Browsing by Subject "Charge transfer"
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Item Open Access Anatase TiO2 nanowires functionalized by organic sensitizers for solar cells: a screened Coulomb hybrid density functional study(American Institute of Physics Inc., 2015) Ünal, H.; Gunceler, D.; Gülseren, O.; Ellialtıoğlu, S.; Mete, E.The adsorption of two different organic molecules cyanidin glucoside (C21O11H20) and TA-St-CA on anatase (101) and (001) nanowires has been investigated using the standard and the range separated hybrid density functional theory calculations. The electronic structures and optical spectra of resulting dye-nanowire combined systems show distinct features for these types of photochromophores. The lowest unoccupied molecular orbital of the natural dye cyanidin glucoside is located below the conduction band of the semiconductor while, in the case of TA-St-CA, it resonates with the states inside the conduction band. The wide-bandgap anatase nanowires can be functionalized for solar cells through electron-hole generation and subsequent charge injection by these dye sensitizers. The intermolecular charge transfer character of Donor-π-Acceptor type dye TA-St-CA is substantially modified by its adsorption on TiO2 surfaces. Cyanidin glucoside exhibits relatively stronger anchoring on the nanowires through its hydroxyl groups. The atomic structures of dye-nanowire systems re-optimized with the inclusion of nonlinear solvation effects showed that the binding strengths of both dyes remain moderate even in ionic solutions.Item Open Access Atomic strings of group IV, III-V, and II-VI elements(American Institute of Physics, 2004) Tongay, S.; Durgun, Engin; Çıracı, SalimA systematic first-principles study of atomic strings made by group IV, III-V, and II-VI elements has revealed interesting mechanical, electronic, and transport properties. The double bond structure underlies their unusual properties. We found that linear chain of C, Si, Ge, SiGe, GaAs, InSb, and CdTe are stable and good conductor, although their parent diamond (zincblende) crystals are covalent (polar) semiconductors but, compounds SiC, BN, AlP, and ZnSe are semiconductors. First row elements do not form zigzag structures.Item Open Access Changes in the resistance to corrosion of thermally passivated titanium aluminide during exposure to sodium chloride solution(Kluwer Academic Publishers, 2015) Saebnoori, E.; Shahrabi, T.; Jafarian H.; Ghaffari, M.In this study the surface of Ti-47Al-2Cr (at. %) was modified by heating and exposure to nitrogen gas flow to form a predominantly oxide layer on the surface. Samples were then immersed in Ringer's solution and 3.5 wt. % sodium chloride solution and electrochemical impedance spectroscopy tests were performed at regular intervals. The results showed that the layer is highly resistant to corrosion. The equivalent circuit proposed for the impedance curves includes a Warburg element, because diffusion is controlling charge transfer through the passive surface layer. The resistance of the layer was not significantly reduced even after 300 h exposure to solutions and scanning electron micrographs showed the surface was not damaged. © 2013 Springer Science+Business Media Dordrecht.Item Open Access Colloidal nanoplatelet/conducting polymer hybrids: excitonic and material properties(American Chemical Society, 2016) Guzelturk, B.; Menk, F.; Philipps, K.; Kelestemur Y.; Olutas M.; Zentel, R.; Demir, Hilmi VolkanHere we present the first account of conductive polymer/colloidal nanoplatelet hybrids. For this, we developed DEH-PPV-based polymers with two different anchor groups (sulfide and amine) acting as surfactants for CdSe nanoplatelets, which are atomically flat semiconductor nanocrystals. Hybridization of the polymers with the nanoplatelets in the solution phase was observed to cause strong photoluminescence quenching in both materials. Through steady-state photoluminescence and excitation spectrum measurements, photoluminescence quenching was shown to result from dominant exciton dissociation through charge transfer at the polymer/nanoplatelet interfaces that possess a staggered (i.e., type II) band alignment. Importantly, we found out that sulfide-based anchors enable a stronger emission quenching than amine-based ones, suggesting that the sulfide anchors exhibit more efficient binding to the nanoplatelet surfaces. Also, shorter surfactants were found to be more effective for exciton dissociation as compared to the longer ones. In addition, we show that nanoplatelets are homogeneously distributed in the hybrid films owing to the functional polymers. These nanocomposites can be used as building blocks for hybrid optoelectronic devices, such as solar cells.Item Open Access Comment on "modeling the electrical conduction in DNA nanowires: Charge transfer and lattice fluctuation theories"(American Physical Society, 2016) Panahi, M.; Chitsazanmoghaddam, M.In a recent paper [S. Behnia and S. Fathizadeh, Phys. Rev. E 91, 022719 (2015)10.1103/PhysRevE.91.022719] an analytical approach is proposed for the investigation of the conductivity properties of DNA. The authors use mean Lyapunov exponent methods as the backbone of their approach and try to interpret properties of the system based on its behavior. Their interpretation regarding the change in nature of the mean Lyapunov exponent at the denaturation temperatures and discussions of stability and instability based on the mean Lyapunov exponent method are questioned. Moreover there is misunderstanding between mean Lyapunov exponent and Lyapunov exponent. © 2016 American Physical Society.Item Open Access Computational modeling of quantum-confined impact ionization in Si nanocrystals embedded in SiO2(2007) Sevik, C.; Bulutay, C.Injected carriers from the contacts to delocalized bulk states of the oxide matrix via Fowler-Nordheim tunneling can give rise to quantum-confined impact ionization (QCII) of the nanocrystal (NC) valence electrons. This process is responsible for the creation of confined excitons in NCs, which is a key luminescence mechanism. For a realistic modeling of QCII in Si NCs, a number of tools are combined: ensemble Monte Carlo (EMC) charge transport, ab initio modeling for oxide matrix, pseudopotential NC electronic states together with the closed-form analytical expression for the Coulomb matrix element of the QCII. To characterize the transport properties of the embedding amorphous SiO2, ab initio band structure and density of states of the α-quartz phase of SiO2 are employed. The confined states of the Si NC are obtained by solving the atomistic pseudopotential Hamiltonian. With these ingredients, realistic modeling of the QCII process involving a SiO2 bulk state hot carrier and the NC valence electrons is provided.Item Open Access Electronic structure of the contact between carbon nanotube and metal electrodes(American Institute of Physics, 2003) Dag, S.; Gülseren, O.; Çıracı, Salim; Yildirim, T.Our first-principles study of the contact between a semiconducting single-walled carbon nanotube ~s-SWNT! and metal electrodes shows that the electronic structure and potential depend strongly on the type of metal. The s-SWNT is weakly side-bonded to the gold surface with minute charge rearrangement and remains semiconducting. A finite potential barrier forms at the contact region. In contrast, the molybdenum surface forms strong bonds, resulting in significant charge transfer and metallicity at the contact. The radial deformation of the tube lowers the potential barrier at the contact and increases the state density at the Fermi level.Item Open Access Fabrication of supramolecular n/p-nanowires via coassembly of oppositely charged peptide-chromophore systems in aqueous media(American Chemical Society, 2017-07) Khalily, M. A.; Bakan, G.; Kucukoz, B.; Topal, A. E.; Karatay, A.; Yaglioglu, H. G.; Dana, A.; Güler, Mustafa O.Fabrication of supramolecular electroactive materials at the nanoscale with well-defined size, shape, composition, and organization in aqueous medium is a current challenge. Herein we report construction of supramolecular charge-transfer complex one-dimensional (1D) nanowires consisting of highly ordered mixed-stack π-electron donor-acceptor (D-A) domains. We synthesized n-type and p-type β-sheet forming short peptide-chromophore conjugates, which assemble separately into well-ordered nanofibers in aqueous media. These complementary p-type and n-type nanofibers coassemble via hydrogen bonding, charge-transfer complex, and electrostatic interactions to generate highly uniform supramolecular n/p-coassembled 1D nanowires. This molecular design ensures highly ordered arrangement of D-A stacks within n/p-coassembled supramolecular nanowires. The supramolecular n/p-coassembled nanowires were found to be formed by A-D-A unit cells having an association constant (KA) of 5.18 × 105 M-1. In addition, electrical measurements revealed that supramolecular n/p-coassembled nanowires are approximately 2400 and 10 times more conductive than individual n-type and p-type nanofibers, respectively. This facile strategy allows fabrication of well-defined supramolecular electroactive nanomaterials in aqueous media, which can find a variety of applications in optoelectronics, photovoltaics, organic chromophore arrays, and bioelectronics.Item Open Access High-efficiency optical gain in type-II semiconductor nanocrystals of alloyed colloidal quantum wells(American Chemical Society, 2017) Guzelturk, B.; Kelestemur Y.; Olutas M.; Li, Q.; Lian, T.; Demir, Hilmi VolkanColloidal nanocrystals having controlled size, tailored shape, and tuned composition have been explored for optical gain and lasing. Among these, nanocrystals having Type-II electronic structure have been introduced toward low-threshold gain. However, to date, their performance has remained severely limited due to diminishing oscillator strength and modest absorption cross-section. Overcoming these problems, here we realize highly efficient optical gain in Type-II nanocrystals by using alloyed colloidal quantum wells. With composition-tuned core/alloyed-crown CdSe/CdSexTe1-x quantum wells, we achieved amplified spontaneous emission thresholds as low as 26 μJ/cm2, long optical gain lifetimes (τgain ≈ 400 ps), and high modal gain coefficients (gmodal ≈ 930 cm-1). We uncover that the optical gain in these Type-II quantum wells arises from the excitations localized to the alloyed-crown region that are electronically coupled to the charge-transfer state. These alloyed heteronanostructures exhibiting remarkable optical gain performance are expected to be highly appealing for future display and lighting technologies.Item Open Access Lateral and vertical heterostructures of h-GaN/h-AlN: electron confinement, band lineup, and quantum structures(American Chemical Society, 2017-11) Onen, A.; Kecik, D.; Durgun, Engin; Çıracı, SalimLateral and vertical heterostructures constructed of two-dimensional (2D) single-layer h-GaN and h-AlN display novel electronic and optical properties and diverse quantum structures to be utilized in 2D device applications. Lateral heterostructures formed by periodically repeating narrow h-GaN and h-AlN stripes, which are joined commensurately along their armchair edges, behave as composite semiconducting materials. Direct-indirect characters of the fundamental band gaps and their values vary with the widths of these stripes. However, for relatively wider stripes, electronic states are confined in different stripes and make a semiconductor-semiconductor junction with normal band alignment. This way one-dimensinonal multiple quantum well structures can be generated with electrons and holes confined to h-GaN stripes. Vertical heterostructures formed by thin stacks of h-GaN and h-AlN are composite semiconductors with a tunable fundamental band gap. However, depending on the stacking sequence and number of constituent sheets in the stacks, the vertical heterostructure can transform into a junction, which displays staggered band alignment with electrons and holes separated in different stacks. The weak bonds between the cations and anions in adjacent layers distinguish these heterostructures from those fabricated using thin films of GaN and AlN thin films in wurtzite structure, as well as from van der Waals solids. Despite the complexities due to confinement effects and charge transfer across the interface, the band diagram of the heterostructures in the direct space and band lineup are conveniently revealed from the electronic structure projected to the atoms or layers. Prominent features in the optical spectra of the lateral composite structures are observed within the limits of those of 2D parent constituents; however, significant deviations from pristine 2D constituents are observed for vertical heterostructures. Important dimensionality effects are revealed in the lateral and vertical heterostructures.Item Open Access Mo2C as a high capacity anode material: a first-principles study(Royal Society of Chemistry, 2016) Çakir, D.; Sevik, C.; Gülseren, O.; Peeters, F. M.The adsorption and diffusion of Li, Na, K and Ca atoms on a Mo2C monolayer are systematically investigated by using first principles methods. We found that the considered metal atoms are strongly bound to the Mo2C monolayer. However, the adsorption energies of these alkali and earth alkali elements decrease as the coverage increases due to the enhanced repulsion between the metal ions. We predict a significant charge transfer from the ad-atoms to the Mo2C monolayer, which indicates clearly the cationic state of the metal atoms. The metallic character of both pristine and doped Mo2C ensures a good electronic conduction that is essential for an optimal anode material. Low migration energy barriers are predicted as small as 43 meV for Li, 19 meV for Na and 15 meV for K, which result in the very fast diffusion of these atoms on Mo2C. For Mo2C, we found a storage capacity larger than 400 mA h g-1 by the inclusion of multilayer adsorption. Mo2C expands slightly upon deposition of Li and Na even at high concentrations, which ensures the good cyclic stability of the atomic layer. The calculated average voltage of 0.68 V for Li and 0.30 V for Na ions makes Mo2C attractive for low charging voltage applications.Item Open Access Morphological control of mesoporosity and nanoparticles within Co3O4-CuO electrospun nanofibers: quantum confinement and visible light photocatalysis performance(American Chemical Society, 2017-09) Pradhan, A. C.; Uyar, TamerThe one-dimensional (1D) mesoporous and interconnected nanoparticles (NPs) enriched composite Co3O4-CuO nanofibers (NFs) in the ratio Co:Cu = 1/4 (Co3O4-CuO NFs) composite have been synthesized by electrospinning and calcination of mixed polymeric template. Not merely the mesoporous composite Co3O4-CuO NFs but also single mesoporous Co3O4 NFs and CuO NFs have been produced for comparison. The choice of mixed polymer templates such as polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) for electrospinning is responsible for the formation of 1D mesoporous NFs. The HR-TEM result showed evolution of interconnected nanoparticles (NPs) and creation of mesoporosity in all electrospun NFs. The quantum confinement is due to NPs within NFs and has been proved by the surface-enhanced Raman scattering (SERS) study and the UV-vis-NRI diffuse reflectance spectra (DRS). The high intense photoluminescence (PL) spectra showing blue shift of all NFs also confirmed the quantum confinement phenomena. The lowering of PL spectrum after mixing of CuO in Co3O4 nanofibers framework (Co3O4-CuO NFs) proved CuO as an efficient visible light response low cost cocatalyst/charge separator. The red shifting of the band gap in composite Co3O4-CuO NFs is due to the internal charge transfer between Co2+ to Co3+ and Cu2+, proved by UV-vis absorption spectroscopy. Creation of oxygen vacancies by mixing of CuO and Co3O4 also prevents the electron-hole recombination and enhances the photocatalytic activity in composite Co3O4-CuO NFs. The photocurrent density, Mott-Schottky (MS), and electrochemical impedance spectroscopy (EIS) studies of all NFs favor the high photocatalytic performance. The mesoporous composite Co3O4-CuO NFs exhibits high photocatalytic activity toward phenolic compounds degradation as compared to the other two NFs (Co3O4 NFs and CuO NFs). The kinetic study of phenolic compounds followed first order rate equation. The high photocatalytic activity of composite Co3O4-CuO NFs is attributed to the formation of mesoporosity and interconnected NPs within NFs framework, quantum confinement, extended light absorption property, internal charge transfer, and effective photogenerated charge separations.Item Open Access Nanograined surface shell wall controlled ZnO–ZnS core–shell nanofibers and their shell wall thickness dependent visible photocatalytic properties(Royal Society of Chemistry, 2017) Ranjith, K. S.; Senthamizhan A.; Balusamy, B.; Uyar, TamerThe core-shell form of ZnO-ZnS based heterostructural nanofibers (NF) has received increased attention for use as a photocatalyst owing to its potential for outstanding performance under visible irradiation. One viable strategy to realize the efficient separation of photoinduced charge carriers in order to improve catalytic efficiency is to design core-shell nanostructures. But the shell wall thickness plays a vital role in effective carrier separation and lowering the recombination rate. A one dimensional (1D) form of shell wall controlled ZnO-ZnS core-shell nanofibers has been successfully prepared via electrospinning followed by a sulfidation process. The ZnS shell wall thickness can be adjusted from 5 to 50 nm with a variation in the sulfidation reaction time between 30 min and 540 min. The results indicate that the surfaces of the ZnO nanofibers were converted to a ZnS shell layer via the sulfidation process, inducing visible absorption behavior. Photoluminescence (PL) spectral analysis indicated that the introduction of a ZnS shell layer improved electron and hole separation efficiency. A strong correlation between effective charge separation and the shell wall thickness aids the catalytic behavior of the nanofiber network and improves its visible responsive nature. The comparative degradation efficiency toward methylene blue (MB) has been studied and the results showed that the ZnO-ZnS nanofibers with a shell wall thickness of ∼20 nm have 9 times higher efficiency than pristine ZnO nanofibers, which was attributed to effective charge separation and the visible response of the heterostructural nanofibers. In addition, they have been shown to have a strong effect on the degradation of Rhodamine B (Rh B) and 4-nitrophenol (4-NP), with promising reusable catalytic efficiency. The shell layer upgraded the nanofiber by acting as a protective layer, thus avoiding the photo-corrosion of ZnO during the catalytic process. A credible mechanism for the charge transfer process and a mechanism for photocatalysis supported by trapping experiments in the ZnO-ZnS heterostructural system for the degradation of an aqueous solution of MB are also explicated. Trapping experiments indicate that h+ and OH are the main active species in the ZnO-ZnS heterostructural catalyst, which do not effectively contribute in a bare ZnO catalytic system. Our work also highlights the stability and recyclability of the core-shell nanostructure photocatalyst and supports its potential for environmental applications. We thus anticipate that our results show broad potential in the photocatalysis domain for the design of a visible light functional and reusable core-shell nanostructured photocatalyst.Item Open Access Physics of nonradiative energy transfer in the complex media of 0D, 2D and 3D materials(Bilkent University, 2016-07) Yeltik, AydanQuantum-confined colloidal nanostructures with strong excitonic properties have emerged as promising light harvesting components in photonics and optoelectronics over the past 20 years. With their favorable photophysical characteristics, three-dimensional-confined colloidal quantum dots and 2D-confined colloidal quantum wells have garnered great attention in the fields ranging from biology and chemistry to physics and engineering. It is technologically significant to utilize the key characteristics of these brightly luminescent nanomaterials through hybridizing and/or interfacing with various technological materials including 3D bulk silicon, graphene based 2D structures such as graphene oxide and reduced graphene oxide, and 2D layered transition metal dichalcogenides such as molybdenum disulphide. Compelling partnership of these appealing materials can be achieved through the nonradiative energy transfer (NRET), which is a phenomenon involving both the exciton and charge transfer mechanisms. Along with the hybrids of low dimensional particles with the conventional bulk materials, the closely interacting structures of these colloidal and layered nanomaterials have widespread interest at both the fundamental science and application levels. From these physical and technological points of view, in this thesis, we addressed important scientific problems and proposed innovative solutions including both the experimental and theoretical approaches in interfacing complex media of 0D, 2D and 3D materials and showing strong NRET interactions. Our key achievements include high excitonic enhancement in silicon and graphene based materials with the integration of nanoparticles, comprehensive photophysical investigation of the newly emerging nanomaterials and successful tailoring of the colloidal nanostructures to the next-generation optoelectronic applications.Item Open Access Plasmon-coupled photocapacitor neuromodulators(American Chemical Society, 2020) Melikov, R.; Srivastava, S. B.; Karatum, O.; Doğru-Yüksel, I. B.; Jalali, H. B.; Sadeghi, S.; Dikbaş, U. M.; Ülgüt, Burak; Kavaklı, İ. H.; Çetin, A. E.; Nizamoğlu, SedatEfficient transduction of optical energy to bioelectrical stimuli is an important goal for effective communication with biological systems. For that, plasmonics has a significant potential via boosting the light−matter interactions. However, plasmonics has been primarily used for heat-induced cell stimulation due to membrane capacitance change (i.e., optocapacitance). Instead, here, we demonstrate that plasmonic coupling to photocapacitor biointerfaces improves safe and efficacious neuromodulating displacement charges for an average of 185% in the entire visible spectrum while maintaining the faradic currents below 1%. Hotelectron injection dominantly leads the enhancement of displacement current in the blue spectral window, and the nanoantenna effect is mainly responsible for the improvement in the red spectral region. The plasmonic photocapacitor facilitates wireless modulation of single cells at three orders of magnitude below the maximum retinal intensity levels, corresponding to one of the most sensitive optoelectronic neural interfaces. This study introduces a new way of using plasmonics for safe and effective photostimulation of neurons and paves the way toward ultrasensitive plasmon-assisted neurostimulation devices.Item Open Access Selective manipulation of ICT and PET processes in styryl-bodipy derivatives: Applications in molecular logic and fluorescence sensing of metal ions(2010) Bozdemir, O. A.; Guliyev, R.; Buyukcakir, O.; Selcuk, S.; Kolemen, S.; Gulseren, G.; Nalbantoglu, T.; Boyaci, H.; Akkaya, E. U.Remarkably versatile chemistry of Bodipy dyes allows the design and straightforward synthesis of multivalent-multitopic derivatives, which, with judicious selection of metal ion-ligand pairs based on known affinities, affords control and manipulation of photoinduced electron transfer and internal charge transfer processes as desired. We have demonstrated that metal ions acting as modulators (or inputs, in digital design parlance) can generate absorbance changes in accordance with the operation of a half-adder. In addition, an AND logic gate in the emission mode was delivered using a different binucleating arrangement of ligands. A molecular equivalent of a three-input AND logic gate was also obtained exploiting differential binding affinities of metal ions for different ligands. The results suggest that different metal ions can be used as nonannihilating inputs, selectively targeting various ligands incorporated within a single fluorophore, and with careful design, diverse photophysical processes can be selectively modulated, resulting in a range of signals, useful in molecular logic design, and offering an enticing potential for multianalyte chemosensors.Item Open Access Tuned range-separated hybrids in density functional theory(2010) Baer, R.; Livshits, E.; Salzner, U.We review density functional theory (DFT) within the Kohn-Sham (KS) and the generalized KS (GKS) frameworks from a theoretical perspective for both time-independent and time-dependent problems. We focus on the use of range-separated hybrids within a GKS approach as a practical remedy for dealing with the deleterious long-range self-repulsion plaguing many approximate implementations of DFT. This technique enables DFT to be widely relevant in new realms such as charge transfer, radical cation dimers, and Rydberg excitations. Emphasis is put on a new concept of system-specific range-parameter tuning, which introduces predictive power in applications considered until recently too difficult for DFT.