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; Balcı, Sinan; Toso, Stefano; Ivanov, Yurii P.; Saleh, Gabriele; Balcı, Sinan; Divitini, Giorgio; Manna, Liberato; 04.04. Department of Photonics; 04. Faculty of Science; 01. Izmir Institute of TechnologyWe 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; Balcı, Fadime Mert; Güvenç, Çetin Meriç; Kocabaş, Çoşkun; Balcı, Sinan; Balcı, Sinan; Polat, Nahit; 04.04. Department of Photonics; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyCarbon 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: 7Citation - Scopus: 6L2[gaxfa1–xpbi3]pbi4 (0 ≤ X ≤ 1) Ruddlesden–popper Perovskite Nanocrystals for Solar Cells and Light-Emitting Diodes(American Chemical Society, 2022) Güvenç, Çetin Meriç; Balcı, Sinan; Tunç, İlknur; Balcı, Sinan; 04.04. Department of Photonics; 04. Faculty of Science; 01. Izmir Institute of TechnologyThe main challenges to overcome for colloidal 2D Ruddlesden–Popper (RP) organo-lead iodide perovskite nanocrystals (NCs) are phase instability and low photoluminescence quantum yield (PLQY). Herein, we demonstrate colloidal synthesis of guanidinium (GA)-L2[GAPbI3]PbI4, formamidinium (FA)-L2[FAPbI3]PbI4, and GA and FA alloyed L2[GA0.5FA0.5PbI3]PbI4 NCs without using polar or high boiling point nonpolar solvents. Importantly, we show that optical properties and phase stability of L2[APbI3]PbI4 NCs can be affectively tuned by alloying with guanidinium and formamidinium cations. Additionally, the band gap of NCs can be rapidly engineered by bromide ion exchange in L2[GAxFA1–xPbI3]PbI4 (0 ≤ x ≤ 1) NCs. Our approach produces a stable dispersion of L2[FAPbI3]PbI4 NCs with 12.6% PLQY that is at least three times higher than the previously reported PLQY in the nanocrystals. Furthermore, L2[GAPbI3]PbI4 and L2[GA0.5FA0.5PbI3]PbI4 NC films exhibit improved ambient stability over 10 days, which is significantly higher than L2[FAPbI3]PbI4 NC films, which transform to an undesired 1D phase within 6 days. The colloidally synthesized guanidinium- and formamidinium-based 2D RP organo-lead iodide perovskite NCs with improved stability and high PLQY demonstrated in this study may find applications in solar cells and light-emitting diodes. Therefore, large A-site cation-alloyed 2D RP perovskite NCs may provide a new way to rationalize high-performance and stable perovskite solar cells and light-emitting diodes.Article Citation - WoS: 16Citation - Scopus: 16Silylethynyl substitution for preventing aggregate formation in perylene diimides(American Chemical Society, 2021) Aksoy, Erkan; Varlıklı, Canan; Danos, Andrew; Li, Chunyong; Monkman, Andrew P.; Varlıklı, Canan; 04.04. Department of Photonics; 04. Faculty of Science; 01. Izmir Institute of TechnologyEthynylene-bridged perylene diimides (PDIs) with different sized silane groups have been synthesized as a steric blocking group to prevent the formation of non-radiative trap sites, for example, strong H-aggregates and other dimers or excimers. Excited singlet-state exciton dynamics were investigated by time-resolved photoluminescence and ultrafast pump-probe transient absorption spectroscopy. The spectra of the excimer or dimer aggregates formed by the PDIs at high concentrations were also determined. Although the photophysical properties of the bare and shielded PDIs are identical at micromolar concentrations, more shielded PDI2 and PDI3 exhibited resistance to aggregation, retaining higher photoluminescence quantum yield even at 10 mM concentration and in neat films. The PDIs also exhibited high photostability (1 h of continuous excitation), as well as electrochemical stability (multiple cycles with cyclic voltammetry). Prevention of dimer/aggregate formation in this manner will extend the uses of PDIs to a variety of high concentration photonics and optoelectronic applications, such as organic light-emitting diodes, organic photovoltaics, and luminescent solar concentrators.Article Citation - WoS: 2Citation - Scopus: 31-Octanol Is a Functional Impurity Modifying Particle Size and Photophysical Properties of Colloidal Zncdsse/Zns Nanocrystals(American Chemical Society, 2021) Sevim Ünlütürk, Seçil; Özçelik, Serdar; Çağır, Ali; Varlıklı, Canan; Varlıklı, Canan; Çağır, Ali; Özçelik, Serdar; 04.01. Department of Chemistry; 04.04. Department of Photonics; 04. Faculty of Science; 01. Izmir Institute of TechnologyImpurities in trioctylphophine (TOP) strongly affect nanocrystal synthesis. 1-Octanol among other contaminants in TOP is identified for the first time as a functional impurity by H-1 NMR. The deliberate addition of 1-octanol into trioctylphosphine reduced particle size and modified photophysical properties of ZnCdSSe/ZnS colloidal nanocrystals. NMR analysis furthermore revealed that 1-octanol is bonded to the nanocrystal surfaces. The ratio of integrals for the O-CH2 protons of 1-octanol, which is the lowest compared to the other ligands, suggests that 1-octanol plays a critical role to tune the particle size of nanocrystals. The increased amount of 1-octanol added into TOP reduces the particle size from 9.8 to 7.2 nm, causing a progressive blue shift in the UV-vis and PL spectra but leaving the alloy composition unaffected. The rate of nonradiative processes is enhanced with the amount of 1-octanol added into TOP, correlating with higher dislocation density observed in the nanocrystals. As a conclusion, 1-octanol is proposed as a functional impurity that varies particle size and nonradiative photophysical processes in the ZnCdSSe/ZnS colloidal nanocrystals.Article Citation - WoS: 13Citation - Scopus: 15Hybrid J-aggregate-graphene phototransistor(American Chemical Society, 2020) Yakar, Ozan; Polat, Nahit; Balcı, Osman; Arı, Ozan; Uzlu, Burkay; Balcı, Sinan; Polat, Nahit; Arı, Ozan; Tunç, İlknur; Balcı, Sinan; 04.04. Department of Photonics; 01. Izmir Institute of Technology; 04. Faculty of ScienceJ-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: 25Citation - Scopus: 25Colloidal Bimetallic Nanorings for Strong Plasmon Exciton Coupling(American Chemical Society, 2020) Güvenç, Çetin Meriç; Polat, Nahit; Mert Balcı, Fadime; Balcı, Sinan; Sarısözen, Sema; Balcı, Fadime Mert; Polat, Nahit; Balcı, Sinan; 04.04. Department of Photonics; 04.01. Department of Chemistry; 04. Faculty of Science; 01. Izmir Institute of TechnologyNobel-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; Varlıklı, Canan; Tsvetanova, Martina; Kap, Özlem; Klaysyuk, Andrey L.; Zandvliet, Harold J. W.; Sotthewes, Kai; Kap, Özlem; Varlıklı, Canan; 04.04. Department of Photonics; 03.09. Department of Materials Science and Engineering; 03. Faculty of Engineering; 04. Faculty of Science; 01. Izmir Institute of TechnologyWe 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.Article Citation - WoS: 7Citation - Scopus: 7Fabrication of a Postfunctionalizable, Biorepellent, Electroactive Polyurethane Interface on a Gold Surface by Surface-Assisted Polymerization(American Chemical Society, 2020) Özenler, Sezer; Özenler, Sezer; Sözen, Yiğit; Sözen, Yiğit; Şahin, Hasan; Yıldız, Ümit Hakan; Yıldız, Ümit Hakan; Şahin, Hasan; 04.01. Department of Chemistry; 01. Izmir Institute of Technology; 04.04. Department of Photonics; 04. Faculty of ScienceThis study describes surface-assisted (SurfAst) urethane polymerization, providing a modular/postfunctionalizable, biorepellent, electroactive similar to 10 to 100 nm-thick polyurethane (PU) interface on a gold surface. SurfAst is a functionalization methodology based on sequential incubation steps of alkane diisocyanates and alkanediol monomers. The gold surface is functionalized by alkane diisocyanates in the first incubation step, and our theoretical calculations reveal that while the isocyanate group atoms (N, C, and O) at one end of the molecule exhibits strong interactions (similar to 900 meV) with surface atoms, the other end group remains unreacted. After the first incubation step, sequential alkanediol and alkane diisocyanate incubations provide formation of the PU interface. The extensive analysis of the PU interface has been conducted via X-ray photoelectron spectroscopy, and the chemical mapping verifies that the interface is made of PU moieties. The topographical analysis of the surface conducted by the atomic force microscopy shows that the PU interface consists of mostly a nanoporous texture with 150 nm total roughness. The adherence force mapping of the PU interface reveals that the nanoporous matrix exhibits an adhesion force of about 14 nN. The electrostatic force microscopy characterizing long-range electrostatic interactions (40 nm) shows that the PU interface has been attracted by positively charged species as compared to negative objects. Finally, it is demonstrated that the PU interface is readily postfunctionalizable by polyethylene glycol (PEG 1000), serving as a biorepellent interface and preserving electroactivity. We foresee that SurfAst polymerization will have potential for the facile fabrication of a postfunctionalizable and modular biointerface which might be utilized for biosensing and bioelectronic applications.