oscillator strength for such separation distances. At shorter separation distances, both constructive and destructive coupling produce oscillator strength due to wave-function overlap, which results in multiple features in the calculated spectra. Our analysis shows that a charge-transfer plasmon (CTP) mode arises from destructive coupling of transitions, whereas the BDP results from constructive coupling of the same transitions at shorter separation distances. Furthermore, the coupling elements between these transitions are shown to depend heavily on the amount of exact Hartree-Fock exchange (HFX) in the functional, which affects the splitting of CTP and BDP modes. With 50% HFX or more, the CTP and BDP modes mainly merge into a single feature in the spectra. These findings suggest that the effects of exact exchange must be assessed during the prediction of CTP modes in plasmonic systems.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: 25Citation - Scopus: 25Triisopropylsilylethynyl-Substituted Indenofluorenes: Carbonyl Versus Dicyanovinylene Functionalization in One-Dimensional Molecular Crystals and Solution-Processed N-Channel Ofets(Royal Soc Chemistry, 2018) Ozdemir, Resul; Park, Sangyun; Deneme, Ibrahim; Park, Yonghan; Zorlu, Yunus; Alidagi, Husniye Ardic; Usta, HakanThe design and synthesis of novel electron-deficient and solution-processable polycyclic aromatic hydrocarbons offers great opportunities for the development of low-cost and large-area (opto)electronics. Although (trialkylsilyl)ethynyl (R3Si-C?C-) has emerged as a very popular unit to solubilize organic semiconductors, it has been applied only to a limited class of materials that are mostly substituted on short molecular axes. Herein, two novel solution-processable indenofluorene-based semiconductors, TIPS-IFDK and TIPS-IFDM, bearing (triisopropylsilyl)ethynyl end units at 2,8-positions (long molecular axis substitution) were synthesized, and their single-crystal structures, optoelectronic properties, solution-sheared thin-film morphologies/microstructures, and n-channel field-effect responses were studied. In accordance with the DFT calculations, the HOMO/LUMO energies of the new compounds are found to be -5.77/-3.65 eV and -5.84/-4.18 eV for TIPS-IFDK and TIPS-IFDM, respectively, reflecting the high electron deficiency of the new -backbones. Both semiconductors exhibit slightly S-shaped molecular frameworks with highly coplanar IFDK/IFDM -cores, and they form slipped -stacked one-dimensional (1-D) columnar motifs in the solid state. However, substantial differences in the degree of - interactions and stacking distances (4.04 angstrom vs. 3.47 angstrom) were observed between TIPS-IFDK and TIPS-IFDM as a result of carbonyl vs. dicyanovinylene functionalization, which results in a three orders of magnitude variation in the charge carrier mobility of the corresponding thin films. Top-contact/bottom-gate OFETs fabricated via solution-shearing TIPS-IFDM yielded one of the best performances in the (trialkylsilyl)ethynyl literature ((e) = 0.02 cm(2) V-1 s(-1), I-on/I-off = 10(7)-10(8), and V-T approximate to 2 V under ambient atmosphere) for a 1-D polycrystalline semiconductor microstructure. To the best of our knowledge, the molecules presented here are the first examples of n-type semiconductors substituted with (trialkylsilyl)ethynyl groups on their long molecular axes.Article Citation - WoS: 16Citation - Scopus: 16The Hansen Solubility Approach Towards Green Solvent Processing: N-Channel Organic Field-Effect Transistors Under Ambient Conditions(Royal Soc Chemistry, 2024) Deneme, Ibrahim; Yildiz, Tevhide Ayca; Kayaci, Nilgun; Usta, HakanThe adoption of green solvents is of utmost importance for the solution-based fabrication of semiconductor thin films and for the commercialization of (opto)electronic devices, especially in response to evolving regulatory mandates for handling organic materials. Despite the increasing interest in this area, the scarcity of green solvent-processed n-channel OFETs, especially functioning under ambient conditions, highlights the need for further research. In this study, we demonstrated the Hansen solubility approach to study the solubility behavior of an ambient-stable n-type semiconductor, 2,2' -(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile (beta,beta'-C-12-TIFDMT), and to analyze potential green solvents for thin-film processing. The Hansen solubility parameters were determined to be delta(D) = 20.8 MPa1/2, delta(P) = 5.8 MPa1/2, and delta(H) = 5.5 MPa1/2 with a radius (R-0) of 8.3 MPa1/2. A green solvent screening analysis based on the minimal distance constraint and quantitative sustainability score identified ethoxybenzene, anisole, 2-methylanisole, and 2-methyltetrahydrofuran as suitable green solvents (R-a's = 5.17-7.93 MPa1/2 < R-0). A strong thermodynamic correlation was identified between the solubility and the semiconductor-solvent distance in the 3D Hansen solubility space, in which the maximum solubility limit could be estimated with the enthalpy of fusion (Delta H-fus) and melting temperature (T-mp) of the semiconductor. To the best of our knowledge, this relationship between the maximum solubility limit and thermal properties has been established for the first time for organic semiconductors. Bottom-gate/top-contact OFETs fabricated by spin-coating the semiconductor green solutions exhibited mu es reaching similar to 0.2 cm(2) V-1 s(-1) (I-on/I-off similar to 10(6)-10(7) and V-on similar to 0-5 V) under ambient conditions. This device performance, to our knowledge, is the highest reported for an ambient-stable green solvent-processed n-channel OFET. Our HSP-based rational approach and unique findings presented in this study can shed critical light on how green solvents can be efficiently incorporated in solution processing in organic (opto)electronics, and whether ambient-stable n-type semiconductors can continue to play an important role in green OFETs.Article Citation - WoS: 22Citation - Scopus: 24The Design and Fabrication of Supramolecular Semiconductor Nanowires Formed by Benzothienobenzothiophene (BTBT)-Conjugated Peptides(Royal Soc Chemistry, 2018) Khalily, Mohammad Aref; Usta, Hakan; Ozdemir, Mehmet; Bakan, Gokhan; Dikecoglu, F. Begum; Edwards-Gayle, Charlotte; Guler, Mustafa O.pi-Conjugated small molecules based on a [1]benzothieno[3,2-b]benzothiophene (BTBT) unit are of great research interest in the development of solution-processable semiconducting materials owing to their excellent charge-transport characteristics. However, the BTBT -core has yet to be demonstrated in the form of electro-active one-dimensional (1D) nanowires that are self-assembled in aqueous media for potential use in bioelectronics and tissue engineering. Here we report the design, synthesis, and self-assembly of benzothienobenzothiophene (BTBT)-peptide conjugates, the BTBT-peptide (BTBT-C-3-COHN-Ahx-VVAGKK-Am) and the C-8-BTBT-peptide (C-8-BTBT-C-3-COHN-Ahx-VVAGKK-Am), as -sheet forming amphiphilic molecules, which self-assemble into highly uniform nanofibers in water with diameters of 11-13(+/- 1) nm and micron-size lengths. Spectroscopic characterization studies demonstrate the J-type - interactions among the BTBT molecules within the hydrophobic core of the self-assembled nanofibers yielding an electrical conductivity as high as 6.0 x 10(-6) S cm(-1). The BTBT -core is demonstrated, for the first time, in the formation of self-assembled peptide 1D nanostructures in aqueous media for potential use in tissue engineering, bioelectronics and (opto)electronics. The conductivity achieved here is one of the highest reported to date in a non-doped state.Article Citation - WoS: 28Citation - Scopus: 29Symmetric Naphthalenediimidequaterthiophenes for Electropolymerized Electrochromic Thin Films(Royal Soc Chemistry, 2015) Figa, V.; Chiappara, C.; Ferrante, F.; Casaletto, M. P.; Principato, F.; Cataldo, S.; Pignataro, B.A new symmetric naphthalenediimidequaterthiophene (s-NDI2ODT4) was synthesized and exhibited the capability to electropolymerize alone or with EDOT affording polymers with controlled donor/acceptor monomer ratios. s-NDI2ODT4-EDOT-based copolymers showed low band gaps, wide optical absorption ranges extending to the near IR region, tuned electrical properties, thin-film surface morphology and hydrophilicity as well as high coloration efficiency in electrochromic devices.Article Sustainable Next-Generation Color Converters From P. Harmala Seed Extracts for Solid-State Lighting(Royal Soc Chemistry, 2024) Erdem, Talha; Orenc, Ali; Akcan, Dilber; Duman, Fatih; Soran-Erdem, ZelihaTraditional solid-state lighting heavily relies on color converters, which often have a significant environmental footprint. As an alternative, natural materials such as plant extracts could be employed if their low quantum yields (QYs) in liquid and solid states were higher. With this motivation, here, we investigate the optical properties of aqueous P. harmala extract, develop efficient color-converting solids through a cost-effective and environmentally friendly method, and integrate them with light-emitting diodes (LEDs). To achieve high-efficiency solid hosts for P. harmala-based fluorophores, we optically and structurally compare two crystalline and two cellulose-based platforms. Structural analyses reveal that sucrose crystals, cellulose-based cotton, and paper platforms enable a relatively homogeneous distribution of fluorophores compared to KCl crystals. Optical characterization demonstrates that the extracted solution and the extract-embedded paper possess QYs of 75.6% and 44.7%, respectively, whereas the QYs of the cotton, sucrose, and KCl crystals remain below 10%. We demonstrated that the paper host with the highest efficiency causes a blueshift in the P. harmala fluorescence, whereas the cotton host induces a redshift. We attribute this to the passivation of nonradiative transitions related to the structure of the hosts. Subsequently, as a proof-of-concept demonstration, we integrate the as-prepared efficient solids of P. harmala for the first time with a light-emitting diode (LED) chip to produce a color-converting LED. The resulting blue-emitting LED achieves a luminous efficiency of 21.9 lm W-elect(-1) with CIE color coordinates of (0.139, 0.070). These findings mark a significant step toward the utilization of plant-based fluorescent biomolecules in solid-state lighting, offering promising environmentally friendly organic color conversion solutions for future lighting applications.Article Citation - WoS: 25Citation - Scopus: 27Selective Removal of Cationic Micro-Pollutants Using Disulfide-Linked Network Structures(Royal Soc Chemistry, 2017) Atas, Mehmet Sahin; Dursun, Sami; Akyildiz, Hasan; Citir, Murat; Yavuz, Cafer T.; Yavuz, Mustafa SelmanMicropollutants are found in all water sources, even after thorough treatments that include membrane filtration. New ones emerge as complex molecules are continuously produced and discarded after used. Treatment methods and sorbent designs are mainly based on non-specific interactions and, therefore, have been elusive. Here, we developed swellable covalent organic polymers (COP) with great affinity towards micropollutants, such as textile industry dyes. Surprisingly, only cationic dyes in aqueous solution were selectively and completely removed. Studies of the COPs surfaces led to a gating capture, where negatively charged layer attracts cationic dyes and moves them inside the swollen gel through diffusive and hydrophobic interaction of the hydrocarbon fragments. Despite its larger molecular size, crystal violet has been taken the most, 13.4 mg g(-1), surpassing all competing sorbents. The maximum adsorption capacity increased from 12.4 to 14.6 mg and from 8.9 to 11.4 mg when the temperature of dye solution was increased from 20 to 70 degrees C. The results indicated that disulfide-linked COPs are attractive candidates for selectively eliminating cationic dyes from industrial wastewater due to exceptional swelling behaviour, low-cost and easy synthesis.Article Citation - WoS: 16Citation - Scopus: 17Organic and Inorganic Semiconducting Materials-Based SERS: Recent Developments and Future Prospects(Royal Soc Chemistry, 2024) Ozdemir, Resul; Ozkan Hukum, Kubra; Usta, Hakan; Demirel, GokhanSurface-enhanced Raman spectroscopy (SERS) with high sensitivity/selectivity is a powerful analytical tool and has been widely used, particularly in the fields of chemistry, spectroscopy, molecular detection, food safety, anti-counterfeiting, and environmental monitoring. Conventional SERS detection relies on plasmonic materials (e.g., Au and Ag nanostructures) with exceedingly high enhancement factors up to 1012. However, these substrates encounter significant limitations, including poor reproducibility, high cost, lack of selectivity, limited SERS active area leading to inconsistent field enhancement and SERS signals, and the possibility of the photothermal decomposition of the analyte species. These drawbacks have the potential to impede detection accuracy and hinder large-scale practical applications. This review focuses on alternative approaches based on noble metal-free SERS substrates. Considering recent advancements in the field of SERS active platforms, we first introduce the implementation of inorganic compounds, including metal oxides, transition metal sulfides/-selenides/-tellurides, 2-D layered transition metal carbides and nitrides (Mxenes), metal-organic frameworks (MOFs), and single elemental inorganic materials for Raman signal enhancement applications. In the second part of the review, we highlight the fast-growing field of SERS-active organic platforms. Moreover, we discuss the promises and challenges for the future direction of organic and inorganic material-based SERS. Surface-enhanced Raman spectroscopy (SERS) is a powerful analytical tool and has been widely used, in different fields including molecular detection, food safety, anti-counterfeiting, and environmental monitoring.
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