Browsing by Subject "Thin films."

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Open Access
BaOx
(2011) Emmez, Emre
In this work, formation anddecomposition pathways of of Ba(NO3)2 on BaOBaO2 /Pt(111) surfaces were investigated at the molecular levelfordifferent BaOBaO2coverages starting from small 2D islands of 0.5 MLE (MLE: monolayer equivalent) to thick multilayers of 10 MLE via temperature-programmed desorption (TPD), and X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). BaOxoverlayerswith a surface coverage of ~ 1 MLEreveallong range ordering with (2×2) and/or (1×2) structures while BaOx films with a surface coverage of1.5 MLEyields aBaO(110) termination and thicker films ( ≥ 5 MLE) were observed to be amorphous. Saturation of thick (10 MLE) BaOxoverlayers with NO2 leads to the formation of nitrates. Nitrate thermal decomposition was demonstrated to proceed through nitrite intermediates. In TPD experimentstwo major pathwaysfornitrate decomposition were observed: 1) nitrate decomposition yielding only NO evolutionat ~650 K, and 2) nitrate decomposition withNO + O2evolutionat ~700 K. This multi-step decomposition behavior was explained by BaO2 formation during the first stage. The influence of the BaOxdeposition method on the morphology of the BaOxoverlayers were established: when a thick BaOx layer is prepared using NO2 for Ba oxidation, BaOx overlayer efficiently wets the Pt(111) substrate forming a well-dispersed film. On the other hand, ifa thick BaOx layer is heated in O2 (to 873 K), BaOx overlayer agglomerates into 3D clusters, resulting in the formation of exposed (uncovered) Pt sites. BaOxoverlayers with uncoveredPt sitescan be “cured” by nitration – thermal decomposition procedures. When the BaOx layer coverage is below 2.5 MLE, nitrate decomposition temperature is observed at significantly lower temperatures, demonstrating the catalytic influence of the Pt sites facilitating the nitrate decomposition. It is proposed that initially, Ba(NO3)2 decomposesatthe boundary/peripheralsites of the Pt/BaOx interface, followed by the nitrate decomposition originating from 2D BaOx islands, and eventually from the 3D BaOx agglomerates. Catalytic deactivation of TiO2-promoted NOx-storage reduction (NSR) catalysts due to thermal aging effects was investigated using a BaO/TiO2/Pt(111) model catalyst system. At room temperature, metallic Ba overlayers on TiO2/Pt(111) was found to be very reactive towards oxide ions on TiO2/Pt(111) resulting in the formation of BaOx and partial reduction of TiO2. Ba films adsorbed on TiO2/Pt(111) that are further oxidized in O2 at 523 K lead to BaO and BaO2 surface domains which can efficiently adsorb both NO2 and CO2. Thermal treatment of BaOBaO2/TiO2/Pt(111) surface at T ≥ 300 K leads to a monotonic decrease in the surface Ba/Ti atomic ratio indicating the diffusion of BaO-BaO2 domains into the underlying TiO2 framework. Solid state reactions between BaOx and TiO2 particularly within 473-873K facilitate the formation of BaTiO3/Ba2TiO4/BaxTiyOz overlayers. After oxidation at higher temperatures (T > 873 K), surface becomes Badeficient and the enrichment of the surface with the Ti4+ sites results in a TiO2- terminated surface. Diffusion of BaOx into the TiO2 matrix and the enrichment of the surface with Ti sites drastically suppress the NO2 and CO2 adsorption/storage capacity of the model NOx storage system. These results reveal a direct evidence for the structural changes associated with the thermal deactivation of TiO2-promoted NSR catalysts.
Open Access
BaOx/ Pt(111) AND BaOx/ TiO2/ Pt(111) MODEL CATALYSTS FOR UNDERSTANDING NOx STORAGE-REDUCTION (NSR) CATALYSIS AT THE MOLECULAR LEVEL
(2011) Emmez, Emre
In this work, formation anddecomposition pathways of of Ba(NO3)2 on BaOBaO2 /Pt(111) surfaces were investigated at the molecular levelfordifferent BaOBaO2coverages starting from small 2D islands of 0.5 MLE (MLE: monolayer equivalent) to thick multilayers of 10 MLE via temperature-programmed desorption (TPD), and X-ray Photoelectron Spectroscopy (XPS) and Low Energy Electron Diffraction (LEED). BaOxoverlayerswith a surface coverage of ~ 1 MLEreveallong range ordering with (2×2) and/or (1×2) structures while BaOx films with a surface coverage of1.5 MLEyields aBaO(110) termination and thicker films ( ≥ 5 MLE) were observed to be amorphous. Saturation of thick (10 MLE) BaOxoverlayers with NO2 leads to the formation of nitrates. Nitrate thermal decomposition was demonstrated to proceed through nitrite intermediates. In TPD experimentstwo major pathwaysfornitrate decomposition were observed: 1) nitrate decomposition yielding only NO evolutionat ~650 K, and 2) nitrate decomposition withNO + O2evolutionat ~700 K. This multi-step decomposition behavior was explained by BaO2 formation during the first stage. The influence of the BaOxdeposition method on the morphology of the BaOxoverlayers were established: when a thick BaOx layer is prepared using NO2 for Ba oxidation, BaOx overlayer efficiently wets the Pt(111) substrate forming a well-dispersed film. On the other hand, ifa thick BaOx layer is heated in O2 (to 873 K), BaOx overlayer agglomerates into 3D clusters, resulting in the formation of exposed (uncovered) Pt sites. BaOxoverlayers with uncoveredPt sitescan be “cured” by nitration – thermal decomposition procedures. When the BaOx layer coverage is below 2.5 MLE, nitrate decomposition temperature is observed at significantly lower temperatures, demonstrating the catalytic influence of the Pt sites facilitating the nitrate decomposition. It is proposed that initially, Ba(NO3)2 decomposesatthe boundary/peripheralsites of the Pt/BaOx interface, followed by the nitrate decomposition originating from 2D BaOx islands, and eventually from the 3D BaOx agglomerates. Catalytic deactivation of TiO2-promoted NOx-storage reduction (NSR) catalysts due to thermal aging effects was investigated using a BaO/TiO2/Pt(111) model catalyst system. At room temperature, metallic Ba overlayers on TiO2/Pt(111) was found to be very reactive towards oxide ions on TiO2/Pt(111) resulting in the formation of BaOx and partial reduction of TiO2. Ba films adsorbed on TiO2/Pt(111) that are further oxidized in O2 at 523 K lead to BaO and BaO2 surface domains which can efficiently adsorb both NO2 and CO2. Thermal treatment of BaOBaO2/TiO2/Pt(111) surface at T ≥ 300 K leads to a monotonic decrease in the surface Ba/Ti atomic ratio indicating the diffusion of BaO-BaO2 domains into the underlying TiO2 framework. Solid state reactions between BaOx and TiO2 particularly within 473-873K facilitate the formation of BaTiO3/Ba2TiO4/BaxTiyOz overlayers. After oxidation at higher temperatures (T > 873 K), surface becomes Badeficient and the enrichment of the surface with the Ti4+ sites results in a TiO2- terminated surface. Diffusion of BaOx into the TiO2 matrix and the enrichment of the surface with Ti sites drastically suppress the NO2 and CO2 adsorption/storage capacity of the model NOx storage system. These results reveal a direct evidence for the structural changes associated with the thermal deactivation of TiO2-promoted NSR catalysts.
Open Access
Chemistry and structure of sputter deposited boron-carbon-nitrogen thin films
(2012) Genişel, Mustafa Fatih
There is a growing interest in synthesizing new materials with unique mechanical properties like hardness or electrical and optical properties. For this purpose, Boron-Carbon-Nitrogen (BCN) ternary phase diagram promises new materials with potentially unique properties, such as variable band gap semiconductors or phases with extreme hardness. On the other hand, the physical or mechanical properties of these new BCN materials strongly depend on the chemical environment of the atoms and their atomic structure. In this thesis, atomic structure and chemical environment of the atoms in BCN thin films were investigated. BCN films were synthesized by Reactive Magnetron Sputtering (RMS) technique from a B4C target. Various process parameters of synthesis were changed during deposition, such as the substrate bias, substrateto-target distance and N2 flow. The effect of process parameters are investigated with respect to their fundamental effects on the growing BCN films. Several sets of experiments were planned and conducted in order to gain insight as per their effect on the final chemistry and atomic structure. The characterization of the chemical composition of the films was done using data from Infrared Spectroscopy, Raman Spectroscopy, X-ray Photoelectron Spectroscopy, X-Ray Diffraction, and Electron Energy Loss Spectroscopy. Also, electron transparent thin crosssections from the BCN films were prepared using focused-ion beam technique for conducting High Resolution Transmission Electron Microscopy analysis for the verification of atomic structure. In the first series, named B series, the energy is supplied to growing film by applying a radio frequency generated d.c. bias on the substrate. Magnitude of the applied bias was changed throughout the series. In the second and third series, namely P and D series, the effect of substrate-to-target distance was investigated. In these series, BCN and BN films were deposited on substrates that were located at different distances from the target surface. In sub-series, effect of, i) the magnitude of applied bias, ii) type of applied substrate bias on the chemistry of the BCN films were scrutinized. In addition, the effect of atomic composition on the bonding preferences was studied. For this purpose, a series of BCN films were r.f. sputter deposited from B4C target with different N2 flow rate at the process gas. After the careful analysis of the data from mainly the spectroscopic techniques, several important results were obtained. First, a prevailing bonding preference, i.e. phase segregation, was observed in the films deposited regardless of the process parameters used, such that a dominant presence of B-N and C-C or C-N bonding were observed in the films. Furthermore, increasing the substrate bias or decreasing the substrate-to-target distance resulted in the atomic ordering and layered (turbostratic) BCN films. Examination of the spectroscopic data in detail also indicated that the individual layers were made out of separate domains of h-BN like and graphitic like carbon regions, which supports the phase-segregation assertion. Two main regimes are identified for the growth of BCN films; thermodynamically or kinetically controlled regimes. BCN films synthesized with large substrate bias or close to target surface were overall more ordered as the adatoms arriving on the substrate surface had enough energy to diffuse and find energetically most favorable sites. Such a case could be termed as thermodynamically controlled regime. In the opposite case, where adatoms were in a diffusion-limited environment, the final chemistry and structure was dictated by the kinetics. However, the prevalence of B-N bonding in both cases, and failure to observe hybridized chemistry suggests that bonding energy consideration is the major deciding factor for the chemistry of BCN films. As a conclusion, the work presented herein suggests that phase segregation in BCN films reveal as an innate character, while hybridization is not observed in the process parameter space explored. The main reason for this is the relative energies of the B-N and C-C bonding.
Open Access
Electrical properties and device applications of atomic layer deposited ZnO and GaN thin films
(2014) Bolat, Sami
Zinc oxide (ZnO), a semiconducting material with a wide band gap of 3.37 eV, has become a promising material for wide range of electronic and optoelectronic applications. One of the most important properties of this material is its large exciton binding energy of 60 meV, which makes ZnO a strong candidate for ultraviolet light emitting diodes and lasers. In addition, potentially high electron mobility and the transparency in the visible region strengthen the future of the ZnO based transparent electronics. Although several applications of ZnO have taken their places in the literature, use of ZnO in the thermal imaging applications is yet to be explored. In the parts of this thesis related to ZnO, the temperature coefficient of resistance and electrical noise together with resistivity and contact resistance properties of atomic layer deposition based ZnO are investigated. Due to its remarkably high temperature coefficient of resistance value and suitable 1/f noise corner frequency, this material is proposed as an alternative material to be used in the active layers of uncooled microbolometers. GaN is another wide gap semiconductor which has been intensely investigated throughout the last decades for its potential usage in both optical and electrical applications. Especially, high saturation velocity of the electric carriers of this material has made it a strong candidate to be used in high power applications. Furthermore the high electron mobility transistors based on the 2-dimensional electron gas region formed between the AlGaN and GaN, have found wide range of applications in radio frequency (RF) electronics area. Currently, most commonly used techniques for growing GaN, are metal organic chemical vapor deposition and molecular beam epitaxy. Both of these techniques offer single crystalline layers; however, the process temperatures used in the growth of the GaN disable the use of this material in low temperature flexible electronic/optoelectronic applications. In order to solve this problem, hollow cathode plasma assisted atomic layer deposition technique is utilized and GaN thin films with polycrystalline structures are successfully grown at 200°C. In the parts of this thesis related to GaN, the electrical properties, the effect of contact annealing on the resistivity of the GaN thin films and the contact resistance between this material and Ti/Au metallization scheme are investigated. Afterwards, we present the world’s first thin film transistor with atomic layer deposition based GaN channel and discuss its electrical characteristics in detail. Finally, the GaN thin film transistors are fabricated by performing all fabrication steps at temperatures below 250°C. This is the lowest process thermal budget for the GaN based thin film transistors reported so far. Electrical characteristics as well as the stability of the proposed device are investigated and the results obtained are discussed. Proposed devices are believed to pave the way for the GaN-based stable flexible/transparent electronics after further materials and process optimization.
Open Access
Fluorescent aerogel films for TNT sensing
(2009) Yıldırım, Adem
Silica aerogels are unique materials with extraordinary properties such as, high porosity, large surface area and low refractive indices. Due to these properties, they can be applied to a wide range of areas including, insulation, catalyst support, sensors and dielectric materials. However, until know because of their poor mechanical properties and costly production a few applications of aerogels were realized. Ambient pressure drying method is a promising way to produce low cost aerogels and thus expanding the realized application areas of aerogels. This method is based on lowering the surface tension on the gel network, in order to minimize the collapse of the gel during drying. For this purpose gel surface can be modified to make it hydrophobic. In the first part of this work, ambient pressure production of fluorescent aerogel thin films are described. The produced fluorescent films were characterized to identify their morphological, optical and surface properties. The gel was produced by using methlyltrimethoxysilane (MTMS) to produce hydrophobic gel. A porphyrin derivative (TCPPH2) was simply mixed with the sol before gelation for the fluorescence property. After gelation and aging the produced gels are homogenized and spin coated on glass substrates. The produced films were found to be highly porous (60.3-77.1%), fluorescent and transparent in visible region (82-89%). In the second part, sensing performances of the films were examined by using the common explosive trinitrotoluene (TNT). All films show fluorescence quenching based sensing against TNT exposure. The quenching efficiency of the films is highly thickness dependent. For the thinnest film (120 nm) the quenching efficiency was found to be 8.6% in 10 seconds and for the thickest film (1100 nm) film 2.1% in 10 seconds.
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 pyrene excimers in mesoporous organically modified silica thin films for visual detection of nitroaromatic explosives
(2013) Beyazkılıç, Pınar
Pyrene is a polycyclic aromatic hydrocarbon compound. Pyrene has been extensively applied as probing and sensing molecule because of excimer fluorescence which is formed upon interaction of two pyrene molecules in close proximity. In this thesis, we prepared porous thin films with bright pyrene excimer fluorescence and demonstrated their application in visual and rapid detection of nitroaromatic explosive vapors. The fluorescent films were obtained by physically encapsulating the pyrene molecules in the mesoporous organically modified silica (ormosil) networks which were synthesized via a facile template-free sol-gel method. Formation and stability of pyrene excimers were investigated in both porous and nonporous ormosil thin films. Excimer emission was found to be significantly brighter and more stable in porous films compared to nonporous films. The excellent stability of the pyrene excimers in the porous films is due to the nanoscale confinement of pyrene molecules in the porous ormosil network. We studied the nitroaromatic explosive sensing performances of the pyrene doped porous films. Films exhibited a rapid and visible fluorescence quenching when they were exposed to TNT vapor. Fluorescence quenching efficiency of an approximately 100 nm thick porous film was calculated to be 55.6% after exposure to TNT vapor for 30 seconds revealing a rapid sensing behavior. Fluorescence quenching of the films can be easily observed under UV light enabling naked-eye detection of nitroaromatic explosives. A selective quenching was observed in the excimer emission against vapors of nitroaromatic molecules; trinitrotoluene (TNT), dinitrotoluene (DNT) and nitrobenzene (NB) among various aromatic and nonaromatic compounds. Furthermore, quenched excimer emission of the films can be recovered by simply washing the films with water. It is shown that the films can be reused for at least five times after washing. To this respect, pyrene doped ormosil thin films can be presented as facile materials for nitroaromatic explosive sensing applications.
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
Micro and nanostructured devices for thermal analysis
(2008) Şenlik, Özlem
The recent advent of micro and nano devices increased the interest in small scale material properties, such as elasticity, conductivity or heat capacity, which are considerably different from their bulk counterparts due to, primarily, increasing surface to volume ratios. These novel properties must be analyzed by using ultra-sensitive devices since characterization of these properties is not possible with conventional probing instrumentation due to their large mass or volume which decreases signal to noise ratio. Microelectromechanical systems (MEMS) with short response time and high sensitivity are suitable for such measurements, such as very small mass detection (zeptograms) and calorimetry of small volume materials (yoctocalories). In this thesis a MEMS cantilever was used for thermomechanical characterization of thin film amorphous semiconductors. 100 nm thick As2S3 and Ge-As-Se-Te glasses were thermally evaporated onto a bilayer microcantilever. The microcantilever was deflected and vibrated by electrothermal actuation. By monitoring deflection, amplitude and phase of the cantilever oscillation, multiple glass transition and melting points were identified; the effects of the variation of thermal expansion coefficients (CTE), reversible and irreversible heat capacities and Young’s modulus of the thin film samples were observed simultaneously. Hence the possibility of the integration of calorimetry, thermomechanical analysis (TMA) and dynamical mechanical thermal analysis (DMTA) in a single MEMS device was demonstrate
Open Access
Molten Salt Assisted Self-Assembly (MASA) : synthesis of mesoporous silica-ZnO and mesoporous CdO thin films
(2012) Karakaya, Cüneyt
A series of mesostructured salt-silica-two surfactants (salt is [Zn(H2O)6](NO3)2, ZnX or [Cd(H2O)4](NO3)2, CdYand surfactants are cetyltrimethylammonium bromide (CTAB) and 10-lauryl ether, C12H25(OCH2CH2)10OH, C12EO10) thin films were synthesized by changing the Zn(II) or Cd(II)/SiO2 mole ratios. The films were prepared through spin coating of a clear solution of all the ingredients (salt, CTAB, C12E10, silica source (tetramethyl orthosilicate,TMOS, and water) and denoted as meso-silica-ZnX-n and meso-silica-CdY-n, where n is Zn(II) or Cd(II)/SiO2 mole ratios. The synthesis conditions were optimized by using the meso-silica-ZnX-1.14 and meso-silica-CdY-1.14 films and XRD, FT-IR spectroscopy, POM and SEM techniques. The stability of the films, especially in the high salt concentrations, was achieved above the melting point of salts. Slow calcination of the films, starting from the melting point of the salt to 450 oC has produced the mesoporous silica-metal oxide (ZnO and CdO) thin films, and denoted as meso-silica-ZnO-n and meso-silica-CdO-n, with n of 0.29, 0.57, 0.86, 1.14, and 1.43. The calcination process was monitored by measuring the FT-IR spectra and XRD patterns at different temperatures. Structural properties of the mesoporous films have been investigated using FT-IR spectroscopy, XRD, N2 sorption measurements, UV-Vis spectroscopy, SEM, TEM and EDS techniques. It has been found that the meso-silicaZnO-n and meso-silica-CdO-n films consist of nanocrystalline metal oxide nanoplates on the silica pore walls of the mesoporous framework. The formation of nanoplates of metal oxides was confirmed by etching the silica walls using diluted HF solution and by reacting with H2S and H2Se gases. The etching process produced CdO nanoplates without silica framework. The H2S and H2Se reactions with the CdO nanoplates or meso-silica-CdO have converted them to CdS and CdSe nanoplates or meso-silica-CdS and meso-silica-CdSe, respectively. Finally, a hypothetical surface coverage of metal oxide nanoplates has been calculated by combining the data of N2 sorption measurements, UV-Vis spectroscopy and TEM images and found that there is a full coverage of CdO and partial coverage of ZnO over silica walls in the meso-silica-CdO-n and meso-silica-ZnO-n thin films, respectively.
Open Access
Novel implantable distributively loaded flexible resonators for MRI
(2011) Gökyar, Sayım
Magnetic resonance imaging (MRI) is an enabling technology platform for imaging applications. In MRI, the imaging frequency falls within the radio frequency (RF) range where the tissue absorption of electromagnetic power is conveniently very low (e.g., compared to X-ray imaging), making MRI medically safe. As a result, MRI has evolved into a major imaging tool in medicine. However, in MRI, it is typically difficult to receive a magnetic resonance signal from tissue near a metallic implant, which hinders imaging of the implant device neighborhood to observe, monitor, and make assessment of the recovery and tissue compatibility. This can be accomplished by using locally resonating implants, but such implantable local resonators compatible with MRI that simultaneously feature reasonable chip size are currently not available (although there are some MRI-guided catheter applications). In this thesis, we proposed and developed a new class of implantable chip-scale local resonators that operate at radio frequencies of MRI, despite their small size, for the purposes of enhancing the signal-to-noise ratio (SNR) and thus the resolution in their vicinity. Here we addressed the scientific challenge of achieving low resonance frequency while maintaining chip-scale size suitable for potential MR-compatible implants. Using only biocompatible materials (gold, nitrides, and silicon or polyimide) within a substantially reduced footprint (miniaturized by 2 orders of magnitude), we demonstrated novel chip-scale designs based on the basic concept of split ring resonators (SRRs). Different than classical SRRs or those loaded with lumped elements (e.g., thin-film lumped loading), however, in our designs we loaded the SRR geometry in a distributive manner with a micro-fabricated dielectric thin-film layer to increase effective capacitance. For a proof-of-concept demonstration, we fabricated 20 mm ´ 20 mm resonators that operate at the resonance frequency of 130 MHz (compatible with 3 T MRI system) when distributively loaded with the capacitive film, which would otherwise operate around 1.2 GHz as a classical SRR of the same size if not loaded. It is worth noting that this resonance frequency of 130 MHz would normally require a classical SRR of 20 cm ´ 20 cm, a chip size 100-fold larger than ours. Designing and fabricating flexible thin-film resonators, we also showed that this architecture can be tuned by bending and is appropriate for non-planar surfaces, which is often the case for in vivo imaging. The phantom images indicated that, depending on the resonator configuration, these novel self-resonating structures increase SNR of the received signal by a maximum factor of 4 to 150 and over an enhancement penetration up to 10 mm into the phantom. This corresponds to a resolution enhancement in the 2D image by a factor of 2 to 12, respectively, under the same RF power. These in vitro experiments prove that it is possible to operate our local resonators at reduced frequencies via the help of distributive loading on the same chip. These findings suggest that proposed implantable resonator chips make promising candidates for self-resonating MR-compatible implants.
Open Access
Novel materials for thin-film memory cells
(2014) Çimen, Furkan
The tremendous growth in consumer electronics market increased the need for low-cost, low-power and high quality memory chips. This challenge is further aggravated by the continuous increase in density and scaling of the gate length, since it creates a major challenge for current nonvolatile flash memory devices to maintain reliability and retention. Therefore, it is imperative to find new materials and novel fabrication processes to be incorporated in memory cells in order to keep up with the enormous rate of increase in consumer needs. In the first part of this thesis, we demonstrate a charge trapping memory with graphene nanoplatelets embedded in atomic layer deposited ZnO. We first introduce the fabrication process for the memory device and then investigate the memory characteristics. Our experimental analysis on the memory cell shows a large threshold voltage Vt shift (4V ) at low operating voltages (6/ − 6V ), good retention (> 10 years), and good endurance characteristics (> 104 cycles). The resulting memory behavior is also verified by theoretical computations. In the second part, we demonstrate the use of laser-synthesized indium-nitride nanoparticles (InN-NPs) as the charge trapping layer in the memory cell. We first introduce the indium-nitride nanoparticle synthesis and then detail the fabrication process of the memory device. The experimental analysis of the memory cell results in a noticeable threshold voltage Vt shift (2V ) at low operating voltages (4V ) in addition to the similar retention and endurance performance with the graphene-based memory cells. The memory behavior was also verified with theoretical computations for the InN-NPs based memory cells. In the last part of this thesis, we demonstrate a memory device with a gate stack fabricated in a single ALD step. Single-step all-ALD approach avoids the risk of contamination and incorporation of impurities in the gate stack. It also allows low-cost production by eliminating multiple equipment utilization. Motivated by these, we first present the fabrication process of the memory device and then explain the experimental and theoretical characterization and analysis. The memory effect of the thin-film ZnO charge-trapping memory cell is verified by a 2.35V hysteresis in drain current vs. gate voltage curve. The resulting memory behavior is also verified by physics-based TCAD simulations.
Open Access
Novel nanocomposite coatings of nanoparticles
(2011) Toru, Refik Sina
Incorporating nanoparticles into nanocomposite thin-films enables coatings with multi-functionality depending on the particle type and size, and the film morphology. These multiple functions may include, for example, combinations of photocatalysis, hydrophobicity, scratch resistance, and antibacterial property. Here we proposed and demonstrated a new encapsulation nanocomposite with controllable refractive index and potentially additional functional properties for coating photonic devices, for instance, light-emitting diodes (LEDs). To design and implement this nanocomposite coating with tunable refractive index, we employed TiO2 nanoparticles of various diameters because of their relatively high refractive index. We embedded these nanoparticles in our encapsulation sol-gel material during synthesis. In addition, we incorporated several polymerforming chemicals during synthesis to control additional functions such as hydrophobicity and scratch resistance. We used characterization tools of atomic force microscopy, refractometry, contact angle measurement, and scanning electron microscopy to study material properties.
Open Access
Novel volumetric plasmonic resonator architectures for enhanced absorption in thin-film organic solar cells
(2010) Sefünç, Mustafa Akın
There has been a growing interest in decreasing the cost and/or increasing the efficiency of clean renewable energy resources including those of photovoltaic approaches for conversion of sunlight into electricity. Today, although photovoltaics is considered a potential candidate in diversification of energy sources, the cost of photovoltaic systems remains yet to be reduced by several factors to compete with fossil fuel based energy production. To this end, new generation solar cells are designed to feature very thin layers of active (absorbing) materials in the order of tens of nanometers. Though this approach may possibly decrease the cost of solar cells, these ultra-thin absorbing layers suffer from undesirably low optical absorption of incident photons. Recently revolutionary efforts on increasing light trapping using nanopatterned metal layers in the active photovoltaic material via surface plasmon excitations have been demonstrated, which attracted interest of the academic community as well as the industry. In these prior studies, plasmonic structures, placed either on the top or at the bottom of absorbing layers, have been investigated to enhance the absorption in the active material. However, all these previous efforts were based only on using a single layer of plasmonic structures. In this thesis, different than the previous reports of our group and the others, we focus on a new design concept of volumetric plasmonic resonators that relies on the idea of incorporating two (or more) layers of coupled plasmonic structures embedded in the organic solar cells. For proof-of-concept demonstration, here we embody one silver grating on the top of the absorbing layer and another at the bottom of the active layer to couple them with each other such that the resulting field localization is further increased and extended within the volume of the active material. In addition to individual plasmonic resonances of these metallic structures, this allows us to take the advantage of the vertical interaction in the volumetric resonator. Our computational results show that this architecture exhibits a substantial absorption enhancement performance particularly under the transverse-magnetic polarized illumination, while the optical absorption is maintained at a similar level as the top grating alone under the transverseelectric polarized illumination. As a result, the optical absorption in the active layer is enhanced up to ~67%, surpassing the improvement limit of individual gratings, when the total film thickness is kept fixed. This volumetric interaction contributes to further enhancement of optical absorption in the active layer, beyond the limited photon absorption in non-metallic (bare) organic solar cell.
Open Access
Organically modified silica based nanomaterials for functional surfaces
(2012) Budunoğlu, Hülya
Organically modified silicas (ormosils) are unique materials due to their combined properties achieved from organics and inorganics. Ormosils contain at least one non-hydrolysable organic groups which results in a decrease of rigid Si-O-Si bonds, introducing a flexible character. Therefore, ormosils exhibit both flexibility of organics and atmospheric stability of inorganics. Organic group determines the functionalities of ormosils, thus their properties can be adjusted by choice of appropriate organic modification. Ormosils can be easily prepared in mild conditions of sol-gel technique, and can be applied on different surfaces by low cost and simple techniques. In this thesis, we prepared superhydrophobic-superhydrophilic, antireflectiveantifogging, anticorrosion and antiicing (ice retarding) functional surfaces using organically modified silica and its nano-composites in thin film form. Methyltrimethoxysilane (MTMS) is used in the synthesis of all films due to its intrinsically hydrophobic nature. This monomer is found to enable porous film formation without any modifications at ambient temperature and pressure. Superhydrophobic ormosil aerogel films with water contact angles reaching 179.9 and porosity of 86 % have been prepared using phase separated colloidal suspensions of MTMS, which exhibited flexibility, thermal stability and superhydrophilic transition after annealing at 600 C. Antireflective films with high mechanical stability are prepared from co-condensation of MTMS with tetraethylorthosilicate monomer, which exhibited transmission as high as 99.6 % with flexibility and transition to antifogging after annealing at 600 C. Anticorrosion films for glass surfaces have been prepared by encapsulation of ZnO and ZrO2 nanoparticles to yield nano-composites of porous and nonporous ormosil films, which resulted in four times less corrosion compared to bare glass and acts as a barrier layer for corrosion of glass substrates against alkaline corrosion. In formation of antiicing coatings various combinations of ormosil films mentioned are used and correlation between contact angle, stability of contact angle against cooling, surface roughness and freezing times are investigated. Compared to bare glass, freezing times are increased two order of magnitudes.
Open Access
The phase behavior and synthesis of mesostructured coupled semiconductor thin films : MESO-CdS-TiO2
(2009) Okur, Halil İbrahim
Mesostructured [Cd(H2O)4](NO3)2 - titania - P123 ((PEO)20(PPO)70(PEO)20, PEO = -OCH2CH2-, PPO = -OCH(CH3)CH2-) materials have been investigated by changing the [Cd(H2O)4](NO3)2 and titania content of the structures. This has been achieved by making thick samples by casting and thin film samples by spin coating of a butanol solution of [Cd(H2O)4](NO3)2, P123, nitric acid and Ti(OC4H9)4. The film samples are named as meso-xCd(II)-yTiO2, where x is the Cd(II)/P123 and y is TiO2/P123 mole ratios. Increasing the titania amount in the media has transformed the samples from LC-like to soft and then to rigid mesostructured materials. Changing the amount of [Cd(H2O)4](NO3)2 salt in the media only influenced the mesostructure, such that no change on the mechanical properties is observed. However, the synthesis of rigid mesostructured titania materials required controlled humidity. The rigid film samples were prepared first by spin coating and then by aging under a 50% humidity oven. The mesostructure remains stable upon H2S reaction, in the soft and rigid materials region. However, only rigid samples stand to removal of nitrates from the media that is important to keep the CdS nanoparticles stable in or on the pore walls of mesostructured film samples. The phase behavior of the meso-Cd(II)-TiO2, the structural properties of the meso-xCdS-yTiO2 samples, coordination and elimination of the NO3 - ions and the particle size of the CdS nanocrystallites were investigated using diffraction (XRD), spectroscopy (FT-IR, Raman and UV-Vis absorption, EDS) and microscopy (POM, SEM, and TEM) techniques.
Open Access
Plasma-assisted atomic layer deposition of III-nitride thin films
(2014) Özgit-Akgün, Çağla
III-nitride compound semiconductors and their alloys have emerged as versatile and high-performance materials for a wide range of electronic and optoelectronic device applications. Besides possessing very unique material properties individually, members of the III-nitride family with wurtzite (hexagonal) crystal structure also exhibit direct band gaps, which cover a wide range with values of 6.2, 3.4 and 0.64 eV for AlN, GaN and InN, respectively. In this respect, ternary and quaternary alloys of this family are particularly important since their bandgaps can easily be tuned by adjusting the alloy composition. Although high quality IIInitride thin lms can be grown at high temperatures (>1000 XC) with signi cant rates, deposition of these lms on temperature-sensitive device layers and substrates necessitates the adaptation of low-temperature methods such as atomic layer deposition (ALD). ALD is a special type of chemical vapor deposition, in which the substrate surface is exposed to sequential pulses of two or more precursors separated by purging periods. When compared to other low-temperature thin lm deposition techniques, ALD stands out with its self-limiting growth mechanism, which enables the deposition of highly uniform and conformal thin lms with sub-angstrom thickness control. Moreover, alloy thin lms can be easily deposited by ALD, where lm composition is digitally controlled by the relative number of subcycles. In this thesis, we report on the development of plasma-assisted ALD (PAALD) processes for III-nitrides, and present detailed characterization results for the deposited thin lms and fabricated nanostructures. PA-ALD of polycrystalline wurtzite AlN thin lms was realized at temperatures ranging from 100- 500 XC using trimethylaluminum (AlMe3) as the Al precursor. Films deposited at temperatures within the ALD window (100-200 XC for both ammonia (NH3) and N2/H2 plasma processes) were C-free and had relatively low O concentrations (<3 at.%). We also demonstrated the conformality of AlMe3-NH3 plasma process by fabricating high surface area AlN hollow nano bers using electrospun nylon nano ber mats as sacri cial templates. Our initial e orts for depositing GaN and InN resulted in thin lms with high O concentrations. Although - at rst - the most probable source of this contamination was presumed as the O-containing impurities in the unpuri ed 5N-grade NH3 gas, subsequent experiments revealed the true source as the quartz tube of inductively coupled RF-plasma (ICP) source itself. In view of these circumstances, the choice of N-containing plasma gas (NH3, N2/H2 or N2) determined the severity of O incorporation into AlN and GaN lms deposited by PA-ALD. As an e ort to completely avoid this plasma-related oxygen contamination problem, we replaced the original quartz-based ICP source of the ALD system with a stainless steel hollow cathode plasma (HCP) source. Thereby we demonstrated the low-temperature hollow cathode PA-ALD (HCPAALD) of crystalline AlN, GaN and AlxGa1−xN thin lms with low impurity concentrations (O, C <1 at.%) using AlMe3 and trimethylgallium (GaMe3) as the Al and Ga precursors, respectively. Optical band edge values of the AlxGa1−xN lms shifted to lower wavelengths with the increasing Al content, indicating the tunability of band edge values with alloy composition. HCPA-ALD of InN was also investigated within the scope of this study. Initial results revealed the possibility to obtain single-phase wurtzite InN thin lms using cyclopentadienyl indium (CpIn) as the In precursor.
Open Access
Plasmonic nanoparticles by laser dewetting of thin metallic films
(2013) Sarıtaş, Seval
In this work, formation of metal nanoparticles via laser induced dewetting and their plasmonic properties have been investigated. The effects of metal film, substrate type, laser power density and dwell time on dewetting phenomenon were analyzed. Silver and gold thin films were fabricated with thermal evaporation on various substrates. Next, they were characterized by the ellipsometry, UV-VIS spectroscopy and atomic force microscopy (AFM) as the characteristic of the thin film affects dewetting. Samples were then processed by a cw argon laser. Varying the dwell time and power density, Ag and Au nanoparticles with different morphology were obtained. At the final stages of dewetting, nanoparticles attained spherical shapes. Particle size distribution and length scale analysis were performed using the images obtained from scanning electron microscope (SEM). Using these results, relations between the average particle size and film thickness, as well as the relation between length scale and film thickness were obtained to verify the occurrence of dewetting. Substrate and film type were observed to affect the particle morphology and particle size. Moreover, plasmonic resonance effect of Ag and Au nanoparticles were observed via the optical absorbance measurements. Multilayered metallic nanoparticles and embedded nanoparticles were fabricated and were found to display plasmonic properties.
Open Access
Resistive switching mechanism and device applications of ZnO and Ain thin films
(2014) Özcan, Ayşe
Resistive switching memories are potential candidates for next generation nonvolatile memory device applications due to natural simplicity in structure, fast switching speed, long retention time, low power consumption, suitability for 3D integration, excellent scalability and CMOS compatibility. However, the atomic scale mechanisms behind resistive switching are still being debated. In this work we investigate resistive switching mechanisms in ZnO and AlN thin films. The structural and physical changes in ZnO thin films during resistive switching are investigated via TEM, EDX, EFTEM techniques. We also investigate application of resisitive switching to reconfigurable optical surfaces. Recently, resistive switching in nitride films such as AlN is attracting increasing attention. The wide band gap, high electrical resistivity, and high thermal conductivity of AlN make it a good candidate for a resistive switching memory device. We report self-compliant resistive switching behavior in AlN films which is deposited by atomic layer deposition.
Open Access
Synthesis and characterization of mesoporous metal sulfide and metal selenide thin films using liquid crystalline mesophases
(2012) Türker, Yurdanur
In this thesis, synthesis of the mesoporous CdS and CdSe by using of liquid crystalline templating (LCT) approach has been investigated. In the first part of the thesis, the thermal and structural behavior of the [Cd(H2O)4](NO3)2/surfactant (P85 = ((PEO)26(PPO)40(PEO)26)) binary lyotropic liquid crystalline (LLC) systems have been investigated towards synthesis of the mesoporous cadmium sulfide, CdS, or cadmium selenide (CdSe) directly from the mesostructured CdS (or CdSe) thin films. However, the mesostructured CdS/P85 films (at low salt concentrations), which were obtained by reacting [Cd(H2O)4](NO3)2/P85 LLC thin films under H2S atmosphere, are not stable to calcination process and always produced bulk CdO and CdS domains over the thin films. More metal ion containing [Cd(H2O)4](NO3)2-C12EO10-CTAB mesostructured films produced vast amount of HNO3 under the H2S atmosphere and caused decomposition of CdS back to their nitrates. To overcome above problems, a polymerizing agent, such as titania or silica precursors have been added to salt/surfactant LLC mesophase. Both titania and silica overcame the collapse of the mesophase by rigidifying the structure into mesostructured solid and also by providing stability for a thermal removal of nitrates from the medium. For this investigation, both [Cd(H2O)4](NO3)2 and [Zn(H2O)6](NO3)2 salts and P123 ((PEO)20(PPO)70(PEO)20) and C12EO10-CTAB couple have been used. Well-ordered mesostructured Cd(II) titania films have been obtained up to 15.0 Cd(II)/P123 mole ratio for a 60 mole ratio of Ti(IV)/P123 by spin or dip coating of a mixture of 1-butanol-[Cd(H2O)4](NO3)2-P123-HNO3-Ti(OC4H9)4. Exposing the mesostructured Cd(II)-TiO2 films to H2Se under a N2 atmosphere gave stable CdSe nanoparticles in the channels of the mesostructured rigid titania walls up to 25 mole % Cd(II)/Ti(IV). To further increase the metal ion (Cd(II) and Zn(II)) content in the structure, the C12EO10-CTAB-salt mesophase has been employed. The two surfactant-salt systems, in the presence of a titania precursor, produced sponge like mesoporous CdTiO3 and Zn2TiO4 films up to a mole percent of 57 and 86, respectively, upon calcination. Exposing the mesoporous CdTiO3 to H2S or H2Se atmosphere at RT produced homogeneously distributed CdS or CdSe nanocrystallites on the nanocrystalline TiO2 pore walls, respectively. The reaction of mesoporous Zn2TiO4 with H2Se produced stable ZnSe nanocrystallites on the nanocrystalline TiO2 pore walls. The conversion of titania from CdTiO3 to an anatase and brookite phase under H2S and H2Se atmosphere, respectively, and from Zn2TiO4 to a rutile phase under H2Se were observed for the first time. Adding a silica precursor to the two surfactants (C12EO10-CTAB)-salt mesophase produced mesostructured salted-silica, and its calcination produced sponge-like mesoporous silica-metal oxide (dumped meso-SiO2-CdO and mesoSiO2-ZnO) thin films. Up to ~100 % and ~50 % surface coverage could be achieved by CdO and ZnO as nano-islands over the SiO2 pore walls. Exposing the mesoporous SiO2-CdO and SiO2-ZnO thin film precursors to H2S and H2Se at RT enabled the synthesis of mesoporous SiO2-CdS, SiO2-CdSe, SiO2-ZnS, and SiO2- ZnSe thin films. The MS or MSe nanoflakes could homogenously cover the pore walls of mesoporous silica by retaining the pore morphology of the MO precursors. The H2S and H2Se reactions are slow and can be monitored using UV-Vis absorption spectroscopy and EDS to elucidate the reaction mechanism and kinetics. These data showed that the reaction starts from the top surface of the MO domains and proceeds until Si-O-M bond break. Finally, the SiO2 walls were removed from the meso-SiO2-CdS and meso-SiO2-CdSe films through etching in a dilute HF solution to produce mesoporous CdS (meso-CdS) and mesoporous CdSe (meso-CdSe). Surface of the meso-CdS has been modified using PEI (polyethyleneimine) and photoluminescent meso-CdS were obtained.