Browsing by Subject "Nanocrystals."

Now showing 1 - 13 of 13

Open Access
Carrier dynamics in silicon and Germanium nanocrystals
(2008) Sevik, Cem
This is a computational work on the Si and Ge nanocrystals (NCs) embedded in wide band gap host matrices. As the initial task, extensive ab initio work on the structural and electronic properties of various NC host matrices, namely, SiO2, GeO2, Si3N4, and Al2O3 are preformed. The structural parameters, elastic constants, static and optical dielectric constants are obtained in close agreement with the available results. Furthermore, recently reported high density cubic phase of SiO2 together with GeO2 and SnO2 are studied and their stable highdielectric constant alloys are identified. Based on the ab initio study of host matrices, two related high field phenomena, vital especially for the electroluminescence in Si and Ge NCs, are examined. These are the hot carrier transport through the SiO2 matrix and the subsequent quantum-confined impact ionization (QCII) process which is responsible for the creation of electron-hole pairs within the NCs. First, the utility and the validity of the ab initio density of states results are demonstrated by studying the high field carrier transport in bulk SiO2 up to fields of 12 MV/cm using the ensemble Monte Carlo technique. Next, a theoretical modeling of the impact ionization of NCs due to hot carriers of the bulk SiO2 matrix is undertaken. An original expression governing the QCII probability as a function of the energy of the hot carriers is derived. Next, using an atomistic pseudopotential approach the electronic structures for embedded Si and Ge NCs in wide band-gap matrices containing several thousand atoms are employed. Effective band-gap values as a function of NC diameter reproduce very well the available experimental and theoretical data. To further check the validity of the electronic structure on radiative processes, direct photon emission rates are computed. The results for Si and Ge NCs as a function of diameter are in excellent agreement with the available ab initio calculations for small NCs. In the final part, non-radiative channels, the Auger recombination (AR) and carrier multiplication (CM) in Si and Ge NCs are investigated again based on the atomistic pseudopotential Hamiltonian. The excited electron and excited hole type AR and CM and biexciton type AR lifetimes are calculated for different sized and shaped NCs embedded in SiO2 and Al2O3. Asphericity is also observed to increase the AR and CM rates. An almost monotonous size-scaling and satisfactory agreement with experiment for AR lifetime is obtained considering a realistic interface region between the NC core and the host matrix. It is further shown that the size-scaling of AR can simply be described by slightly decreasing the established bulk Auger constant for Si to 1.0×10−30cm6 s −1 . The same value for germanium is extracted as 1.5×10−30cm6 s −1 which is very close to the established bulk value. It is further shown that both Si and Ge NCs are ideal for photovoltaic efficiency improvement via CM due to the fact that under an optical excitation exceeding twice the band gap energy, the electrons gain lion’s share from the total excess energy and can cause a CM. Finally, the electron-initiated CM is predicted to be enhanced by couple orders of magnitude with a 1 eV of excess energy beyond the CM threshold leading to subpicosecond CM lifetimes.
Open Access
Cascading and modifying nonradiative energy transfer mechanisms in strong coupling region of plasmons and excitons in semiconductor quantum dots
(2010) Akın, Onur
Nonradiative energy transfer finds important applications in nanophotonics and nanobiotechnology including nanoscale optical waveguiding and biological nanosensors. Various fluorophores can take part in such energy transfer interactions in close proximity of each other. Their emission kinetics can be strongly modified and controlled as a result. For example, colloidal semiconductor quantum dots, also known as nanocrystals, have widely been shown to serve as donors and acceptors among themselves or with other fluorescent species to transfer excitation energy nonradiatively. In their close proximity, emission characteristics of such fluorophores can also be altered when coupled with plasmonic structures, e.g., metal nanoparticles. One favored result of these plasmon-exciton interactions is the emission enhancement. In principle it is possible to plasmon-couple acceptor-donor pairs of nonradiative energy transfer to modify their transfer rate. Such plasmon-mediated energy transfer has been demonstrated, where both acceptor-donor pairs are plasmoncoupled. In these cases, however, the resulting plasmon-exciton interactions are not controlled to take place either at the donor site or the acceptor site but at both of the sites. Therefore, it has previously not been possible to identify the coupled interactions. In this thesis, we propose and demonstrate cascaded plasmonic - nonradiative energy transfer interactions that are controlled by selectively plasmon-coupling either only the donor quantum dots or only the acceptor quantum dots. For that, we designed a novel self-assembly architecture of our hybrid layered systems of semiconductor nanocrystals and metal nanoparticles in a bottom-up fashion through precise spatial and spectral control. This scheme uniquely allowed for the ability to spatially control plasmonexciton interactions to take place either at the “start” site (donors) or “finish” site (acceptors) of the energy transfer. This control was achieved by placing the plasmonic layer in the right proximity of the donors (for strong donor-exciton plasmon-coupling) while sufficiently being far away from the acceptors (for weak acceptor-exciton plasmon-coupling), or vice versa. Here we comparatively studied and analyzed consequent modifications of quantum dot emission kinetics in response to both cases of plasmon-coupling to only the donors and to only the acceptors through steady-state and time-resolved photoluminescence measurements, along with their lifetime and rate calculations. Such cascaded energy transfer interactions in the strong exciton-plasmon coupling region hold great promise for innovative near-field photonic devices and biological tags. system.
Open Access
Color science and technology of novel nanophosphors for high-efficiency high-quality LEDs
(2011) Erdem, Talha
Today almost one-fifth of the world‟s electrical energy is consumed for artificial lighting. To revolutionize general lighting to reduce its energy consumption, high-efficiency, high-quality light-emitting diodes (LEDs) are necessary. However, to achieve the targeted energy efficiency, present technologies have important drawbacks. For example, phosphor-based LEDs suffer from the emission tail of red phosphors towards longer wavelengths. This deep-red emission decreases substantially the luminous efficiency of optical radiation. Additionally, the emission spectrum of phosphor powders cannot be controlled properly for high-quality lighting, as this requires careful spectral tuning. At this point, new nanophosphors made of colloidal quantum dots and crosslinkable conjugated polymer nanoparticles have risen among the most promising alternative color convertors because they allow for an excellent capability of spectral tuning. In this thesis, we propose and present high-efficiency, highquality white LEDs using quantum dot nanophosphors that that exhibit luminous efficacy of optical radiation ≥380 lm/Wopt, color rendering index ≥90 and correlated color temperature ≤4000 K. We find that Stoke‟s shift causes a fundamental loss >15%, which limits the maximum feasible luminous efficiency to 326.6 lm/Welect. Considering a state-of-the-art blue LED (with 81.3% photon conversion efficiency), this corresponds to 265.5 lm/Welect. To achieve 100 and 200 lm/Welect, the layered quantum dot films are required to have respective quantum efficiencies of 39 and 79%. In addition, we report our numerical modeling and experimental demonstrations of the quantum dot integrated LEDs for the different vision regimes of human eye. Finally, we present LEDs based on the color tuning capability of conjugated polymer nanoparticles for the first time. Considering the outcomes of this thesis, we believe that our research efforts will help the development and industrialization of white light emitting diodes using nanophosphor components.
Open Access
Environmental friendly InP/ZnS nanocrystals
(2012) Coşkun, Yasemin
Semiconductor nanocrystals are nanometer scale fluorescent crystallites with tunable optical properties, which can be controlled by the material composition and particle size. They can be prepared using various synthesis techniques and find applications in many different areas ranging from life sciences to electronics. In this thesis, indium phosphide based nanocrystals are studied for LED applications. The thesis research work focuses on the colloidal synthesis method and material characterization of these nanocrystals. Using one pot synthesis method, the indium phosphide/zinc sulfide (InP/ZnS) core/shell nanocrystal structures are synthesized. This synthesis technique allows for a reproducible and tunable preparation method. The material characterization techniques used in this thesis include UV-Vis spectroscopy, photoluminescence spectroscopy, transmission electron microscopy (TEM), X-ray diffraction, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma-mass spectrometry (ICP-MS), and Zeta Sizer (or DLS). These properties make InP/ZnS nanocrystals comparable to their cadmium (Cd) containing counterparts with respect to their optical properties, and InP/ZnS nanocrystals offer the potential to replace them because of environmental concerns in LED applications.
Open Access
Exciton harvesting systems of nanocrystals
(2011) Mutlugün, Evren
Semiconductor nanocrystals, also known as colloidal quantum dots, have gained substantial scientific interest for innovative light harvesting applications including those in biolabeling. Organic dyes and fluorescent proteins are widely used in biotargeting and live cell imaging, but their intrinsic optical properties, such as narrow excitation windows, limit their potential for advanced applications, e.g., spectral multiplexing. Compared to these organic fluorophores, favorable properties of the quantum dots including high photoluminescence quantum yields together with tunable emission peaks and narrow spectral emission widths, high extinction coefficients, and broad absorption bands enable us to discover and innovate light harvesting composites. In such systems, however, the scientific challenge is to achieve high levels of energy transfer from one species to the other, with additional features of versatility and tunability. To address these problems, as a conceptual advancement, this thesis proposes and demonstrates a new class of versatile light harvesting systems of semiconductor nanocrystals mediated by excitonic interactions based on Förstertype nonradiative energy transfer. In this thesis, we synthesized near-unity efficiency colloidal quantum dots with as-synthesized photoluminescence quantum yields of >95%. As proof-of-concept demonstrations, we studied and achieved highly efficient exciton harvesting systems of quantum dots bound to fluorescent proteins, where the excitons are zipped from the dots to the proteins in the composite. This led to many folds of light harvesting (tunable up to 15 times) in the case of the green fluorescent protein. Using organic dye molecules electrostatically interacting with quantum dots, we showed high levels of exciton migration from the dots to the molecules (up to 94%). Furthermore, we demonstrated stand-alone, flexible membranes of nanocrystals in unprecedentedly large areas (> 50 cm × 50 cm), which paves the way for highend, large-scale applications. In the thesis, we also developed exciton-exciton coupling models to support the experimental results. This thesis opens up new possibilities for exciton-harvesting in biolabeling and optoelectronics.
Open Access
Formation of Ge nanocrystals with CW laser irradiation of Siox:Ge thin films
(2015) Gümüş, Melike
Germanium and silicon are the materials which have effective absorption in the visible and near infrared region of electromagnetic spectrum; therefore they are preferred for optoelectronic device and solar cell applications. Si and Ge are the material of choice when it comes to solar cell applications due to their being low cost, widely available and inert. They have indirect bandgap and the absorption coefficient of indirect bandgap materials is lower than direct ones. It is known that decreasing dimensions of materials to nanometric sizes cause transition from indirect bandgap to direct bandgap behavior along with increasing band gap. Therefore decreasing their dimensions both a shift of the band gap toward the blue as well as an increase in absorption can be achieved. In this work, thin films of SiOx:Ge were fabricated with different germanium concentrations and annealed with CW Ar+ laser operating at 488 nm that resulted in formation of Ge nanocrystals in the SiOx matrix. Composition analysis of as grown samples were done by Rutherford Backscattering Spectroscopy, optical properties were determined by ellipsometry. Nanocrystal formation within laser irradiated samples was confirmed by Raman spectroscopy. Data were also collected about crystal formation by scanning surface texture with stylus surface profilometer. As a result of all the analysis, it was shown that crystal formation depends on germanium concentration in the SiOx matrix and laser irradiation power density
Open Access
Formation of silicon nanocrystals by laser processing of silicon rich oxides
(2012) Gündoğdu, Sinan
Silicon nanocrystals are well known to exhibit strong luminescence in the visible. Extension of this into a nanocrystal network would be beneficial for many applications. In the light of recent advances on exciton-plasmon interactions and photovoltaic cells, there is renewed interest in the use of nanostructures. Due to quantum confinement, silicon nanoclusters with increased band gaps, are promising for down conversion light and enhanced emission on plasmonic surfaces. Conventional techniques utilize high-temperature processing to obtain the Si-SiO2 phase separation which uses high thermal budget, not suitable for localized applications not compatible with glass substrates or thin-film stacked structures. An alternative approach capable of avoiding high temperature processing is laser irradiation of substochiometric amorphous silicon oxides. In this work, continuous-wave laser processing of Si-rich oxide thin films with varying Si content were performed in order to obtain Si nanocrystals embedded in silica. The role of composition, dwell times and power densities were investigated for Si-SiO2 phase separation. We present cw laser processing of PECVD grown and sputtered SiOx films. XPS, RBS and ERDA techniques were used for the stoichiometry analysis of different composition as grown samples and their optical properties were determined through ellipsometry analysis. Processing was performed with an Ar+ laser at 488 nm. The structural changes due to processing were investigated by Raman and photoluminescence spectroscopy. It has been shown that silicon nanocrystals formation depends both on precursor gas composition (hydrogen-diluted SiH4 and N2O or CO2 gases) and on laser power density. PECVD grown hydrogenated SiOx films were compared with sputtered films with and without hydrogen to identify the role of hydrogen for phase separation.
Open Access
Novel ultraviolet scintillators based on semiconductor quantum dot emitters for significantly enhanced photodetection and photovoltaics
(2007) Mutlugün, Evren
Silicon photonics opens opportunities to realize optoelectronic devices directly on large-scale integrated electronics, leveraging advanced Si fabrication and computation capabilities. However, silicon is constrained in different aspects for use in optoelectronics. Such one limitation is observed in Si based photodetectors, cameras, and solar cells that exhibit very poor responsivity in the ultraviolet (UV) spectral range. Si CMOS photodetectors and CCD cameras cannot be operated in UV, despite the strong demand for UV detection and imaging in security applications. Also, although 95% of the photovoltaics market is dominated by Si based solar cells, silicon is not capable of using UV radiation of the solar spectrum for solar energy conversion, as required especially in space applications. In this thesis for the first time, we demonstrate novel UV scintillators made of semiconductor quantum dot emitters hybridized on Si detectors and cameras to detect and image in UV with significantly improved responsivity and on Si solar cells to generate electrical energy from UV radiation with significantly improved solar conversion efficiency. We present the device conception, design, fabrication, experimental characterization, and theoretical analysis of these UV nanocrystal scintillators. Integrating highly luminescent CdSe/ZnS core-shell nanocrystals, we demonstrate hybrid photodetectors that exhibit two-orders-of-magnitude peak enhancement in their responsivity. We also develop photovoltaic nanocrystal scintillators to enhance open-circuit voltage, short-circuit current, fill factor, and solar conversion efficiency in UV. Hybridizing CdSe/ZnS quantum dots on Si photovoltaic devices, we show that the solar conversion efficiency is doubled under white light illumination (Xe lamp). Such UV scintillator nanocrystals hold great promise to enable photodetection and imaging in UV and extend photovoltaic activity to UV.
Open Access
On the strain in silicon nanocrystals
(2009) Yılmaz, Dündar
In this Thesis we present our achievements towards an understanding of atomistic strain mechanisms and interface chemistry in silicon nanocrystals. The structural control of silicon nanocrystals embedded in amorphous oxide is currently an important technological problem. First, our initial attempt is described to simulate the structural behavior of silicon nanocrystals embedded in amorphous oxide matrix based on simple valence force fields as described by Keatingtype potentials. Next, the interface chemistry of silicon nanocrystals (NCs) embedded in amorphous oxide matrix is studied through molecular dynamics simulations with the chemical environment being governed by the reactive force field model. Our results indicate that the Si NC-oxide interface is more involved than the previously proposed schemes which were based on solely simple bridge or double bonds. We identify different types of three-coordinated oxygen complexes, previously not noted. The abundance and the charge distribution of each oxygen complex is determined as a function of the NC size as well as the transitions among them. Strain has a crucial effect on the optical and electronic properties of nanostructures. We calculate the atomistic strain distribution in silicon NCsup to a diameter of 3.2 nm embedded in an amorphous silicon dioxide matrix. A seemingly conflicting picture arises when the strain field is expressed in terms of bond lengths versus volumetric strain. The strain profile in either case shows uniform behavior in the core, however it becomes nonuniform within 2- 3 ˚A distance to the NC surface: tensile for bond lengths whereas compressive for volumetric strain. We reconcile their coexistence by an atomistic strain analysis. Vibrational density of states (VDOS) affects the optical properties of Si-NCs. VDOS obtained by calculating velocity autocorrelation function (VACF) using velocities of the atoms is extracted from the molecular dynamics simulations. The information on bonding topology enables classification of atoms in the system with respect to their neighbor atoms. With help of this information we separate contributions of different type of atoms to the VDOS. Calculating VACF of different type of atoms such as surface atoms and core atoms of nanocrystal, to the system facilitates understanding of the effects of strain fields and interface chemistry to the VDOS.
Open Access
Semiconductor quantum dots driven by radiative and nonradiative energy transfer for high-efficiency hybrid LEDs and photovoltaics
(2011) Güzeltürk, Burak
Today the world energy demand has overtaken unprecedented consumption levels, which have never been reached before in the history of the world. The current trends indicate that the increasing demand for energy will tend to continue at an increasing pace in the coming decades due to worldwide globalization and industrialization. Scientific community is challenged to devise and develop fundamentally new technologies to cope with the energy problem of the world. To this end, optoelectronics can offer several solutions for energy efficiency both in light harvesting and generation. In this thesis, we propose and demonstrate enhanced light generation and harvesting by utilizing both radiative and nonradiative energy transfer capabilities of semiconductor nanocrystal quantum dots, which are profited for the development of novel hybrid devices combining superior properties of the constituent material systems. One of our proposals in this thesis relies on grafting nanostructured light emitting diodes with nanocrystal quantum dots to realize highly efficient color conversion. To the best of our knowledge, we report the highest nonradiative energy transfer efficiency of 83% obtained at room temperature for this type of colorconversion light emitting diodes owing to the architectural superiorities of their nanostructure. In another proposal, we addressed charge injection problems of electrically pumped nanocrystal-based light emitting diodes. We proposed and demonstrated the utilization of novel excitonic injection scheme to drive such LEDs of nanocrystals, which may become prominent especially for the display technology. Finally, we proposed and implemented quantum dot downconversion layers in nanostructured silicon solar cells to benefit the advantages of their nanostructured architecture. We have shown that nanostructured silicon solar cells lead to stronger enhancements compared to the planar counterparts.
Open Access
Slow light in Germanium nanocrystals
(2009) Keleş, Ümit
The phenomena of quantum coherence has been applied with great success in the atomic systems. For optoelectronic applications the interest is inherently directed towards the semiconductor heterostructures. Large number of works have proposed and analyzed the atomic quantum coherence effects in the semiconductors. In this respect, nanocrystals (NCs) are very promising structures for seeking the quantum coherence phenomena due to their atomic-like electronic structure. Furthermore, their robust structure, integrability and larger excitonic lifetimes with respect to atomic systems makes them more promising candidates for the technological applications. Within an atomistic pseudopotential electronic structure framework, the optical Bloch equations (OBEs) originating from atomic coherence theory are derived and solved numerically for Ge NCs. The results are interpreted in the context of coherent population oscillations (CPO). Narrow dips are observed in the absorption profiles which corresponds to high dispersions within a transparency window and produce slow light. A systematic study of the size-scaling of slow-down factor with respect to NC diameter and controllable slow light by applying external Stark field are provided. The results indicate that Ge NCs can be used to generate optically and electrically controllable slow light. The many-body Coulomb interactions which underlie the quantum coherence and dephasing are of central importance in semiconductor quantum confined systems. The effects of many-body interactions on the optical response of Ge NCs have been analyzed. The semiconductor optical Bloch equations (SBEs) are derived in a semiclassical approach and the Coulomb correlations are included at the level of Hartree-Fock approximation.
Open Access
Solution-processed nanostructures and devices for highly polarized light generation, scattering and sending
(2014) Uran, Can
Recent advancements in photonics have facilitated robust and reliable light sources, displays and photosensors with relatively long lifetimes and high energy efficiency in their classes. However, developing intrinsically polarization selective photonic devices still remains a challenge, although polarization sensitivity is essential to various advanced functions and/or improved performance. One of the main difficulties in making such devices emerges from the compromise on the efficiency while striving to reach high polarization contrast levels. For instance, commercially available birefringent structures including those integrating liquid crystals suffer from major transmission losses. On the other hand, solutionprocessed, high aspect-ratio nanostructures may offer power efficient platforms with high polarization contrasts via selection of the polarization in a preferred direction during emission, absorption and/or scattering process(es) while suppressing efficiency of the relevant ones in the other polarization. In this thesis, we present solution-processed metal and semiconductor nanostructures and optoelectronic devices made from them for highly polarized light generation and enhanced photosensing. Here we developed and demonstrated in-template fabricated suspended arrays of plasmonic thin nanodiscs with tunable disc-heights and gap-widths tailoring absorption and scattering properties for applications ranging from polarized light scattering to photodetection. Also, we proposed and showed highly polarized light emission in coupled thin films of magnetically aligned multisegmented nanowires and colloidal nanocrystals for polarized color enrichment in displays. Here well-controlled in-template synthesis of these nanowires together with their alignment under magnetic field allows for highly parallel orientation of the nanowires in massive numbers over large-area thin films. Integrating with color-enriching nanocrystals, this enabled a record high polarization contrast over 15:1 for the isotropic nanocrystals in the visible range. We believe that such hybrid assemblies of solution-processed nanostructures integrated into optoelectronic devices hold great promise for advanced functions in photonics.
Open Access
Synthesis and characterization of highly efficient CdSe/CdS core/shell nanocrystals with silar technique
(2012) Keleştemur, Yusuf
Owing to their size tunable electronic structure and optical properties, semiconductor nanocrystal quantum dots (NQDs) have become attractive for a wide range of device applications ranging from life sciences to electronics in the last two decades. However, highly efficient and stable NQDs are essential to reaching high performance with these devices utilizing NQDs. In this thesis, to meet these requirements, a new class of CdSe/CdS core/shell NQDs are studied including their colloidal synthesis and nanocharacterization. In this work, CdSe/CdS core/shell NQDs were synthesized with successive ion layer adsorption and reaction (SILAR) technique, which enabled highly precise shell thickness control and uniform coating of the shell material. When compared to the most commonly used CdSe/ZnS core/shell NQDs, CdSe/CdS core/shell NQDs were found to provide important advantages. First, the lattice mismatch within CdSe and CdS (3.9%) is lower than that within CdSe and ZnS (12%), which was very critical for obtaining highly efficient NQDs. Second, as a result of having lower bandgap in CdS, great enhancement in absorption cross section was achieved with more red-shifted emission, which is not possible with CdSe/ZnS core/shell NQDs. Moreover, suppression of Auger recombination was successfully observed with the partial separation of electron and hole wavefunctions in the synthesized CdSe/CdS core/shell NQDs. With all these attractive properties that were experimentally measured, CdSe/CdS core/shell NQDs were found to make better alternatives to CdSe/ZnS core/shell for numerous applications.