Browsing by Subject "Doping"

Now showing 1 - 20 of 21

Open Access
Ab initio study of Ru-terminated and Ru-doped armchair graphene nanoribbons
(Taylor and Francis, 2012) Sarikavak-Lisesivdin, B.; Lisesivdin, S. B.; Özbay, Ekmel
We investigate the effects of ruthenium (Ru) termination and Ru doping on the electronic properties of armchair graphene nanoribbons (AGNRs) using first-principles methods. The electronic band structures, geometries, density of states, binding energies, band gap information, and formation energies of related structures are calculated. It is well founded that the electronic properties of the investigated AGNRs are highly influenced by Ru termination and Ru doping. With Ru termination, metallic band structures with quasi-zero-dimensional, one-dimensional and quasi-one-dimensional density of states (DOS) behavior are obtained in addition to dominant one-dimensional behavior. In contrast to Ru termination, Ru doping introduces small but measurable (12.4 to 89.6meV) direct or indirect band gaps. These results may present an additional way to produce tunable band gaps in AGNRs.
Open Access
Band-Bending at buried SiO2/Si interface as probed by XPS
(American Chemical Society, 2013) Çopuroğlu, M.; Sezen, H.; Opila, R. L.; Süzer, Şefik
X-ray photoelectron spectroscopy is used to probe the photoinduced shifts in the binding energies of Si2p, O1s, and C1s of the SiO2/Si interfaces of a number of samples having oxide and/or thin organic layers on top of p- and n-Si wafers. Whereas the photoinduced shifts, in each and every peak related, vary from 0.2 to 0.5 eV for the p-type samples, the corresponding shifts are substantially smaller (<0.1 eV) for the n-type, regardless of (i) oxidation route (thermal or anodic), (ii) thickness of oxide layer, (iii) nature of organic layer, or (iv) color of three illuminating sources we have used. This leads us to conclude that these particular photoshifts reflect the charge state of the SiO2/Si interface, even in the case of a 20 nm thick oxide, where the interface is buried and cannot be probed directly by XPS.
Open Access
Colloidal synthesis and doping of semiconductor nanocrystals
(2015-07) Akgül, Mehmet Zafer
Colloidal semiconductor nanocrystals have drawn great interest for application areas in photonics and optoelectronics thanks to their superior optical properties including strong bandgap emission and tunability. Also, their suitability for solution-based processing has made them highly attractive for low-cost production of light-emitting diodes and lasers. Our objective in this thesis is to show the potential and versatility of semiconductor nanocrystals via colloidal synthesis and post-processing methods. The thesis work includes the synthesis of colloidal quantum dot and well structures and their post-doping and investigates their exciton decay dynamics. In this thesis a novel colloidal approach for the doping of zinc blende colloidal quantum wells was proposed and demonstrated for the first time. This new doping method uniquely relies on atomic layer deposition (ALD) process. Here we achieved the worlds first manganese-doped CdSe@CdS core@shell nanoplatelets using our technique of ALD-assisted doping. Also, we studied silver-doped CdTe quantum dots under different conditions. Our experimental work proved that the quantum yield enhancement of silver-doped CdTe quantum dots is a strong function of the nanocrystal size and doping concentration. Tuning the nanocrystal size and doping level, our aqueous core-only CdTe nanocrystals reached a record high photoluminescence quantum efficiency of 68%. For these quantum dots, various decay kinetics were proposed and the enhancement in the quantum yield was attributed to the trap state annihilation. The methods and results provided in this thesis contribute to the fundamental understanding of semiconductornanocrystals and pave the way for high-performance colloidal platforms and devices.
Open Access
Colloidal synthesis of Ag(I)-doped CdSe nanoplatelets with partial cation exchange method
(2019-01) Bozdoğan, İrfan Selim
Colloidal nanoplatelets (NPLs) exhibit strong one-dimensional quantum confinement in the vertical direction. This makes them a highly attractive host system for studying variable doping techniques and effects without variation in the quantum confinement effect. Earlier, core-only CdSe NPLs were converted into Cu2Se and HgSe NPLs, and also CdSe/CdS core/shell NPLs were transformed into Cu2Se/Cu2S, ZnSe/ZnS, and PbSe/PbS NPLs by using full cation exchange (CE) methods. Recently, core-only CdSe NPLs have been doped with Cu(I) ions using high-temperature nucleation doping and post-synthesis partial CE approaches. On the other hand, unlike Cu(I), such monovalent doping with Ag(I) ions has previously not been possible in NPLs as a host system, although silver doping had been widely studied in other host systems. Therefore, there has been no previous report on the doping of Ag(I) into CdSe NPLs to date. To address this gap, in this thesis, Ag(I) doping in CdSe NPLs by using a postsynthesis partial CE technique was developed. A systematic study was carried out to investigate the effects of dopant precursor reactivities, reaction timing, and temperature on the evolution of dopant-related emission as compared to the excitonic emission. In controlled experiments, the excitonic emission peak was eliminated and only dopant-related emission peak was successfully obtained. Finally, temperaturedependent emission kinetics of the as-synthesized Ag(I)-doped CdSe NPLs at varied temperatures ranging from 25 to 298 K were investigated. It was observed that both excitonic and dopant-related emission peaks were blue-shifted and their intensities were considerably increased with the decreasing temperature. As a new dopant-host system, these Ag(I)-doped CdSe NPLs hold a great promise for further systematic spectroscopic studies and possibly various optoelectronic applications.
Open Access
Electronic and optical properties of example 2D systems under the vertical electric field
(2024-07) Yüksek, Yılmaz Can
From optics to nanoelectronics, two-dimensional (2D) materials have drawn attention due to their extraordinary properties such as high carrier mobility, good thermal and electrical conductivity, and mechanical strength. Electronic and optical properties of example 2D systems containing single-layer graphene, 2D molybdenum carbide (Mo2C), and 2D tungsten diselenide (WSe2) under the vertical (perpendicular) static electric field (E-field) varying between 0.1 V/˚A and 2.5 V/˚A are investigated by the first principles calculations based on the density functional theory. Contributions of van der Waals interactions are included by selecting a suitable exchange-correlation functional. Electronic band structure and density of states information confirmed that monolayer graphene and single-layer Mo2C exhibit metallic properties whereas 2D WSe2 is a semiconductor with a direct band gap. For all systems up to some magnitude of the E-field, the bands in the valance band were found to be degenerate whereas shifts took place in the conduction band as the E-field was introduced to the system. By increasing E-field amplitudes, the Dirac point shifted upwards in graphene, and σ∗ band shifted below the Fermi level at 0.5 V/˚A. In addition to four well-known interband transitions (π → π∗, σ → σ∗, σ → π∗, π → σ∗), σ∗ → π∗ transition is observed. After an electric field amplitude (Ez) of 0.8 V/˚A, bands due to the s-orbitals of Mo atoms in monolayer Mo2C shifted below the Fermi level. Additionally, π plasmon peaks redshifted up to 0.4 V/˚A and blueshifted for 0.6 V/˚A ≤ Ez ≤ 2.5 V/˚A. For the monolayer WSe2 system, the band gap becomes zero when Ez ≥ 1.0 V/˚A which indicates a semiconductor-to-metal transition under the E-field. Shifts below the Fermi level enabled us to n-dope those systems.
Open Access
Electronic properties of graphene nanoribbons doped with zinc, cadmium, mercury atoms
(Elsevier B.V., 2018) Ömeroğlu, O.; Kutlu, E.; Narin, P.; Lisesivdin, S. B.; Özbay, Ekmel
The effect of substitutional impurities as Zinc (Zn), Cadmium (Cd) and Mercury (Hg) on electronic properties of graphene nanoribbons (GNRs) was investigated by using Density Functional Theory (DFT). A substantial change in the electronic properties of GNR structures was observed while changing the position of dopant atom from the edge to the center of armchair graphene nanoribbons (AGNRs) and zigzag graphene nanoribbons (ZGNRs). The calculations are shown that the electronic band gap of GNRs can be controlled depending on the position of dopant atoms. The calculated electronic band structures for both AGNRs and ZGNRs show spin-dependent metallic or semiconductor behavior according to the position of dopant atoms. From the Density of States (DOS) information, quasi-zero-dimensional (Q0D) and quasi-one-dimensional (Q1D) type behaviors are observed. It is shown that because the doped ZGNRs had the lowest total energies, ZGNRs are energetically more stable than AGNRs.
Open Access
Electronic properties of Li-doped zigzag graphene nanoribbons
(Elsevier B.V., 2016) Narin, P.; Kutlu, E.; Sarikavak-Lisesivdin, B.; Lisesivdin, S. B.; Özbay, Ekmel
Zigzag graphene nanoribbons (ZGNRs) are known to exhibit metallic behavior. Depending on structural properties such as edge status, doping and width of nanoribbons, the electronic properties of these structures may vary. In this study, changes in electronic properties of crystal by doping Lithium (Li) atom to ZGNR structure are analyzed. In spin polarized calculations are made using Density Functional Theory (DFT) with generalized gradient approximation (GGA) as exchange correlation. As a result of calculations, it has been determined that Li atom affects electronic properties of ZGNR structure significantly. It is observed that ZGNR structure exhibiting metallic behavior in pure state shows half-metal and semiconductor behavior with Li atom.
Open Access
Electrooxidation of methanol on doped polypyrrole films in acidic media
(Elsevier, 2001-04-06) Becerık, İ.; Süzer, S.; Kadirgan, F.
Electrooxidation of methanol was realised on platinum and perchlorate anion doped polypyrrole film electrodes in acidic media. A systematic kinetic investigation was performed and optimum experimental conditions for the preparation of the electrocatalytic system were determined. The presence of ClO4- anions was confirmed by XPS analysis of the doped polymer matrix. (C) 2001 Elsevier Science B.V. All rights reserved.
Open Access
An experimental and first-principles study of the effect of B / N doping in TiO2 thin films for visible light photo-catalysis
(Elsevier, 2013) Uddin, M. N.; Shibly, S. U. A.; Ovali, R.; Saiful, I.; Islam, M. S.; Uddin, M. J.; Gulseren, O.; Bengu, E.; Mazumder, M. M. R.
Thin films of TiO2 and boron-nitrogen (B/N) co-doped TiO 2 on glass substrates have been prepared by a simple sol-gel dip coating route. Titanium (IV) isopropoxide, boric acid and urea have been used as titanium, boron and nitrogen sources, respectively. The films were characterized by X-ray diffraction, X-ray photo-electron spectroscopy, scanning electron microscopy, Raman spectroscopy and UV-vis spectroscopy. The TiO 2 thin films with co-doping of different B/N atomic ratios (0.27-20.89) showed better photo-catalytic degradation ability of methylene blue compared to that of bare-TiO2 under visible light. The TiO 2 film doped with the highest atomic concentration of N showed repeatedly the best photo-catalytic performance. The high activity of co-doped TiO2 thin films toward organic degradation can be related to the stronger absorption observed in the UV-vis region, red shift in adsorption edges and surface acidity induced by B/N doping. Furthermore, several atomic models for B/N doping have been used to investigate the effect of doping on electronic structure and density of states of TiO2 through ab-initio density functional theory calculations. The computational study suggested a significant narrowing of the band gap due to the formation of midgap states and the shift of Fermi-level for the interstitial N model supporting the experimental results. © 2013 Elsevier B.V.
Open Access
Fast and quick degradation properties of doped and capped ZnO nanoparticles under UV-Visible light radiations
(Elsevier Ltd, 2016) Mittal, M.; Sharma, M.; Pandey, O. P.
Undoped and Manganese (Mn) doped zinc oxide (ZnO) (Zn1- xMnxO, x=0.005, 0.01, 0.015 and 0.02) nanoparticles (NPs) capped with (1.0%) Thioglycerol (TG) has been successfully synthesized by co-precipitation method. Optical and morphological studies have been done for photophysical and structural analysis of synthesized materials. The photocatalytic activity of undoped and Mn doped ZnO NPs were investigated by degradation of crystal violet (CV) dye under UV-Visible light radiations. It has been found that Mn (1.0%) doping concentration is optimal for photophysical and photocatalytic properties. When the pH of as synthesized optimum doped ZnO NPs varied from natural pH i.e. from 6.7 to 8.0 and 10.0, the degradation of CV dye increases from 92% to 95% and 98% in 180min respectively. Further on increasing the pH of optimum doped synthesized NPs to 12.0, almost 100% degradation has been achieved in 150min. Optimum doped photocatalyst synthesized at pH-12.0 has also effectively degraded the CV dye solution in acidic and basic medium thus showed its utility in various industries. However, it has been found that 100% of CV dye quickly degraded in 30min when only 1.0% of hydrogen peroxide (H2O2) was introduced along with optimized NPs synthesized at pH-12. Kinetic studies show that the degradation of CV dye follows pseudo first and second-order kinetic law. Further an industrial anionic polyazo Sirius red F3B (SRF3B) dye has been degraded to 100% with optimized NPs synthesized at pH-12.0 in 15min only.
Open Access
Formation and functionalization of boron phosphide monolayers
(2015-09) Hallıoğlu, Lütfiye
Since the synthesis of graphene with its unique properties has increased the focus on novel two dimensional (2D) materials, successively new 2D materials from either layered or non-layered materials have been synthesized following the advances in thin film growth and characterization techniques. Hexagonal boron nitride (h-BN) is the runner-up material, which is structurally stable in hexagonal honeycomb form. h-BN is an insulator whereas, it is a good thermal conductor. However, the electronic and structural properties of these 2D materials are very susceptible to doping and adsorption, as such, these properties can be altered extensively. Therefore, we have examined the phosphorization of h-BN with varying concentrations, which leads to stable 2D boron phosphide at the ultimate limit. The lattice constant of the BN16 gap semiconductor with impurity characteristics of adsorbants. Also, we have shown that except for Al and Ga, these impurity adatoms carry small amount of magnetic moment in moderate temperatures. In addition, we have studied the substitution of monolayer BP with Group III-IVV atoms. Based on our calculations, we have found that C and N can substitute P atom under ambient conditions. Nonetheless, only N atom selectively substitute for P atom, whereas C atom substitutes both for B and P giving rise to possible chemical etching of monolayer BP in the presence of excess C atom. Substitution of C for B/P results in metallic state in monolayer BP, while substitution of N for P leaves monolayer BP direct gap semiconductor. It is also found that none of these substitutions makes substrate magnetic. Using state-of-the-art computational tools based on the Density Functional Theory( DFT), we have calculated the structural and electronic properties of phosphorization of monolayer h-BN and doped monolayer h-BP.
Open Access
Functionalization of group V monolayers and their compounds: alloying, doping and surface modification
(2020-11) Kanlı, Muammer
There has been growing interest during the last decade in two-dimensional (2D) materials due to their important roles in various scientific and technological applications such as detectors, lasers and light emitting diodes. In this thesis we present a theoretical investigation of a couple of such 2D materials from group V monolayers and their compounds. Firstly, ordered alloys of GaxAl1−xN hexagonal monolayer are studied and the effect of Al content on mechanical, electronic, thermal and optical properties are investigated. The optimized lattice constants and band gaps change in accordance to Vegard’s Law. Low barrier energies and favorable substitution of Ga by Al may show feasibility of fabrication. Segregation is also checked with mixing energy calculations. The dynamical stability of alloys is shown by phonon spectrum analysis and MD simulations. GaxAl1−xN alloys give lower in-plane stiffness than h-BN or graphene, but higher Poisson’s ratio than most realized 2D systems. Heat capacity of alloys delivers a decrease with Al content at low temperatures but it converges to the classical limit at high temperatures. The absorption onset of GaxAl1−xN alloys remain in the near UV range and prominent absorption peaks blue-shifts with increasing x in compliance with the variation of the band gap. The considered systems, in regard to their stability and tunable fundamental properties seem to be very promising 2D semiconductors for wide range of applications at reduced scales. Then, the interaction of alkali metal atoms (Li, Na, and K) with single layer and periodic structures of hb-As and sw-As phases are revealed by first-principles methods. Arsenene phases are considered to be used as electrodes (anode) for ion-batteries. Strong alkali-electrode binding and low diffusion energy barriers gives out better cycling stability and faster diffusion, respectively. hb-As shows better storage capacity than sw-As. However, deviations from ordered pattern and decline of formation energy with increasing doping level point out a possible structural transformation. By MD calculations, crystalline to amorphous phase transition is seen even for low concentrations level at ambient temperature. The average open-circuit voltages of 0.68-0.88 V (0.65-0.98 V) with specific capacity up to 715 mAhg−1 (358 mAhg−1) are calculated for single layer (periodic) configurations. Overall, non-crystalline phases are calculated to offer more favorable structures than crystalline configurations and they provide more coherent results when compared with experimental data. The obtained voltage profile together with low diffusion barriers and strong metal-electrode binding suggests arsenene as a promising anode material to be used in for alkali-ion battery applications. Lastly, the formation of dumbbell (DB) geometry upon adsorption of Ga, N adatoms to GaN monolayer is investigated. While Ga-N DBs are unstable, Ga-Ga and N-N DB geometries are predicted to form in an exothermic and spontaneous scheme. Cohesive energy of hexagonal GaN monolayer decreases when a DB is formed on its surface. Electronic structures for Ga-Ga DBs for 2×2, 3×3, 4×4 and 5×5 phases show spinpolarized and degenerate bands mainly contributed by p-orbitals of the atoms in impurity zone. Degenarated bands are not observed for N-N dumbbell for HDP, TDP, 2×2 and 3×3 phases. Upon DB formation, semiconductor GaN monolayer become spin-polarized semiconductor with varying band gap, where this functionalization allows electronic structure to be tuned substantionally. This would be highly desired for nanoscale electronic and optical devices. These Ga-Ga and N-N DB geometries may also be used for the synthesis of layered GaN structures.
Open Access
Impurity incorporation and exchange interactions in Co2+-doped CdSe/CdS core/shell nanoplatelets
(American Institute of Physics, 2019) Fainblat, R.; Delikanlı, Savaş; Spee, L.; Czerny, T.; Işık, Furkan; Sharma, V. K.; Demir, Hilmi Volkan; Bacher, G.
The intentional incorporation of transition metal impurities into colloidal semiconductor nanocrystals allows an extension of the host material’s functionality. While dopant incorporation has been extensively investigated in zero-dimensional quantum dots, the substitutional replacement of atoms in two-dimensional (2D) nanostructures by magnetic dopants has been reported only recently. Here, we demonstrate the successful incorporation of Co2+ ions into the shell of CdSe/CdS core/shell nanoplatelets, using these ions (i) as microscopic probes for gaining distinct structural insights and (ii) to enhance the magneto-optical functionality of the host material. Analyzing interatomic Co2+ ligand field transitions, we conclude that Co2+ is incorporated into lattice sites of the CdS shell, and effects such as diffusion of dopants into the CdSe core or diffusion of the dopants out of the heterostructure causing self-purification play a minor role. Taking advantage of the absorption-based technique of magnetic circular dichroism, we directly prove the presence of sp-d exchange interactions between the dopants and the band charge carriers in CdSe/Co2+:CdS heteronanoplatelets. Thus, our study not only demonstrates magneto-optical functionality in 2D nanocrystals by Co2+ doping but also shows that a careful choice of the dopant type paves the way for a more detailed understanding of the impurity incorporation process into these novel 2D colloidal materials.
Open Access
Ligand exchange and impurity doping in 2d cdse nanoplatelet thin films and their applications
(Wiley-VCH Verlag GmbH & Co. KGaA, 2021-09-23) Lee, W, S.; Kang, Y-G.; Lee, Y. M.; Jean, S.; Sharma, A.; Demir, Hilmi Volkan; Han, M. J.; Koh, W-K.; Oh, S. J.
The effects of halide-ligand exchange and Cu and Ag doping are studied on structural, optical, and electrical properties of four monolayer CdSe nanoplatelet (NPL) and NPL thin films. Combinational study shows that NH4Cl-treatment on CdSe NPL and NPL thin films show tetragonal lattice distortion of NPL, side-to-side attachment between NPLs, bathochromic shift in absorption spectra, and complete quenching of band-edge and dopant-induced emissions. First-principle calculations reveal that Cl creates states below valence band maximum while Ag and Cu dopants create acceptor-like states, explaining the change of their optical property. Field-effect transistors are fabricated to investigate the effect of doping and reduced interplatelet distance on electrical properties of CdSe NPL thin films, demonstrating Cu and Ag dopants mitigate n-type character of CdSe NPL thin films. Temperature-dependent electrical characterization is conducted to further understand charge transport behavior depending on the existence of dopants. This work provides scientific information on the influence of surface chemistry and impurity doping on quantum confined semiconductors and new directions for the design of high-performance nanomaterial-based electronic and optoelectronic devices.
Open Access
Near-Infrared-Emitting five-monolayer thick copper-doped CdSe nanoplatelets
(WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2019) Sharma, Ashma; Sharma, Manoj; Güngör, Kıvanç; Olutaş, Murat; Dede, Didem; Demir, Hilmi Volkan
Doped nanocrystals are instrumental to the high‐performance luminescent solar concentrators (LSCs) and the color conversion devices. Recently, copper (Cu)‐doped three and four monolayer (ML) thick CdSe nanoplatelets (NPLs) have been shown superior to the existing Cu‐doped quantum dots (QDs) for their use in LSCs. However, additional improvement in the LSC performance can be achieved by further redshifting the emission into the near‐infrared (NIR) region of electromagnetic spectrum and increasing the absorbed portion of the solar irradiation. Cu‐doping into higher thicknesses of these atomically flat NPLs (e.g., ≥5 ML) can achieve these overarching goals. However, addition of the dopant ions during the nucleation stage disturbs this high‐temperature growth process and leads to multiple populations of NPLs and QDs. Here, by carefully controlling the precursor chemistry the successful doping of Cu in five ML thick NPLs by high‐temperature nucleation doping method is demonstrated. The optimized synthesis method shows nearly pure population of doped five ML thick NPLs, which possess ≈150 nm Stokes‐shifted NIR emission with high quantum yield of 65 ± 2%. Structural, elemental, and optical studies are conducted to confirm the successful doping and understand the detailed photophysics. Finally, these materials are tested experimentally and theoretically for their performance as promising LSC materials.
Open Access
One-step codoping of reduced graphene oxide using boric and nitric acid mixture and its use in metal-free electrocatalyst
(Elsevier, 2015) Tien H.N.; Kocabas, C.; Hur, S.H.
In this study, the preparation of a highly efficient metal-free electrocatalyst, boron and nitrogen codoped reduced graphene oxide (BN-rGO), with an excellent durability is reported. The BN-rGO were prepared in one step using boric and nitric acid mixture, exhibiting highly improved oxygen reduction reaction (ORR) activity than those of the pristine GO and single doped rGOs. The electrocatalyst also showed the excellent long-term durability and CO tolerance than those of the commercial Pt/C catalysts. © 2014 Elsevier B.V.All rights reserved.
Open Access
Physics and applications of photonic crystals
(2000) Temelkuran, Burak
We first fabricated a dielectric based layer-by-layer photonic crystal, with a three-dimensional photonic band gap at microwave frequencies. We investigated the transmission, reflection and defect characteristics of the crystal. A Fabry-Perot cavity analogy was used to understand the localization of the electromagnetic (EM) fields around defects. We then showed the enhancement of the EM held within the defect volumes, and suggested a possible application: resonant cavity enhanced detectors built around photonic crystals. We demonstrated that a detector inserted inside the defect volume benefits from the frequency selectivity and the highly enhanced field of the cavity. Next, we investigated the radiation of the EM fields from a source inserted in the defect volume, and observed that the radiated field has a very high directivity and efficiency. The experimental results agreed well with the theoretical expectations. We demonstrated waveguiding structures built around photonic crystals. We showed that EM waves could be guided through a planar air gap between two photonic crystals, in which the wave is coupled inside the defect volume, and having no where else to go, propagates through this opening. The dispersion diagrams for these planar waveguide structures also agreed well with the theoretical expectations of our waveguide model. We also showed that, the wave could be guided along a single missing rod, and demonstrated the bending of the EM waves for these waveguide structures with “L” shaped openings. We tested metallic photonic crystals built in different dimensions and diflferent filling ratios. We observed many superiorities of these structures when compared to dielectric-based photonic crystals. A full characterisation of various metallic photonic crystals was performed. We also showed that metallic photonic crystals are suitable for some of the applications we have demonstrated for dielectric structures. We also fabricated a new layer-by-layer photonic crystal using highly doped silicon wafers processed by semiconductor micromachining techniques, with a band gap at millimeter wave frequencies. We showed that the transmission and defect characteristics of these structures are analogous to metallic photonic crystals, as we have predicted. The experimental results agree well with the predictions of the transfer matrix method (TMM) simulations. The method can be extended to fabricate these crystals at THz. frequencies.
Open Access
Theoretical analysis of substituent effects on building blocks of conducting polymers: 3, 4'-substituted bithiophenes
(American Chemical Society, 1999) Salzner, U.; Kızıltepe, T.
Substituents are widely used to modify the properties of conducting polymers. To study substituent effects on energy levels and energy gaps systematically, CH3-, OH-, NH2-, CN-, and CCH-substituted bithiophenes were examined with density functional theory and NBO analysis. Total charges and :r-electron densities were analyzed separately to examine π- and σ-effects. Second-order perturbation theory was used to quantify conjugation in terms of orbital interactions. NBO orbital energies were employed to investigate the effect of alternating donor-acceptor substitution. Substituents in 3- and 4- positions shift HOMO and LUMO levels in parallel and hardly influence HOMO- LUMO gaps. For level shifting the π-donating and π-accepting abilities are most important; electronegativity mainly influences the σ-orbitals and is less crucial in determining energy gaps. Alternating donor-acceptor substitution leads to HOMO and LUMO energies that are average between those of the parent systems and has little effect on energy gaps.
Open Access
Thermodynamic silver doping of core/shell colloidal quantum wells imparted with paramagnetic properties emitting at near-infrared
(American Chemical Society, 2023-05-29) Shabani, Farzan; Ahmad, Muhammad; Kumar, Satish; Delikanlı, Savaş; Işık, Furkan; Bhattacharya, A.; Petrou, A.; Demir, Hilmi Volkan
Two-dimensional (2D) core/shell nanoplatelets (NPLs) synthesized via the hot-injection method provide excellent thermal and chemical stability for high-temperature doping, where an expanded and flexible lattice is required. Here, a thermodynamic approach toward silver doping of these NPLs is proposed and demonstrated, which previously proved to be challenging due to the fast self-purification of the dopants with the introduction of the shell. Maintaining the doping procedure in the reversible regime ensured the integrity of the NPLs and allowed a high level of doping; however, the equilibrium condition is further complicated by environmental factors that affect the chemical activity of the cations and the surface composition of the NPLs. Two main deterioration mechanisms in the irreversible regime were observed: ZnS-shelled NPLs suffered preferential etching, while CdS-shelled NPLs underwent cleavage and fragmentation. Alloying of the shell minimized both mechanisms for CdZnS-shelled NPLs and preserved the metastable state of the NPLs, including their 2D shape and crystalline structure. Distribution of silver ions in the lattice of the NPLs directly affected the recombination dynamics and enabled fine-tuning of the near-infrared emission beside the exciton confinement. These silver-doped CdZnS-shelled NPLs are shown further to exhibit enhanced paramagnetic properties with Zeeman splitting and Brillouin-like bound-exciton polarization as a function of the magnetic field, critical for spintronic applications
Open Access
Two-dimensional CdSe-based nanoplatelets: their heterostructures, doping, photophysical properties, and applications
(Institute of Electrical and Electronics Engineers, 2020) Sharma, Manoj; Delikanlı, Savaş; Demir, Hilmi Volkan
In the past decade, colloidal quantum wells, also known as 2-D semiconductor nanoplatelets (NPLs), have been added to the colloidal nanocrystal (NC) family. Through the unique control of the thickness with monolayer precision, these novel materials exhibit strong 1-D quantum confinement that offers unique optical properties along with the possibility of fabricating advanced heterostructures, which are not possible with other quantum-confined nanostructures. The 2-D CdX (X = Se, S)-based NPLs provide high color purities, fast fluorescence lifetimes, and large exciton binding energies. This review covers the latest developments in the successful utilization of these flat NCs in different nanophotonic device applications. The synthesis of the advanced heterostructures of flat 2-D NCs (e.g., core-shell, core-crown, and core-crown-shell) has matured very rapidly, and new exciting optical and electronic applications are emerging. Doping of these atomically thin NCs also offers new possibilities for their utilization in different solar light harvesting, magnetic, electronic, and lasing applications. This review also includes the recent advancements in the understanding of their unique optical properties that are of utmost importance for their practical implementation in light-emitting devices and lasers. Finally, we present a future perspective on their successful utilization in different nanophotonic applications.