Browsing by Author "Dede, Didem"
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Item Open Access CdTe quantum dot-functionalized P25 titania composite with enhanced photocatalytic NO2 storage selectivity under UV and vis irradiation(American Chemical Society, 2019) Balcı-Leinen, Merve; Dede, Didem; Khan, Münir Ullah; Çağlayan, Mustafa; Koçak, Yusuf; Demir, Hilmi Volkan; Özensoy, EmrahComposite systems of P25 (titania) functionalized with thioglycolic acid (TGA)-capped CdTe colloidal quantum dots (QDs) were synthesized, structurally characterized, and photocatalytically tested in the photocatalytic NOx oxidation and storage during NO(g) + O2(g) reaction. Pure P25 yielded moderate-to-high NO conversion (31% in UV-A and 40% in visible (vis)) but exhibited extremely poor selectivity toward NOx storage in solid state (25% in UV-A and 35% in vis). Therefore, P25 could efficiently photooxidize NO(g) + O2(g) into NO2; however, it failed to store photogenerated NO2 and released toxic NO2(g) to the atmosphere. CdTe QD-functionalized P25 revealed a major boost in photocatalytic performance with respect to pure P25, where NO conversion reached 42% under UV-A and 43% under vis illumination, while the respective selectivity climbed up to 92 and 97%, rendering the CdTe/P25 composite system an efficient broad-band photocatalyst, which can harvest both UV-A and vis light efficiently and display a strong NOx abatement effect. Control experiments suggested that photocatalytic active sites responsible for the NO(g) + O2(g) photooxidation and formation of NO2 reside mostly on titania, while the main functions of the TGA capping agent and the CdTe QDs are associated with the photocatalytic conversion of the generated NO2 to the adsorbed NOx species, significantly boosting the selectivity toward solid-state NOx storage. Reuse experiments showed that photocatalytic performance of the CdTe/P25 system can be preserved to a reasonable extent with only a moderate decrease in the photocatalytic performance. Although some decrease in the photocatalytic activity was observed after aging, CdTe/P25 could still outperform P25 benchmark photocatalyst. Increasing CdTe QDs loading from the currently optimized minuscule concentrations could be a useful strategy to increase further the catalytic lifetime/stability of the CdTe/P25 system with only a minor penalty in catalytic activity.Item Open Access Highly stable multicrown heterostructures of type-II nanoplatelets for ultralow threshold optical gain(American Chemical Society, 2019) Dede, Didem; Taghipour, Nima; Quliyeva, Ulviyya; Sak, Mustafa; Kelestemur, Yusuf; Güngör, Kıvanç; Demir, Hilmi VolkanSolution-processed type-II quantum wells exhibit outstanding optical properties, which make them promising candidates for light-generating applications including lasers and LEDs. However, they may suffer from poor colloidal stability under ambient conditions and show strong tendency to assemble into face-to-face stacks. In this work, to resolve the colloidal stability and uncontrolled stacking issues, we proposed and synthesized CdSe/CdSe1–xTex/CdS core/multicrown heteronanoplatelets (NPLs), controlling the amount of Te up to 50% in the crown without changing their thicknesses, which significantly increases their colloidal and photostability under ambient conditions and at the same time preserving their attractive optical properties. Confirming the final lateral growth of CdS sidewalls with X-ray photoelectron spectroscopy, energy-dispersive analysis, and photoelectron excitation spectroscopy, we found that the successful coating of this CdS crown around the periphery of conventional type-II NPLs prevents the unwanted formation of needle-like stacks, which results in reduction of the undesired scattering losses in thin-film samples of these NPLs. Owing to highly efficient exciton funneling from the outmost CdS crown accompanied by the reduced scattering and very low waveguide loss coefficient (∼18 cm–1), ultralow optical gain thresholds of multicrown type-II NPLs were achieved to be as low as 4.15 μJ/cm2 and 2.48 mJ/cm2 under one- and two-photon absorption pumping, respectively. These findings indicate that the strategy of using engineered advanced heterostructures of nanoplatelets provides solutions for improved colloidal stability and enables enhanced photonic performance.Item 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 VolkanDoped 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.Item Open Access Orientation-controlled nonradiative energy transfer to colloidal nanoplatelets: engineering dipole orientation factor(American Chemical Society, 2019) Erdem, Onur; Güngör, Kıvanç; Güzeltürk, Burak; Tanrıöver, İbrahim; Sak, Mustafa; Olutaş, Murat; Dede, Didem; Kelestemur, Yusuf; Demir, Hilmi VolkanWe proposed and showed strongly orientation-controlled Förster resonance energy transfer (FRET) to highly anisotropic CdSe nanoplatelets (NPLs). For this purpose, we developed a liquid–air interface self-assembly technique specific to depositing a complete monolayer of NPLs only in a single desired orientation, either fully stacked (edge-up) or fully nonstacked (face-down), with near-unity surface coverage and across large areas over 20 cm2. These NPL monolayers were employed as acceptors in an energy transfer working model system to pair with CdZnS/ZnS core/shell quantum dots (QDs) as donors. We found the resulting energy transfer from the QDs to be significantly accelerated (by up to 50%) to the edge-up NPL monolayer compared to the face-down one. We revealed that this acceleration of FRET is accounted for by the enhancement of the dipole–dipole interaction factor between a QD-NPL pair (increased from 1/3 to 5/6) as well as the closer packing of NPLs with stacking. Also systematically studying the distance-dependence of FRET between QDs and NPL monolayers via varying their separation (d) with a dielectric spacer, we found out that the FRET rate scales with d–4 regardless of the specific NPL orientation. Our FRET model, which is based on the original Förster theory, computes the FRET efficiencies in excellent agreement with our experimental results and explains well the enhancement of FRET to NPLs with stacking. These findings indicate that the geometrical orientation of NPLs and thereby their dipole interaction strength can be exploited as an additional degree of freedom to control and tune the energy transfer rate.Item Open Access Synthesis and characterization of colloidal quantum wells: from simple size-tuned core to complex multi-crown structures(Bilkent University, 2018-08) Dede, DidemAs a new class of semiconductor nanocrystals, colloidal quantum wells (CQWs), also commonly known as nanoplatelets (NPLs), exhibit remarkable electronic and optical properties that will potentially nd a wide range of use from nanophotonics to optoelectronics. NPLs feature step-like absorption pro les and discrete emission spectra with giant oscillator strength resulting in high recombination rates. All these features make these atomically- at structures highly attractive for light-harvesting and -generating applications. In this thesis, to understand the size-tuned properties of their two-dimensional architecture, we conducted a systematic study on the core-only NPLs by using a set of 4 monolayer (ML) CdSe cores as our working model and carefully altered their aspect ratio while keeping their lateral area constant. In such a core-only NPL structure, electron and hole are both con ned in the core resulting in type-I electronic band alignment. By decreasing the width of these NPLs to a value comparable to or less than their exciton Bohr radius, we observe additional con nement e ects emerge. Subsequently, by growing CdSe1xTex alloyed crown around these starting 4 ML CdSe cores, we nd type-II electronic band alignment is obtained. Thanks to their spatially indirect excitons, these core crown NPLs show extraordinarily long radiative lifetimes. Moreover, with the increased absorption cross-section owing to their added crown, high-performance optical gain is achieved via their core/crown heterostructure. However, in this form, their usage is limited since they are unstable in solution forming gels and they exhibit strong tendency to form stacks in lms. To address this problem, here we proposed and developed a multi-crown architecture by additionally growing a CdS crown around the periphery of the type- II heterostructure, enabling excellent optical gain media with enhanced stability. The structural and optical characterizations of the synthesized multi-crown NPLs indicate that this complex architecture holds great promise for making devices in colloidal nanophotonics and optoelectronics.Item Open Access Ultrahigh-efficiency aqueous flat nanocrystals of CdSe/CdS@Cd1−xZnxS colloidal core/crown@alloyed-shell quantum wells(Royal Society of Chemistry, 2019) Shendre, S.; Delikanlı, Savaş; Li, M.; Dede, Didem; Pan, Z.; Ha, S. T.; Fu, Y. H.; Hernández-Martínez, Pedro L.; Yu, J.; Erdem, Onur; Kuznetsov, A. I.; Dang, C.; Sum, T. C.; Demir, Hilmi VolkanColloidal semiconductor nanoplatelets (NPLs) are highly promising luminescent materials owing to their exceptionally narrow emission spectra. While high-efficiency NPLs in non-polar organic media can be obtained readily, NPLs in aqueous media suffer from extremely low quantum yields (QYs), which completely undermines their potential, especially in biological applications. Here, we show high-efficiency water-soluble CdSe/CdS@Cd1−xZnxS core/crown@shell NPLs formed by layer-by-layer grown and composition-tuned gradient Cd1−xZnxS shells on CdSe/CdS core/crown seeds. Such control of shell composition with monolayer precision and effective peripheral crown passivation, together with the compact capping density of short 3-mercaptopropionic acid ligands, allow for QYs reaching 90% in water, accompanied by a significantly increased photoluminescence lifetime (∼35 ns), indicating the suppression of nonradiative channels in these NPLs. We also demonstrate the controlled attachment of these NPLs without stacking at the nanoscale by taking advantage of their 2D geometry and hydrophilicity. This is a significant step in achieving controlled assemblies and overcoming the stacking process, which otherwise undermines their film formation and performance in optoelectronic applications. Moreover, we show that the parallel orientation of such NPLs achieved by the controlled attachment enables directed emission perpendicular to the surface of the NPL films, which is highly advantageous for light extraction in light-emitting platforms..Item Open Access Universality of dissipative self-assembly from quantum dots to human cells(Nature Research, 2020) Makey, Ghaith; Galioğlu, Sezin; Ghaffari, Roujin; Engin, E. D.; Yıldırım, Gökhan; Yavuz, Özgün; Bektaş, O.; Nizam, Ü. S.; Akbulut, Özge; Şahin, Özgür; Güngör, Kıvanç; Dede, Didem; Demir, Hilmi Volkan; İlday, Fatih Ömer; İlday, SerimAn important goal of self-assembly research is to develop a general methodology applicable to almost any material, from the smallest to the largest scales, whereby qualitatively identical results are obtained independently of initial conditions, size, shape and function of the constituents. Here, we introduce a dissipative self-assembly methodology demonstrated on a diverse spectrum of materials, from simple, passive, identical quantum dots (a few hundred atoms) that experience extreme Brownian motion, to complex, active, non-identical human cells (~1017 atoms) with sophisticated internal dynamics. Autocatalytic growth curves of the self-assembled aggregates are shown to scale identically, and interface fluctuations of growing aggregates obey the universal Tracy–Widom law. Example applications for nanoscience and biotechnology are further provided.