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: 4Citation - Scopus: 4A Polymeric Copper Complex Based on a Pyrazole Derivative: Synthesis, Spectroscopic, X-Ray, and Biological Activity Studies(John Wiley and Sons Inc., 2024) Amin,M.A.; Diker,H.; Şahin,O.; Varlıklı, Canan; Soliman,A.A.A novel 1D coordination polymeric copper complex based on 4-(4′-nitrophenylhydrazono)-5-trifluoromethyl-2,4-dihydropyrazol-3-one was prepared and characterized spectroscopically and thermally and via X-ray crystallographic investigation. The prepared copper-based structure was proved to have a 1D coordination polymer. X-ray studies showed that the polymeric copper complex was of octahedral geometry, the ligand acted as a bidentate ligand, and the nitro group attached to the ligand acted as a bridging group. The cytotoxic activities of the copper polymer were evaluated including against MCF-7 cells (breast cancer cell line), HepG-2 cells (hepatocellular carcinoma), and HCT-116 cells (colon cancer cell line). The morphological alterations of the complex treated cells were investigated using an inverted microscope. The cell cycle and apoptosis were evaluated and reported. The copper polymer exhibited the best antitumor activity against HepG-2 cells (35.22 ± 4.80 μM) while also causing a decline in the G2/M phase and a remarkable enhancement in the early apoptosis. © 2024 John Wiley & Sons, Ltd.Article Anisotropic Tunability of Vibrational Modes in Black Phosphorus Under Uniaxial Compressive/Tensile Strain(Wiley, 2023) Li, Hao; Kutlu, Tayfun; Carrascoso, Felix; Şahin, Hasan; Munuera, Carmen; Castellanos Gomez, AndresStrain engineering is a powerful strategy for tuning the optical, electrical, vibrational properties of 2D nanomaterials. In this work, a four-point bending apparatus is constructed to apply both compressive and tensile strain on 2D anisotropic black phosphorus flake. Further polarized Raman spectroscopy is used to study the vibrational modes of black phosphorus flakes under uniaxial strain applied along various crystalline orientations. Here, a strong anisotropic blue/redshift of A1g, B2g, and A2g modes is found under compressive/tensile strain, respectively. Interestingly, mode A1g exhibits the maximum/minimum shift while mode B2g and mode A2g present the minimum/maximum shift when the strain is applied along armchair/zigzag direction. Density functional theory calculations are carried out to investigate the anisotropic strain response mechanism, finding that the strain-induced regulation of the PP bond angle, bond length, and especially interlayer interaction has a giant influence on the Raman shift. A four-point bending apparatus is constructed to study the effect of uniaxial strain on the vibrational property of anisotropic black phosphorus. Particularly, strong anisotropy on the Raman blueshift/redshift rate upon compressive/tensile strain can be observed, which results from the strain-induced regulation of the bond angle, bond length, and interlayer interactions according to density functional theory calculation analysis.imageArticle Citation - WoS: 9Citation - Scopus: 9Non-Hermitian Hamiltonians for Linear and Nonlinear Optical Response: a Model for Plexcitons(AIP Publishing LLC, 2023) Finkelstein-Shapiro, Daniel; Mante, Pierre-Adrien; Balcı, Sinan; Zigmantas, Donatas; Pullerits, TonuIn polaritons, the properties of matter are modified by mixing the molecular transitions with light modes inside a cavity. Resultant hybrid light-matter states exhibit energy level shifts, are delocalized over many molecular units, and have a different excited-state potential energy landscape, which leads to modified exciton dynamics. Previously, non-Hermitian Hamiltonians have been derived to describe the excited states of molecules coupled to surface plasmons (i.e., plexcitons), and these operators have been successfully used in the description of linear and third order optical response. In this article, we rigorously derive non-Hermitian Hamiltonians in the response function formalism of nonlinear spectroscopy by means of Feshbach operators and apply them to explore spectroscopic signatures of plexcitons. In particular, we analyze the optical response below and above the exceptional point that arises for matching transition energies for plasmon and molecular components and study their decomposition using double-sided Feynman diagrams. We find a clear distinction between interference and Rabi splitting in linear spectroscopy and a qualitative change in the symmetry of the line shape of the nonlinear signal when crossing the exceptional point. This change corresponds to one in the symmetry of the eigenvalues of the Hamiltonian. Our work presents an approach for simulating the optical response of sublevels within an electronic system and opens new applications of nonlinear spectroscopy to examine the different regimes of the spectrum of non-Hermitian Hamiltonians.Research Project Fullerenlere Alternatif Yeni Asetil Köprülü Perilendiimidlerin Sentezi ve Akseptör Özelliklerinin Fotofiziksel Süreçlerle Araştırılması(2019) Varlıklı, CananOrganik güneş hücresi (OGH) nde elektrik üretimi, donörün ışığı soğruması ekziton oluşumu, ekziton difüzyonu, ayrışması ve elektron transfer süreçleri, elektron ve boşlukların katot ve anotta toplanması ile gerçekleşir. Literatürde birçok farklı elektron verici (D) ve alıcı (A) malzeme geliştirilmektedir. A malzemeleri içerisinde en sık kullanılanlardan birisi fulleren ve türevleridir. Bu türevlerin üretimi oldukça zor ve yüksek maliyetlidir. Bu sebeple, literatürde son 10 yıl da, fulleren içermeyen OGHne olan ilginin arttığı görülmektedir. Perilendiimidler (PDIler), görünür bölgedeki yüksek molar soğurma katsayıları ve elektron ilgileri ile dikkat çekmektedir. Ancak, PDIlerin genel organik çözgenlerdeki çözünürlükleri düşük, agregatlaşma eğilimleri fazladır. Güçlü perilen-perilen etkileşimleri film fazında mikroboyutlara ulaşabilecek kristalitler oluşturabilmektedir. Bu durum ise, ekziton haraketliliğini ve elektron ve boşlukların elektrotlarda toplanmasını olumsuz etkilemektedir. Bu proje kapsamında, izomerik saflıkta 1,6- ve 1,7- bis[(trifenil)(4-etinil-fenil)silan)- N,N′-di(2- etilhekzil)-perilen-3, 4, 9, 10-tetrakarboksilikasit diimid [1,6 ve 1,7-Di(TPhSi)APDI] sentezlenmiş, 1H ve 13C NMR ile karakterize edilmiştir. Saf izomerlerin absorpsiyon ve fotoluminesans özellikleri, indirgenme potansiyelleri, en yüksek enerjili elektron içeren moleküler orbital ve en düşük enerjili elektron içermeyen moleküler orbital enerji seviyeleri tespit edilmiştir. Referans olarak sentezlenen N,N′-di(2-etilhekzil)-perilen-3, 4, 9, 10- tetrakarboksilikasit diimid [PDI(2EH)] ve 1,6- ve 1,7-Di-TPhSiAPDI(2EH) in çözelti ve film fazı fotofiziksel özellikleri incelenmiştir. Yeni sentezlenen PDI türevlerinin ve ticari fulleren türevinin (PCBM), ticari bir donör olan poli[N-9'-heptadekanil-2,7-karbazol-alt-5,5-(4',7'-di-2- thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) ile çözelti ve film fazındaki etkileşimleri izlenerek, karşılaştırılmıştır. Filmlerin morjolojik özellikleri atomik kuvvet mikroskobu ölçümleri ile tespit edilmiştir. 1,7-Di-TPhSiAPDI(2EH) in agregatlaşma eğiliminin ve fotokararlılığının PDI(2EH) den düşük, soğurma dalga boyunun, elektron ilgisinin ve yaşam ömrünün PDI(2EH) den yüksek ve molar soğurma katsayısının PDI(2EH) ile aynı seviyede olduğu tespit edilmiştir. Bu özellikleri ile yeni molekülün uygun D malzeme kullanımı ile hazırlanacak OGH aygıtında, PDI(2EH) den yüksek verim vereceği düşünülmüştür.Preprint Electronic, Magnetic and Vibrational Properties of Single Layer Aluminum Oxide(2022) Özyurt, A. Kutay; Molavali, Deniz; Şahin, HasanThe structural, magnetic, vibrational and electronic properties of single layer aluminum oxide (AlO2) are investigated by performing state-of-the-art first-principles calculations. Total energy optimization and phonon calculations reveal that aluminum oxide forms a distorted octahedral structure (1T'-AlO2) in its single layer limit. It is also shown that surfaces of 1T'-AlO2 display magnetic behavior originating from the O atoms. While the ferromagnetic (FM) state is the most favorable magnetic order for 1T'-AlO2, transformation to a dynamically stable antiferromagnetic (AFM) state upon a slight distortion in the crystal structure is also possible. It is also shown that Raman activities (350-400 cm^-1) obtained from the vibrational spectrum can be utilized to distinguish the possible magnetic phases of the crystal structure. Electronically, both FM and the AFM phases are semiconductors with an indirect band gap and they can form a type-III vdW heterojunction with graphene-like ultra-thin materials. Moreover, it is predicted that presence of oxygen defects that inevitably occur during synthesis and production do not alter the magnetic state, even at high vacancy density. Apparently, ultra-thin 1T'-AlO2 with its stable crystal structure, semiconducting nature and robust magnetic state is a quite promising material for nanoscale device applications.Article Citation - WoS: 13Citation - Scopus: 13A Theoretical Investigation on the Physical Properties of Zirconium Trichalcogenides, Zrs3, Zrse3 and Zrte3 Monolayers(MDPI, 2022) Mortazavi, Bohayra; Shojaei, Fazel; Yağmurcukardeş, Mehmet; Makaremi, Meysam; Zhuang, XiaoyingIn a recent advance, zirconium triselenide (ZrSe3) nanosheets with anisotropic and strain-tunable excitonic response were experimentally fabricated. Motivated by the aforementioned progress, we conduct first-principle calculations to explore the structural, dynamic, Raman response, electronic, single-layer exfoliation energies, and mechanical features of the ZrX3 (X = S, Se, Te) monolayers. Acquired phonon dispersion relations reveal the dynamical stability of the ZrX3 (X = S, Se, Te) monolayers. In order to isolate single-layer crystals from bulk counterparts, exfoliation energies of 0.32, 0.37, and 0.4 J/m2 are predicted for the isolation of ZrS3, ZrSe3, and ZrTe3 monolayers, which are comparable to those of graphene. ZrS3 and ZrSe3 monolayers are found to be indirect gap semiconductors, with HSE06 band gaps of 1.93 and 1.01 eV, whereas the ZrTe3 monolayer yields a metallic character. It is shown that the ZrX3 nanosheets are relatively strong, but with highly anisotropic mechanical responses. This work provides a useful vision concerning the critical physical properties of ZrX3 (X = S, Se, Te) nanosheets.Article Citation - WoS: 32Citation - Scopus: 31Wien Effect in Interfacial Water Dissociation Through Proton-Permeable Graphene Electrodes(Nature Research, 2022) Cai, Junhao; Griffin, Eoin; Guarochico-Moreira, Victor H.; Barry, D.; Xin, B.; Yağmurcukardeş, Mehmet; Zhang, Sheng; Geim, Andre K.; Peeters, François M.; Lozada-Hidalgo, MarceloStrong electric fields can accelerate molecular dissociation reactions. The phenomenon known as the Wien effect was previously observed using high-voltage electrolysis cells that produced fields of about 107 V m−1, sufficient to accelerate the dissociation of weakly bound molecules (e.g., organics and weak electrolytes). The observation of the Wien effect for the common case of water dissociation (H2O ⇆ H+ + OH−) has remained elusive. Here we study the dissociation of interfacial water adjacent to proton-permeable graphene electrodes and observe strong acceleration of the reaction in fields reaching above 108 V m−1. The use of graphene electrodes allows measuring the proton currents arising exclusively from the dissociation of interfacial water, while the electric field driving the reaction is monitored through the carrier density induced in graphene by the same field. The observed exponential increase in proton currents is in quantitative agreement with Onsager’s theory. Our results also demonstrate that graphene electrodes can be valuable for the investigation of various interfacial phenomena involving proton transport.Article Citation - WoS: 5Citation - Scopus: 4Electromagnetically Induced Transparency and Absorption Cross-Over With a Four-Level Rydberg System(IOP Publishing, 2022) Oyun, Yağız; Çakır, Özgür; Sevinçli, SevilayElectromagnetically induced transparency (EIT) and absorption (EIA) are quantum coherence phenomena which result from the interference of excitation pathways. Combining these with Rydberg atoms have opened up many possibilities for various applications. We introduce a theoretical model to study Rydberg-EIT and Rydberg-EIA effects in cold Cs and Rb atomic ensembles in a four-level ladder type scheme taking into account van der Waals type interactions between the atoms. The proposed many-body method for analysis of such systems involves a self-consistent mean field approach and it produces results which display a very good agreement with recent experiments. Our calculations also successfully demonstrate experimentally observed EIT-EIA cross-over in the Rb case. Being able to simulate the interaction effects in such systems has significant importance, especially for controlling the optical response of these.Article Citation - WoS: 40Citation - Scopus: 38Gas Permeation Through Graphdiyne-Based Nanoporous Membranes(Nature Research, 2022) Zhou, Zhihua; Tan, Yongtao; Yang, Qian; Bera, Achintya; Xiong, Zecheng; Yağmurcukardeş, Mehmet; Kim, MinsooNanoporous membranes based on two dimensional materials are predicted to provide highly selective gas transport in combination with extreme permeance. Here we investigate membranes made from multilayer graphdiyne, a graphene-like crystal with a larger unit cell. Despite being nearly a hundred of nanometers thick, the membranes allow fast, Knudsen-type permeation of light gases such as helium and hydrogen whereas heavy noble gases like xenon exhibit strongly suppressed flows. Using isotope and cryogenic temperature measurements, the seemingly conflicting characteristics are explained by a high density of straight-through holes (direct porosity of ∼0.1%), in which heavy atoms are adsorbed on the walls, partially blocking Knudsen flows. Our work offers important insights into intricate transport mechanisms playing a role at nanoscale.
