Materials Science and Engineering / Malzeme Bilimi ve Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/4719
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Article Citation - WoS: 7Citation - Scopus: 7Breaking the Boundaries of the Goldschmidt Tolerance Factor With Ethylammonium Lead Iodide Perovskite Nanocrystals(American Chemical Society, 2024) Güvenç, Çetin Meriç; Toso, Stefano; Ivanov, Yurii P.; Saleh, Gabriele; Balcı, Sinan; Divitini, Giorgio; Manna, LiberatoWe report the synthesis of ethylammonium lead iodide (EAPbI3) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large A-cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larger lattice parameter compared to the Cs-, methylammonium- and formamidinium-based lead halide perovskite homologues. As a consequence, EAPbI3 nanocrystals are highly unstable, evolving to a nonperovskite delta-EAPbI3 polymorph within 1 day. Also, EAPbI3 nanocrystals are very sensitive to electron irradiation and quickly degrade to PbI2 upon exposure to the electron beam, following a mechanism similar to that of other hybrid lead iodide perovskites (although degradation can be reduced by partially replacing the EA+ ions with Cs+ ions). Interestingly, in some cases during this degradation the formation of an epitaxial interface between (EA x Cs1-x )PbI3 and PbI2 is observed. The photoluminescence emission of the EAPbI3 perovskite nanocrystals, albeit being characterized by a low quantum yield (similar to 1%), can be tuned in the 664-690 nm range by regulating their size during the synthesis. The emission efficiency can be improved upon partial alloying at the A site with Cs+ or formamidinium cations. Furthermore, the morphology of the EAPbI3 nanocrystals can be chosen to be either nanocube or nanoplatelet, depending on the synthesis conditions.Article Citation - WoS: 17Citation - Scopus: 19Strong Coupling of Carbon Quantum Dots in Liquid Crystals(American Chemical Society, 2022) Sarısözen, Sema; Polat, Nahit; Mert Balcı, Fadime; Güvenç, Çetin Meriç; Kocabaş, Çoşkun; Yağlıoğlu, Halime Gül; Balcı, SinanCarbon quantum dots (CDs) have recently received a tremendous amount of interest owing to their attractive optical properties. However, CDs have broad absorption and emission spectra limiting their application ranges. We herein, for the first time, show synthesis of water-soluble red emissive CDs with a very narrow line width (∼75 meV) spectral absorbance and hence demonstrate strong coupling of CDs and plasmon polaritons in liquid crystalline mesophases. The excited state dynamics of CDs has been studied by ultrafast transient absorption spectroscopy, and CDs display very stable and strong photoluminescence emission with a quantum yield of 35.4% and a lifetime of ∼2 ns. More importantly, we compare J-aggregate dyes with CDs in terms of their absorption line width, photostability, and ability to do strong coupling, and we conclude that highly fluorescent CDs have a bright future in the mixed light-matter states for emerging applications in future quantum technologies.Article Citation - WoS: 12Citation - Scopus: 14Laser Assisted Synthesis of Anisotropic Metal Nanocrystals and Strong Light-Matter Coupling in Decahedral Bimetallic Nanocrystals(Royal Society of Chemistry, 2021) Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Güvenç, Çetin Meriç; Karadeniz, Uğur; Tertemiz, Necip Ayhan; Balcı, SinanThe advances in colloid chemistry and nanofabrication allowed us to synthesize noble monometallic and bimetallic nanocrystals with tunable optical properties in the visible and near infrared region of the electromagnetic spectrum. In the strong coupling regime, surface plasmon polaritons (SPPs) of metal nanoparticles interact with excitons of quantum dots or organic dyes and plasmon-exciton hybrid states called plexcitons are formed. Until now, various shaped metal nanoparticles such as nanorods, core-shell nanoparticles, hollow nanoparticles, nanoprisms, nanodisks, nanorings, and nanobipyramids have been synthesized to generate plasmon-exciton mixed states. However, in order to boost plasmon-exciton interaction at nanoscale dimensions and expand the application of plexcitonic nanocrystals in a variety of fields such as solar cells, light emitting diodes, and nanolasers, new plexcitonic nanocrystals with outstanding optical and chemical properties remain a key goal and challenge. Here we report laser-assisted synthesis of decahedral shaped noble metal nanocrystals, tuning optical properties of the decahedral shaped nanocrystals by galvanic replacement reactions, colloidal synthesis of bimetallic decahedral shaped plexcitonic nanocrystals, and strong plasmon-plasmon interaction in bimetallic decahedral shaped noble metal nanocrystals near a metal film. We photochemically synthesize decahedral Ag nanoparticles from spherical silver nanoparticles by using a 488 nm laser. The laser assisted synthesis of silver nanoparticles yields decahedral (bicolored) and prism (monocolored) shaped silver nanocrystals. The decahedral shaped nanoparticles were selectively separated from prism shaped nanoparticles by centrifugation. The optical properties of decahedral nanocrystals were tuned by the galvanic replacement reaction between gold ions and silver atoms. Excitons of J-aggregate dyes and SPPs of decahedral bimetallic nanoparticles strongly couple and hence decahedral shaped plexcitonic nanoparticles are prepared. In addition, localized SPPs of decahedral shaped bimetallic nanocrystals interact strongly with the propagating SPPs of a flat silver film and hence new hybrid plasmonic modes (plasmonic nanocavities) are generated. The experimental results are further fully corroborated by theoretical calculations including decahedral shaped plexcitonic nanoparticles and decahedral nanoparticles coupled to flat metal films.Article Citation - WoS: 13Citation - Scopus: 14Strong Plasmon-Exciton Coupling in Colloidal Halide Perovskite Nanocrystals Near a Metal Film(Royal Society of Chemistry, 2020) Güvenç, Çetin Meriç; Polat, Nahit; Balcı, SinanAll inorganic colloidal halide perovskite nanoplatelets and nanowires are highly anisotropic shaped semiconductor nanocrystals with highly tunable optical properties in the visible spectrum. These nanocrystals have large exciton binding energies and high oscillator strengths due to their strongly quantum confined natures. The optical properties of the halide perovskites are tunable by variation of halide composition and morphology of the nanocrystals. We herein demonstrate that colloidal perovskite nanocrystals (NCs) placed in close proximity to chemically functionalized metal films show mixed plasmon-exciton formation, plexciton formation, in the strong coupling regime. The optical properties of all-inorganic lead halide perovskite NCs were controlled by colloidally synthesizing NCs with different morphologies such as nanowires and nanoplatelets or by controlling the composition of the halides in the NCs. The experimentally observed Rabi splitting energies are around 90 meV, 70 meV, and 55 meV for CsPbI3 nanoplatelets, CsPbI3 nanowires, and CsPb(Br/I)(3) nanoplatelets, respectively. In addition, the numerical simulations are in good agreement with the experimentally obtained data. The results show that colloidal all-inorganic halide perovskite NCs are promising and strong candidates for studying light-matter interaction at nanoscale dimension.Article Citation - WoS: 3Citation - Scopus: 3Green Fabrication of Lanthanide-Doped Hydroxide-Based Phosphors: Y(oh)(3):eu3+ Nanoparticles for White Light Generation(Beilstein-Institut Zur Forderung der Chemischen Wissenschaften, 2019) Güner, Tuğrul; Kuş, Anılcan; Özcan, Mehmet; Genç, Aziz; Şahin, Hasan; Demir, Mustafa MuammerPhosphors can serve as color conversion layers to generate white light with varying optical features, including color rendering index (CRI), high correlated color temperature (CCT), and luminous efficacy. However, they are typically produced under harsh synthesis conditions such as high temperature, high pressure, and/or by employing a large amount of solvent. In this work, a facile, water-based, rapid method has been proposed to fabricate lanthanide-doped hydroxide-based phosphors. In this sense, sub-micrometer-sized Y(OH)(3):Eu3+ particles (as red phosphor) were synthesized in water at ambient conditions in <= 60 min reaction time. The doping ratio was controlled from 2.5-20 mol %. Additionally, first principle calculations were performed on Y(OH)(3):Eu3+ to understand the preferable doping scenario and its optoelectronic properties. As an application, these fabricated red phosphors were integrated into a PDMS/YAG:Ce3+ composite and used to generate white light. The resulting white light showed a remarkable improvement (approximate to 24%) in terms of luminous efficiency, a slight reduction of CCT (from 3900 to 3600 K), and an unchanged CRI (approximate to 60) as the amount of Y(OH)(3):Eu3+ was increased.Article Citation - WoS: 4Citation - Scopus: 4Color-Tunable All-Inorganic Cspbbr3 Perovskites Nanoplatelet Films for Photovoltaic Devices(American Chemical Society, 2019) Özcan, Mehmet; Özen, Sercan; Topçu, Gökhan; Demir, Mustafa Muammer; Şahin, HasanHerein, we demonstrate a novel coating approach to fabricate CsPbBr3 perovskite nanoplatelet film with heat-free process via electrospraying from precursor solution. A detailed study is carried out to determine the effect of various parameters such as ligand concentration, electric field, flow rate, etc. on the optical properties. By controlling the volume ratios of the oleylamine (OAm) and oleic acid (OA), the coalescing and thickness of the resulting nanoplatelets can be readily tuned that results in control over emission in the range of 100 nm without any antisolvent crystallization or heating processes. The varying electrical field and flow rate was found as inefficient on the emission characteristics of the films. In addition, the crystal films were obtained under ambient conditions on the ITO coated glass surfaces as in the desired pattern. As a result, we demonstrated a facile and reproducible way of synthesizing and coating of CsPbBr3 perovskite nanoplatelets which is suitable for large-scale production. In this method, the ability of tuning the degree of quantum confinement for perovskite nanoplatelets is promising approach for the one-step fabrication of crystal films that may enable the use in optoelectronics.Article Citation - WoS: 30Citation - Scopus: 32Perylene-Embedded Electrospun Ps Fibers for White Light Generation(Elsevier Ltd., 2019) Güner, Tuğrul; Aksoy, Erkan; Demir, Mustafa Muammer; Varlıklı, CananPerylene dyes have been employed in the fabrication of white light due to their superior photophysical properties and relatively easy synthetic methods. However, their molecular aggregation in solid state is one of the main handicaps since it causes deviation in their optical properties and quenches photoluminescence quantum yields (Phi(f)). Investigation of the photophysical properties of a green (PTE), a yellow (PDI) and a new red (DiPhAPDI) emitting perylene derivative in solution, drop-casted films, polystyrene (PS) fibers and PS fibers embedded in poly (dimethyl siloxane) (PDMS) showed that PS:dye fibers prevent aggregation to some extend and allows high Of of dyes. The Of values of PTE, PDI and DiPhAPDI were all higher than 93.0% in solution and 84.8%, 94.3% and 73.6%, respectively in PS:dye fibers. Embedding the fibers in PDMS improved the photostabilities of the dyes two folds compared to their solution phases. The prepared dye containing fibers were combined together into a single PDMS film and utilized as a frequency conversion layer on a blue LED. Fabricated samples were found to show high color rendering index (>= 90), adjustable CCT (7500 K-5000 K), and power efficiency values exceeding 2001m/W depending on the used fiber amount in mass.Article Citation - WoS: 93Citation - Scopus: 95Single-Layer Janus-Type Platinum Dichalcogenides and Their Heterostructures(American Chemical Society, 2019) Kahraman, Zeynep; Kandemir, Ali; Yağmurcukardeş, Mehmet; Şahin, HasanUltrathin two-dimensional Janus-type platinum dichalcogenide crystals formed by two different atoms at opposite surfaces are investigated by performing state-of-the-art density functional theory calculations. First, it is shown that single-layer PtX2 structures (where X = S, Se, or Te) crystallize into the dynamically stable IT phase and are indirect band gap semiconductors. It is also found that the substitutional chalcogen doping in all PtX2 structures is favorable via replacement of surface atoms with a smaller chalcogen atom, and such a process leads to the formation of Janus-type platinum dichalcogenides (XPtY, where X and Y stand for S, Se, or Te) which are novel single-layer crystals. While all Janus structures are indirect band gap semiconductors as their binary analogues, their Raman spectra show distinctive features that stem from the broken out-of-plane symmetry. In addition, it is revealed that the construction of Janus crystals enhances the piezoelectric constants of PtX2 crystals significantly both in the in plane and in the out-of-plane directions. Moreover, it is shown that vertically stacked van der Waals heterostructures of binary and ternary (Janus) platinum dichalcogenides offer a wide range of electronic features by forming bilayer heterojunctions of type-I, type-II, and type-III, respectively. Our findings reveal that Janus-type ultrathin platinum dichalcogenide crystals are quite promising materials for optoelectronic device applications.Article Citation - WoS: 10Citation - Scopus: 12The Effect of Dopa Hydroxyl Groups on Wet Adhesion To Polystyrene Surface: an Experimental and Theoretical Study(Elsevier, 2020) Yıldız, Remziye; Özen, Sercan; Şahin, Hasan; Akdoğan, YaşarMussels wet adhesive performance has been arousing curiosity for a long time. It is found that 3,4-dihydroxyphenylalanine (DOPA) is responsible for adhesive properties of mussels. Despite a large body of research characterizing the interactions DOPA with hydrophilic surfaces, relatively few works have addressed the mechanism of interactions with hydrophobic surfaces. The benzene ring of DOPA is the main attributor to the adhesion on hydrophobic polystyrene (PS) surface. However, here we showed that two hydroxyl groups of catechol have also effects on wet adhesion. We studied wet adhesive properties of DOPA, tyrosine and phenylalanine functionalized PEG polymers, PEG-(N-Boc-L-DOPA)(4), PEG-(N-Boc-L-Tyrosine)(4), PEG-(N-Boc-L-Phenylalanine)(4), on spin labeled PS nanobeads (SL-PS) by electron paramagnetic resonance (EPR) spectroscopy. Surface coverage ratio of SL-PS upon additions of PEG-(N-Boc-L-DOPA)(4), PEG-(N-Boc-L-Tyrosine)(4) and PEG-(N-Boc-L-Phenylalanine)(4) showed that SL-PS was covered with 70%, 50% and 0%, respectively. This showed that spontaneous wet adhesion on PS increases with the number of amino acids hydroxyl groups. This is also supported with the density functional theory (DFT) energy calculations and ab-initio molecular dynamics (AIMD) simulations. In water, interactions between water molecules and hydroxyl groups on the catechol induce catechol adhesion via 7C-7C stacking between the catechol and double styrene rings which were already tilted out with water.Article Citation - WoS: 25Citation - Scopus: 25Colloidal Bimetallic Nanorings for Strong Plasmon Exciton Coupling(American Chemical Society, 2020) Güvenç, Çetin Meriç; Mert Balcı, Fadime; Sarısözen, Sema; Polat, Nahit; Balcı, SinanNobel-metal nanostructures strongly localize and manipulate light at nanoscale dimension by supporting surface plasmon polaritons. In fact, the optical properties of the nobel-metal nanostructures strongly depend on their morphology and composition. Until now, various metal nanostructures such as nanocubes, nanoprisms, nanorods, and recently hollow nanostructures have been demonstrated. In addition, the plasmonic field can be further enhanced at nanoparticle dimers and aggregates because of highly localized and intense optical fields, which is known as "plasmonic hot spots". However, colloidally synthesized and circular-shaped nanoring nanostructures with plasmonic hot spots are still lacking. We, herein, show for the first time that colloidal bimetallic nanorings with plasmonic nanocavities and tunable plasmon resonance wavelengths can be synthesized via colloidal synthesis and galvanic replacement reactions. In addition, in the strong coupling regime, plasmons in nanorings and excitons in J-aggregates interact strongly and nanoring-shaped colloidal plexcitonic nanoparticles are demonstrated. The results reveal that the optical properties of the nanoring and the onset of strong coupling can be tamed by the galvanic replacement reaction. Further, the plasmonic nanocavity in the nanorings has immense potential for applications in sensing and spectroscopy because of the space, enclosed by the plasmonic nanocavity, is empty and accessible to a variety of molecules, ions, and quantum dots.
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