Photonics / Fotonik
Permanent URI for this collectionhttps://hdl.handle.net/11147/2590
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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: 13Citation - Scopus: 15Hybrid J-aggregate-graphene phototransistor(American Chemical Society, 2020) Yakar, Ozan; Balcı, Osman; Uzlu, Burkay; Polat, Nahit; Arı, Ozan; Tunç, İlknur; Balcı, SinanJ-aggregates are fantastic self-assembled chromophores with a very narrow and extremely sharp absorbance band in the visible and near-infrared spectrum, and hence they have found many exciting applications in nonlinear optics, sensing, optical devices, photography, and lasing. In silver halide photography, for example, they have enormously improved the spectral sensitivity of photographic process due to their fast and coherent energy migration ability. On the other hand, graphene, consisting of single layer of carbon atoms forming a hexagonal lattice, has a very low absorption coefficient. Inspired by the fact that J-aggregates have carried the role to sense the incident light in silver halide photography, we would like to use Jaggregates to increase spectral sensitivity of graphene in the visible spectrum. Nevertheless, it has been an outstanding challenge to place isolated J-aggregate films on graphene to extensively study interaction between them. We herein noncovalently fabricate isolated J-aggregate thin films on graphene by using a thin film fabrication technique we termed here membrane casting (MC). MC significantly simplifies thin film formation of water-soluble substances on any surface via porous polymer membrane. Therefore, we reversibly modulate the Dirac point of graphene in the J-aggregate/graphene van der Waals (vdW) heterostructure and demonstrate an all-carbon phototransistor gated by visible light. Owing to the hole transfer from excited excitonic thin film to graphene layer, graphene is hole-doped. In addition, spectral and power responses of the all-carbon phototransistor have been measured by using a tunable laser in the visible spectrum. The first integration of J-aggregates with graphene in a transistor structure enables one to reversibly write and erase charge doping in graphene with visible light that paves the way for using J-aggregate/graphene vdW heterostructures in optoelectronic applications.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: 35Citation - Scopus: 40Two-Dimensional Covalent Crystals by Chemical Conversion of Thin Van Der Waals Materials(American Chemical Society, 2019) Sreepal, Vishnu; Yağmurcukardeş, Mehmet; Vasu, Kalangi S.; Kelly, Daniel J.; Taylor, Sarah F. R.; Şahin, Hasan; Kravets, Vasyl G.; Nair, Rahul R.Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.Article Citation - WoS: 28Citation - Scopus: 28Enhanced Stability of Single-Layer W-Gallenene Through Hydrogenation(American Chemical Society, 2018) Badalov, S. V.; Yağmurcukardeş, Mehmet; Peeters, François M.; Şahin, HasanUsing density functional theory based first-principles calculations, the effect of surface hydrogenation on the structural, dynamical, electronic, and mechanical properties of monolayer washboard-gallenene (w-gallenene) is investigated. It is found that the dynamically stabilized strained monolayer of w-gallenene has a metallic nonmagnetic ground state. Both one-sided and two-sided hydrogenations of w-gallenene suppress its dynamical instability even when unstrained. Unlike one-sided hydrogenated monolayer w-gallenene (os-w-gallenene), two-sided hydrogenated monolayer w-gallenene (ts-w-gallenene) possesses the same crystal structure as w-gallenene. Electronic band structure calculations reveal that monolayers of hydrogenated derivatives of w-gallenene exhibit also metallic nonmagnetic ground state. Moreover, the linear-elastic constants, in-plane stiffness and Poisson ratio, are enhanced by hydrogenation, which is opposite to the behavior of other hydrogenated monolayer crystals. Furthermore, monolayer w-gallenene and ts-w-gallenene remain dynamically stable up to relatively higher biaxial strains as compared to borophene. With its enhanced dynamical stability, robust metallic character, and enhanced linear-elastic properties, hydrogenated monolayer w-gallenene is a potential candidate for nanodevice applications as a two-dimensional flexible metal.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: 15Citation - Scopus: 15Vertical van der waals heterostructure of single layer InSe and SiGe(American Chemical Society, 2019) Eren, İsmail; Özen, Sercan; Sözen, Yiğit; Yağmurcukardeş, Mehmet; Şahin, HasanWe present a first-principles investigation on the stability, electronic structure, and mechanical response of ultrathin heterostructures composed of single layers of InSe and SiGe. First, by performing total energy optimization and phonon calculations, we show that single layers of InSe and SiGe can form dynamically stable heterostructures in 12 different stacking types. Valence and conduction band edges of the heterobilayers form a type-I heterojunction having a tiny band gap ranging between 0.09 and 0.48 eV. Calculations on elastic-stiffness tensor reveal that two mechanically soft single layers form a heterostructure which is stiffer than the constituent layers because of relatively strong interlayer interaction. Moreover, phonon analysis shows that the bilayer heterostructure has highly Raman active modes at 205.3 and 43.7 cm(-1), stemming from the out-of-plane interlayer mode and layer breathing mode, respectively. Our results show that, as a stable type-I heterojunction, ultrathin heterobilayer of InSe/SiGe holds promise for nanoscale device applications.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.Article Citation - WoS: 11Citation - Scopus: 11Structural Stability of Physisorbed Air-Oxidized Decanethiols on Au(111)(American Chemical Society, 2020) Kabanoy, Nikolai; Tsvetanova, Martina; Klaysyuk, Andrey L.; Zandvliet, Harold J. W.; Sotthewes, Kai; Kap, Özlem; Varlıklı, CananWe have studied the dynamic behavior of decanethiol and air-oxidized decanethiol self-assembled monolayers (SAMs) on Au(111) using time-resolved scanning tunneling microscopy at room temperature. The air-oxidized decanethiols arrange in a lamellae-like structure leaving the herringbone reconstruction of the Au(111) surface intact, indicating a rather weak interaction between the molecules and the surface. Successive STM images show that the air-oxidized molecules are structurally more stable as compared to the nonoxidized decanethiol molecules. This is further confirmed by performing current-time traces with the feedback loop disabled at different locations and at different molecular phases. Density function theory calculations reveal that the diffusion barrier of the physisorbed oxidized decanethiol molecule on Au(111) is about 100 meV higher than the diffusion barrier of a chemisorbed Au-decanethiol complex on Au(111). A two-dimensional activity map of individual current-time traces performed on the air-oxidized decanethiol phase reveals that all the dynamic events take place within the vacancy lines between the air-oxidized decanethiols. These results reveal that the oxidation of thiols provides a pathway to produce more robust and stable self-assembled monolayers at ambient conditions.
