Browsing by Subject "Ionic liquids"
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Item Open Access Dielectric anisotropy in polar solvents under external fields(Institute of Physics Publishing, 2015) Buyukdagli, S.We investigate dielectric saturation and increment in polar liquids under external fields. We couple a previously introduced dipolar solvent model to a uniform electric field and derive the electrostatic kernel of interacting dipoles. This procedure allows an unambiguous definition of the liquid dielectric permittivity embodying non-linear dielectric response and correlation effects. We find that the presence of the external field results in a dielectric anisotropy characterized by a two-component dielectric permittivity tensor. The increase of the electric field amplifies the permittivity component parallel to the field direction, i.e. dielectric increment is observed along the field. However, the perpendicular component is lowered below the physiological permittivity εu ≈ 77, indicating dielectric saturation perpendicular to the field. By comparison with Molecular Dynamics simulations from the literature, we show that the mean-field level dielectric response theory underestimates dielectric saturation. The inclusion of dipolar correlations at the weak-coupling level intensify the mean-field level dielectric saturation and improves the agreement with simulation data at weak electric fields. The correlation-corrected theory predicts as well the presence of a metastable configuration corresponding to the antiparallel alignment of dipoles with the field. This prediction can be verified by solvent-explicit simulations where solvent molecules are expected to be trapped transiently in this metastable state.Item Open Access Electrically controlled terahertz spatial light modulators with graphene arrays(IEEE, 2016) Kakenov, Nurbek; Takan, T.; Özkan, V. A.; Balcı, Osman; Polat, Emre Ozan; Altan, H.; Kocabaş, CoşkunGate-tunable high-mobility electrons on atomically thin graphene layers provide a unique opportunity to control electromagnetic waves in a very broad spectrum. In this paper, we describe an electrically-controlled multipixel terahertz light modulators. The spatial light modulator is fabricated using two large-area graphene layers grown by chemical vapor deposition and transferred on THz transparent and flexible substrates. Room temperature ionic liquid, inserted between the graphene, provides mutual gating between the graphene layers. We used passive matrix addressing to control local charge density thus the THz transmittance. With this device configuration, we were able to obtain 5×5 arrays of graphene modulator with 65% modulation between 0.1 to 1.5 THz.Item Open Access Enhanced tunability of V-shaped plasmonic structures using ionic liquid gating and graphene(Elsevier Ltd, 2016) Ozdemir, O.; Aygar, A. M.; Balci, O.; Kocabas, C.; Caglayan, H.; Özbay, EkmelGraphene is a strong candidate for active optoelectronic devices because of its electrostatically tunable optical response. Current substrate back-gating methods are unable to sustain high fields through graphene unless a high gate voltage is applied. In order to solve this problem, ionic liquid gating is used which allows substrate front side gating, thus eliminating the major loss factors such as a dielectric layer and a thick substrate layer. On the other hand, due to its two dimensional nature, graphene interacts weakly with light and this interaction limits its efficiency in optoelectronic devices. However, V-shaped plasmonic antennas can be used to enhance the incident electric field intensity and confine the electric field near graphene thus allowing further interaction with graphene. Combining V-shaped nanoantennas with the tunable response of graphene, the operation wavelength of the devices that utilize V-shaped antennas can be tuned in situ. In the present paper, we demonstrate a graphene-based device with ionic liquid gating and V- shaped plasmonic antennas to both enhance and more effectively tune the total optical response. We are able to tune the transmission response of the device for up to 389 nm by changing the gate voltage by 3.8 V in the mid-infrared regime.Item Open Access Investigation of electronic properties of ionic liquid electrochemical devices by X-ray photoelectron spectroscopy(Bilkent University, 2016-12) Camcı, MerveAttention towards electrochemical energy storage devices assembled with innovative solvent-free electrolytes ‘ionic liquids’ (ILs) has been progressively rising over the last two decades. In order to design a particular electrochemical device it becomes crucial to understand the structure of interfacial region and the electrical response of ILs. Accordingly, this thesis focuses on Xray Photoelectron Spectroscopic (XPS) investigations of electrochemical devices containing ILs, that is compatible with ultra high vacuum condition needed for XPS. Towards better understanding the fundamental aspects of certain electrochemical issues, electrochemical devices consisting of two metalelectrodes, which contains N,N – Diethyl -N- methyl -N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, (DEME-TFSI) IL-electrolyte between them, have been investigated by XPS under external electrical stimuli control, as a novel analytical tool for elucidating; (i) charging/ discharging phenomena, (ii) electrical double layer (EDL) formation and (iii) electrochemical reaction products. In the first part, a co-planar electrochemical device, with two gold electrodes on porous polyethylene membrane (PEM) plus DEME-TFSI impregnated between the electrodes, has been studied using external DC bias, for recording the position dependent electrical potential variations. In addition, AC bias is used to harvest temporal behavior. For the AC bias a square wave excitation is used, for which two frequencies are adopted corresponding to slow (10 mHz) and fast (1 kHz) time scales, for probing the response of the system at infinite- and zero-time onset, respectively. In all cases XP spectra have been recorded at different lateral positions. As a result of these DC and AC applications a new understanding has surfaced. Accordingly, although at the metal-electrolyte interface the EDL formation is limited to lateral dimensions at the nanometer scale, its visualization through the analysis of the XPS-probed voltage transients can be extended to very large distances from the interface, in the millimeters scale. These responses have also been modeled using a simple equivalent circuit with two oppositely polarized electrodes and an ionic conducting medium in between. In the second part, re-arrangement of the DEME-TFSI’s ionic constituents at the Au electrode/IL-electrolyte interface has been monitored by the dynamic-XPS approach under application of electrical pulses in the form of a slow (1 mHz) triangular wave with an amplitude of 5V, while recording the intensity fluctuations of the two N1s peaks corresponding to the anionic and the cationic fragments. In the last part, the externally bias XPS analysis has been used for insitu and in-vacuo monitoring of anodically triggered electrochemical preparation and characterization of Au NPs in both a co-planar and also in a wire-plane electrode electrochemical geometries. The small sized Au NPs’ formation within the DEME-TFSI medium has been confirmed by the characteristic peak around 470 nm in the Visible spectrum and with the spherical and well-dispersed (~4 nm) particles in TEM images.Item Open Access Lyotropic liquid-crystalline mesophase of lithium triflate-nonionic surfactant as gel electrolyte for graphene optical modulator(American Chemical Society, 2023) Balci, F. M.; Balci, S.; Kocabas, C.; Dag, Ö.Lithium salt (noncoordinating anions, such as lithium triflate (Ltf)) gel electrolytes may be key for the practical use of electrochemical devices. We introduce a new lyotropic liquid-crystalline (LLC) mesophase using Ltf, a small amount of water (as low as 1.3 water per Ltf), and nonionic surfactant (C18H37(OCH2CH2)10OH, C18E10). The LLC phase forms over a broad range of Ltf/C18E10 mole ratios, 2-18. The clear ethanol solution of the ingredients can be either directly spin-coated over a glass substrate to form a gel phase or it can be prepared as a gel by mixing Ltf, water, and C18E10. The mesophase leaches out surfactant molecules at low salt concentrations, but at a salt/surfactant mole ratio of above 8, the phase is homogeneous with a cubic mesostructure, fully transparent in the visible optical region, mechanically flexible, and an effective gel electrolyte. We have observed a large electrostatic doping on graphene with the Fermi energy level of ∼1.0 eV using Ltf-C18E10 gel electrolytes. The Ltf-based gels demonstrate better properties than commonly used ionic liquid electrolyte in graphene optical modulators. The stability of the new gel electrolytes and their superior performance make them suitable electrolytes for use in graphene-based optical modulators.Item Open Access Studies directed toward the synthesis of aspidophytine: construction of its perhydroquinoline core(American Chemical Society, 2016) Türkmen, Y. E.; Gravel, M.; Rawal, V. H.We have developed an efficient route for the synthesis of the perhydroquinoline core of the indole alkaloid aspidophytine (2), starting from commercially available and inexpensive 3-acetylpyridine. This densely functionalized perhydroquinoline core displays four contiguous stereocenters including an all-carbon quaternary center. The synthetic sequence features a highly effective Diels-Alder reaction using a carbamate-substituted siloxy diene accompanied by a spontaneous intramolecular substitution of the newly formed 3°-alkyl bromide with a carbamate group. The installation of the electron-rich aniline moiety was accomplished via a TBSOTf-mediated intramolecular aza-Michael reaction, and the relative stereochemistry of the aza-Michael product (30) was confirmed by X-ray crystallographic analysis. Among the useful transformations that were developed through this study is a highly enantioselective Diels-Alder reaction of a versatile cyclic carbamate siloxy diene.Item Open Access XPS-evidence for in-situ electrochemically-generated carbene formation(Elsevier Ltd., 2017) Gokturk, A. P.; Salzner, U.; Nyulászi, L.; Ulgut, B.; Kocabas, C.; Süzer, ŞefikStable N-heterocyclic carbenes (NHC) are a class of compounds that has attracted a huge amount of interest in the last decade. One way to prepare NHCs is through chemical or electrochemical reduction of 1,3-disubstituted imidazolium cations. We are presenting an in-situ electrochemical X-ray Photoelectron Spectroscopy (XPS) study where electrochemically reduced imidazolium cations lead to production of stable NHC. The electroactive imidazolium species is not only the reactant, but also part of the ionic liquid which serves as the electrolyte, the medium and the electroactive material. This allows us to directly probe the difference between the parent imidazolium ion and the NHC through the use of XPS. The interpretation of the results is supported by both observation of reversible redox peaks in the voltammogram and the density functional theory calculations.