Browsing by Subject "High resolution transmission electron microscopy"

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Open Access
Amorphous to tetragonal zirconia anostructures and evolution of valence and core regions
(American Chemical Society, 2015) Vempati S.; Kayaci-Senirmak, F.; Ozgit-Akgun, C.; Bıyıklı, Necmi; Uyar, Tamer
In this report, we study the evolution of valence band (VB) structure during a controlled amorphous to tetragonal transformation of ZrO2 core-shell nanostructures fabricated from electrospun nanofiber template (at 130, 200, and 250 °C). Shell-ZrO2 was formed with atomic layer deposition. X-ray diffraction and transmission electron microscopy are employed to unveil the transformation of amorphous to crystalline structure of ZrO2. O 1s core-level spectra indicated chemisorbed oxygen (OCh) of almost invariant fraction for the three samples. Zr 3s level suggested that the sample deposited at 130 °C has depicted a peak at relatively higher binding energy. Analyses on Zr 3d spectra indicated the presence of metallic-Zr (Zr+ζ, 0 ≤ |ζ| < 4), the fraction of which decreases with increasing template temperature. VB region is analyzed until ∼64 eV below the Fermi level (EF). The region close to EF depicted features that are dissimilar to the literature. This discrepancy is explained on the basis of the analyses from O 1s, Zr 3d, and Zr 4p levels including hybridization of orbitals from chemisorbed species. These levels were analyzed in terms of peak characteristics such as spectral position, area under the peak, etc. The results of this study would enhance the understanding of the evolution of various bands in the presence of OCh and changes to the crystallinity enabling the functionalities that are not available in the single-phase ZrO2.
Open Access
CdSe/CdSe1-xTex core/crown heteronanoplatelets: tuning the excitonic properties without changing the thickness
(American Chemical Society, 2017) Kelestemur Y.; Guzelturk, B.; Erdem, O.; Olutas M.; Erdem, T.; Usanmaz, C. F.; Gungor K.; Demir, Hilmi Volkan
Here we designed and synthesized CdSe/CdSe1-xTex core/crown nanoplatelets (NPLs) with controlled crown compositions by using the core-seeded-growth approach. We confirmed the uniform growth of the crown regions with well-defined shape and compositions by employing transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. By precisely tuning the composition of the CdSe1-xTex crown region from pure CdTe (x = 1.00) to almost pure CdSe doped with several Te atoms (x = 0.02), we achieved tunable excitonic properties without changing the thickness of the NPLs and demonstrated the evolution of type-II electronic structure. Upon increasing the Te concentration in the crown region, we obtained continuously tunable photoluminescence peaks within the range of ∼570 nm (for CdSe1-xTex crown with x = 0.02) and ∼660 nm (for CdSe1-xTex crown with x = 1.00). Furthermore, with the formation of the CdSe1-xTex crown region, we observed substantially improved photoluminescence quantum yields (up to ∼95%) owing to the suppression of nonradiative hole trap sites. Also, we found significantly increased fluorescence lifetimes from ∼49 up to ∼326 ns with increasing Te content in the crown, suggesting the transition from quasi-type-II to type-II electronic structure. With their tunable excitonic properties, this novel material presented here will find ubiquitous use in various efficient light-emitting and -harvesting applications.
Open Access
A complementary electrochromic device with highly improved performance based on brick-like hydrated tungsten trioxide film
(American Scientific Publishers, 2012) Jiao, Z.; Wang, J.; Ke, L.; Sun, X. W.; Demir, Hilmi Volkan
Uniform and well adhesive nanostructured hydrated tungsten trioxide (3WO 3•H 2O) films were grown on fluorine doped tin oxide (FTO) substrate via a facile and template-free crystal-seed-assisted hydrothermal method by addition of ammonium sulfate ((NH 4) 2SO 4) and hydrogen peroxide (H 2O 2). X-ray diffraction (XRD) studies indicated that the films are of orthorhombic structure. Scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) analysis showed that the film was composed of brick-like nanostructures with a preferred growing direction along (002). The influence of seed layer, (NH 4) 2SO 4 and H 2O 2 on the products were also studied. The film showed good cyclic stability, comparable switching speed and coloration efficiency (30.1 cm 2 C -1). A complementary electrochromic device based on the film and Prussian blue depicted highly improved color contrast, coloration/bleaching response (1.8 and 3.7 s respectively) and coloration efficiency (164.6 cm 2 C -1).
Open Access
Confined linear carbon chains as a route to bulk carbyne
(Nature Publishing Group, 2016-04) Shi, L.; Rohringer, P.; Suenaga, K.; Niimi, Y.; Kotakoski, J.; Meyer, J. C.; Peterlik, H.; Wanko, M.; Cahangirov, S.; Rubio, A.; Lapin, Z. J.; Novotny, L.; Ayala, P.; Pichler, T.
Strong chemical activity and extreme instability in ambient conditions characterize carbyne, an infinite sp1 hybridized carbon chain. As a result, much less has been explored about carbyne as compared to other carbon allotropes such as fullerenes, nanotubes and graphene. Although end-capping groups can be used to stabilize carbon chains, length limitations are still a barrier for production, and even more so for application. We report a method for the bulk production of long acetylenic linear carbon chains protected by thin double-walled carbon nanotubes. The synthesis of very long arrangements is confirmed by a combination of transmission electron microscopy, X-ray diffraction and (near-field) resonance Raman spectroscopy. Our results establish a route for the bulk production of exceptionally long and stable chains composed of more than 6,000 carbon atoms, representing an elegant forerunner towards the final goal of carbyne's bulk production.
Open Access
Cubic-phase zirconia nano-island growth using atomic layer deposition and application in low-power charge-trapping nonvolatile-memory devices
(Institute of Physics Publishing Ltd., 2017) El-Atab, N.; Ulusoy, T. G.; Ghobadi, A.; Suh, J.; Islam, R.; Okyay, Ali Kemal; Saraswat, K.; Nayfeh, A.
The manipulation of matter at the nanoscale enables the generation of properties in a material that would otherwise be challenging or impossible to realize in the bulk state. Here, we demonstrate growth of zirconia nano-islands using atomic layer deposition on different substrate terminations. Transmission electron microscopy and Raman measurements indicate that the nano-islands consist of nano-crystallites of the cubic-crystalline phase, which results in a higher dielectric constant (κ ∼ 35) than the amorphous phase case (κ ∼ 20). X-ray photoelectron spectroscopy measurements show that a deep quantum well is formed in the Al2O3/ZrO2/Al2O3 system, which is substantially different to that in the bulk state of zirconia and is more favorable for memory application. Finally, a memory device with a ZrO2 nano-island charge-trapping layer is fabricated, and a wide memory window of 4.5 V is obtained at a low programming voltage of 5 V due to the large dielectric constant of the islands in addition to excellent endurance and retention characteristics.
Open Access
Gold catalysts supported on ceria doped by rare earth metals for water gas shift reaction: influence of the preparation method
(2009) Andreeva, D.; Ivanov, I.; Ilieva, L.; Abrashev, M. V.; Zanella, R.; Sobczak, J. W.; Lisowski, W.; Kantcheva, M.; Avdeev, G.; Petrov, K.
Gold catalysts based on ceria, doped by various RE metals (La, Sm, Gd, Yb, Y) were studied. The influence of the preparation methods on structure, properties and catalytic activity in the WGS reaction was investigated. The catalysts' supports were prepared using two different methods: co-precipitation (CP) and mechanochemical activation (MA). The catalysts were tested in a wide temperature interval without and after reactivation. All samples were characterized using a combination of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy (RS) and X-ray photoelectron spectroscopy (XPS) and TPR. It was found that the catalytic activity of MA catalysts is higher than CP ones. The gold catalysts based on ceria doped by Yb and Sm exhibited the highest activity. After reactivation in air the MA samples almost kept the WGS activity same, while the CP catalysts increased it. The catalysts of a single- and double-phase structure are formed as a result of CP and MA preparation, respectively. There are no big differences in the gold particles size (2-3 nm) depending on dopants and on the preparation techniques. The RS spectra analysis indicates that most probably the oxygen vacancies are adjacent to Me3+ dopant and the ceria structure seems to be better ordered than in the case of alumina as a dopant. There is no distinct correlation between reducibility and WGS activity. The XPS analysis disclose positively charged gold particles in addition to metallic gold within a surface region of fresh samples and only metallic gold on the samples after catalytic processing. There is no simple correlation between the concentration of Ce3+ in the samples and their WGS activity.
Open Access
Investigation on the formation of Cu-Fe nano crystalline super-saturated solid solution developed by mechanical alloying
(2013) Mojtahedi, M.; Goodarzi, M.; Aboutalebi, M.R.; Ghaffari, M.; Soleimanian V.
In this study, the formation of super saturated solid solution in the binary Cu-Fe system was investigated. Three powder blends with 30, 50 and 70 wt.% of Fe were milled for different times to 96 h. The variations of lattice parameter and inter-planar spacing were calculated and analyzed using X-ray diffraction analysis (XDA). The anisotropy of lattice deformation in the FCC phase was studied and the obtained results were compared to milled pure Cu powder. Furthermore, crystallite size was calculated using Scherer formula in comparison with Rietveld full profile refinement method. Considering the previous studies about the formation of non-equilibrium FCC and BCC phases, the phase evolution has been discussed and the proportion of each phase was calculated using Rietveld refinement method. Supplementary studies on the evolution of microstructure and formation of solid solution were carried out using high resolution transmission electron microscopy (HRTEM). Finally, high angle annular dark field (HAADF) imaging was utilized to find out the level of homogeneity in the resulting phases. While true alloying takes place in each phase, the final structure consists of both FCC and BCC nano-crystallites. © 2012 Elsevier B.V. All rights reserved.
Open Access
Low-temperature grown wurtzite InxGa1−xN thin films via hollow cathode plasma-assisted atomic layer deposition
(Royal Society of Chemistry, 2015-08) Haider A.; Kizir S.; Ozgit Akgun, C.; Goldenberg, E.; Leghari, S. A.; Okyay, Ali Kemal; Bıyıklı, Necmi
Herein, we report on atomic layer deposition of ternary InxGa1−xN alloys with different indium contents using a remotely integrated hollow cathode plasma source. Depositions were carried out at 200 °C using organometallic Ga and In precursors along with N2/H2 and N2 plasma, respectively. The effect of In content on structural, optical, and morphological properties of InxGa1−xN thin films was investigated. Grazing incidence X-ray diffraction showed that all InxGa1−xN thin films were polycrystalline with a hexagonal wurtzite structure. X-ray photoelectron spectroscopy depicted the peaks of In, Ga, and N in bulk of the film and revealed the presence of relatively low impurity contents. In contents of different InxGa1−xN thin films were determined by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. Transmission electron microscopy also confirmed the polycrystalline structure of InxGa1−xN thin films, and elemental mapping further revealed the uniform distribution of In and Ga within the bulk of InxGa1−xN films. Higher In concentrations resulted in an increase of refractive indices of ternary alloys from 2.28 to 2.42 at a wavelength of 650 nm. The optical band edge of InxGa1−xN films red-shifted with increasing In content, confirming the tunability of the band edge with alloy composition. Photoluminescence measurements exhibited broad spectral features with an In concentration dependent wavelength shift and atomic force microscopy revealed low surface roughness of InxGa1−xN films with a slight increase proportional to In content.
Open Access
Low-temperature self-limiting atomic layer deposition of wurtzite InN on Si(100)
(American Institute of Physics Inc., 2016) Haider, A.; Kizir, S.; Bıyıklı, Necmi
In this work, we report on self-limiting growth of InN thin films at substrate temperatures as low as 200 °C by hollow-cathode plasma-assisted atomic layer deposition (HCPA-ALD). The precursors used in growth experiments were trimethylindium (TMI) and N2 plasma. Process parameters including TMI pulse time, N2 plasma exposure time, purge time, and deposition temperature have been optimized for self-limiting growth of InN with in ALD window. With the increase in exposure time of N2 plasma from 40 s to 100 s at 200 °C, growth rate showed a significant decrease from 1.60 to 0.64 Å/cycle. At 200 °C, growth rate saturated as 0.64 Å/cycle for TMI dose starting from 0.07 s. Structural, optical, and morphological characterization of InN were carried out in detail. X-ray diffraction measurements revealed the hexagonal wurtzite crystalline structure of the grown InN films. Refractive index of the InN film deposited at 200 °C was found to be 2.66 at 650 nm. 48 nm-thick InN films exhibited relatively smooth surfaces with Rms surface roughness values of 0.98 nm, while the film density was extracted as 6.30 g/cm3. X-ray photoelectron spectroscopy (XPS) measurements depicted the peaks of indium, nitrogen, carbon, and oxygen on the film surface and quantitative information revealed that films are nearly stoichiometric with rather low impurity content. In3d and N1s high-resolution scans confirmed the presence of InN with peaks located at 443.5 and 396.8 eV, respectively. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) further confirmed the polycrystalline structure of InN thin films and elemental mapping revealed uniform distribution of indium and nitrogen along the scanned area of the InN film. Spectral absorption measurements exhibited an optical band edge around 1.9 eV. Our findings demonstrate that HCPA-ALD might be a promising technique to grow crystalline wurtzite InN thin films at low substrate temperatures.
Open Access
Phase transformation during mechano-synthesis of nanocrystalline/amorphous Fe–32Mn–6Si alloys
(Elsevier, 2013) Amini, R.; Shamsipoor, A.; Ghaffari, M.; Alizadeh, M.; Okyay, Ali Kemal
Mechano-synthesis of Fe-32Mn-6Si alloy by mechanical alloying of the elemental powder mixtures was evaluated by running the ball milling process under an inert argon gas atmosphere. In order to characterize the as-milled powders, powder sampling was performed at predetermined intervals from 0.5 to 192 h. X-ray florescence analyzer, X-ray diffraction, scanning electron microscope, and high resolution transmission electron microscope were utilized to investigate the chemical composition, structural evolution, morphological changes, and microstructure of the as-milled powders, respectively. According to the results, the nanocrystalline Fe-Mn-Si alloys were completely synthesized after 48 h of milling. Moreover, the formation of a considerable amount of amorphous phase during the milling process was indicated by quantitative X-ray diffraction analysis as well as high resolution transmission electron microscopy image and its selected area diffraction pattern. It was found that the α-to-γ and subsequently the amorphous-to-crystalline (especially martensite) phase transformation occurred by milling development.
Open Access
Polyhedral oligomeric silsesquioxane-based hybrid networks obtained via thiol-epoxy click chemistry
(Springer, 2017) Bekin Acar, S.; Ozcelik, M.; Uyar, Tamer; Tasdelen, M. A.
A series of hybrid networks based on polyhedral oligomeric silsesquioxane (POSS) were prepared by thiol-epoxy click reaction using commercially available octakis-glycidyl-POSS (G-POSS), trimethylolpropane triglycidyl ether, and trimethylolpropane tris(3-mercaptopropionate) as monomers. The click reaction was simply catalyzed by lithium hydroxide which proceeded readily at ambient conditions in very good yields. The incorporation of G-POSS into the network was clearly determined by transmission electron microscopy, FTIR, and 1H-NMR spectroscopy techniques performed with a model study using 1-butane thiol and G-POSS molecules. The homogeneous distribution of G-POSS up to 5 wt% in the hybrid network was apparently confirmed by morphological investigations. By increasing G-POSS content higher than 5 wt%, the heterogeneous dispersion of G-POSS was determined from the tensile strength measurements. The significant decrease in tensile strength was possible due to the agglomeration of G-POSS. On the other hand, thermal properties of hybrid networks were compared together by thermogravimetric analyses, where all samples exhibited one-step degradation in the range of 220–500 °C. The thermal decomposition of hybrid network led to complete degradation of the organic part and favored the formation of stable carbonaceous and inorganic residues as char. Thus, the char yields of hybrid networks were increased to 6.2, 7.8, 10.1, 12.7, and 15.1% by G-POSS loadings from 0 to 15 wt%. This improvement was also a proof of the incorporation of G-POSS into the hybrid networks that resulted in high heat-resistant POSS-based hybrid networks compared to a sample without G-POSS.
Open Access
Quantitative phase evolution during mechano-synthesis of Ti-Ni-Cu shape memory alloys
(Elsevier, 2012-05-29) Amini, R.; Alijani, F.; Ghaffari, M.; Alizadeh, M.; Okyay, Ali Kemal
Ti-41Ni-9Cu shape memory alloy was synthesized by mechanical alloying of pure elemental Ti, Ni, and Cu powders using high-energy ball milling. The qualitative and quantitative phase analyses of the as-milled powders were done by X-ray diffraction (XRD) using Rietveld refinement and the alloys microstructure was studied by scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM). Concerning the results, by milling evolution, the dissolution of the primary materials occurred at different rates and a considerable amount of the amorphous phase as well as B19′-martensite and B2-austenite was created. The formation of Ni solid solution was also evidenced prior to its dissolution. It was found that at sufficient milling time, the mechano-crystallization of the amorphous phase occurred and at the end of milling, the B19′-martensite is the dominant phase of the structure.
Open Access
Self-limiting low-temperature growth of crystalline AlN thin films by plasma-enhanced atomic layer deposition
(2012) Ozgit, C.; Donmez I.; Alevli, M.; Bıyıklı, Necmi
We report on the self-limiting growth and characterization of aluminum nitride (AlN) thin films. AlN films were deposited by plasma-enhanced atomic layer deposition on various substrates using trimethylaluminum (TMA) and ammonia (NH 3). At 185 °C, deposition rate saturated for TMA and NH 3 doses starting from 0.05 and 40 s, respectively. Saturative surface reactions between TMA and NH 3 resulted in a constant growth rate of ∼ 0.86 Å/cycle from 100 to 200 °C. Within this temperature range, film thickness increased linearly with the number of deposition cycles. At higher temperatures (≤ 225 °C) deposition rate increased with temperature. Chemical composition and bonding states of the films deposited at 185 °C were investigated by X-ray photoelectron spectroscopy. High resolution Al 2p and N 1s spectra confirmed the presence of AlN with peaks located at 73.02 and 396.07 eV, respectively. Films deposited at 185 °C were polycrystalline with a hexagonal wurtzite structure regardless of the substrate selection as determined by grazing incidence X-ray diffraction. High-resolution transmission electron microscopy images of the AlN thin films deposited on Si (100) and glass substrates revealed a microstructure consisting of nanometer sized crystallites. Films exhibited an optical band edge at ∼ 5.8 eV and an optical transmittance of > 95% in the visible region of the spectrum. © 2011 Elsevier B.V. All rights reserved.
Open Access
Simultaneous photoinduced electron transfer and photoinduced CuAAC processes for antibacterial thermosets
(Elsevier, 2017) Oz, E.; Uyar, T.; Esen, H.; Tasdelen, M. A.
A combination of simultaneous photoinduced electron transfer and photoinduced CuAAC processes enables the in-situ preparation of antibacterial thermosets containing silver nanoparticles (AgNPs) in one-pot. Upon photolysis of photoinitator, the generated radicals not only reduce Cu(II) into Cu(I) activator to catalyst the CuAAC click reaction, but also simultaneously generate AgNPs from AgNO3 through electron transfer reaction. Due to their reduction potentials difference, the polymer matrix is formed before the formation of AgNPs, assisting to eliminate the agglomeration of them. The thermoset structures are confirmed by FT-IR and solubility tests, whereas the presence of AgNPs is proven by transmission electron microscopy with energy dispersive X-ray system analyzer. The samples containing 5 and 10% AgNPs exhibited strong inhibition zones, where all kinds of bacteria (gram-positive (Staphylococcus Aureus) and gram-negative (Escherichia Coli)) were killed in the surrounding of the film samples.
Open Access
Structural superlubricity of platinum on graphite under ambient conditions: the effects of chemistry and geometry
(American Institute of Physics Inc., 2017) Özoǧul, A.; Ipek, S.; Durgun, Engin; Baykara, M. Z.
An investigation of the frictional behavior of platinum nanoparticles laterally manipulated on graphite has been conducted to answer the question of whether the recent observation of structural superlubricity under ambient conditions [E. Cihan, S. Ipek, E. Durgun, and M. Z. Baykara, Nat. Commun. 7, 12055 (2016)] is exclusively limited to the gold-graphite interface. Platinum nanoparticles have been prepared by e-beam evaporation of a thin film of platinum on graphite, followed by post-deposition annealing. Morphological and structural characterization of the nanoparticles has been performed via scanning electron microscopy and transmission electron microscopy, revealing a crystalline structure with no evidence of oxidation under ambient conditions. Lateral manipulation experiments have been performed via atomic force microscopy under ambient conditions, whereby results indicate the occurrence of structural superlubricity at mesoscopic interfaces of 4000-75 000 nm2, with a noticeably higher magnitude of friction forces when compared with gold nanoparticles of similar contact areas situated on graphite. Ab initio simulations of sliding involving platinum and gold slabs on graphite confirm the experimental observations, whereby the higher magnitude of friction forces is attributed to stronger energy barriers encountered by platinum atoms sliding on graphite, when compared with gold. On the other hand, as predicted by theory, the scaling power between friction force and contact size is found to be independent of the chemical identity of the sliding atoms, but to be determined by the geometric qualities of the interface, as characterized by an average "sharpness score" assigned to the nanoparticles.
Open Access
Ultrasensitive electrospun fluorescent nanofibrous membrane for rapid visual colorimetric detection of H2O2
(Springer Verlag, 2016-02) Senthamizhan A.; Balusamy, B.; Aytac Z.; Uyar, Tamer
We report herein a flexible fluorescent nanofibrous membrane (FNFM) prepared by decorating the gold nanocluster (AuNC) on electrospun polysulfone nanofibrous membrane for rapid visual colorimetric detection of H2O2. The provision of AuNC coupled to NFM has proven to be advantageous for facile and quick visualization of the obtained results, permitting instant, selective, and on-site detection. We strongly suggest that the fast response time is ascribed to the enhanced probabilities of interaction with AuNC located at the surface of NF. It has been observed that the color change from red to blue is dependent on the concentration, which is exclusively selective for hydrogen peroxide. The detection limit has been found to be 500 nM using confocal laser scanning microscope (CLSM), visually recognizable with good accuracy and stability. A systematic comparison was performed between the sensing performance of FNFM and AuNC solution. The underlying sensing mechanism is demonstrated using UV spectra, transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The corresponding disappearance of the characteristic emissions of gold nanoclusters and the emergence of a localized surface plasmon resonance (LSPR) band, stressing this unique characteristic of gold nanoparticles. Hence, it is evident that the conversion of nanoparticles from nanoclusters has taken place in the presence of H2O2. Our work here has paved a new path for the detection of bioanalytes, highlighting the merits of rapid readout, sensitivity, and user-friendliness.