Browsing by Subject "X ray photoelectron spectroscopy"

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Open Access
Analysis of Fe nanoparticles using XPS measurements under d.c. or pulsed-voltage bias
(2010) Süzer, Şefik; Baer, D. R.; Engelhard, M. H.
The impact of solution exposure on the charging properties of oxide coatings on Fe metal-core oxide-shell nanoparticles has been examined by sample biasing during XPS measurements. The Fe nanoparticles were suspended in relatively unreactive acetone and analyzed after particles containing solutions were deposited on SiO2/Si or Au substrates. The particle and substrate combinations were subjected to ±10V d.c. or ±5V a.c., biasing in the form of square wave (SQW) pulses. The samples experienced variable degrees of charging for which low-energy electrons at ∼1eV, 20 μA and low-energy Ar+ ions were used to minimize it. Application of d.c. bias and/or SQW pulses significantly influences the extent of charging, which is utilized to gather additional analytical information about the sample under investigation. This approach allows separation of otherwise overlapping peaks. Accordingly, the O1s peaks of the silicon oxide substrate, the iron oxide nanoparticles, and that of the casting solvent can be separated from each other. Similarly, the C1s peak belonging to the solvent can be separated from that of the adventitious carbon. The charging shifts of the iron nanoparticles are strongly influenced by the solvent to which the particles were exposed. Hence, acetone exhibited the largest shift, water the smallest, and methanol in between. Dynamical measurements performed by application of the voltage stress in the form of SQW pulses provides information about the time constants of the processes involved, which leads us to postulate that these charging properties we probe in these systems stem mainly from ionic movement(s).
Open Access
Area-selective atomic layer deposition using an inductively coupled plasma polymerized fluorocarbon layer: A case study for metal oxides
(American Chemical Society, 2016) Haider, A.; Deminskyi, P.; Khan, T. M.; Eren, H.; Bıyıklı, Necmi
Area-selective atomic layer deposition (AS-ALD) has attracted immense attention in recent years for self-aligned accurate pattern placement with subnanometer thickness control. Here, we demonstrate a methodology to achieve AS-ALD by using inductively couple plasma (ICP) grown fluorocarbon polymer film as hydrophobic blocking layer for selective deposition. Our approach has been tested for metal-oxide materials including ZnO, Al2O3, and HfO2. Contact angle, X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometer, and scanning electron microscopy (SEM) measurements were performed to investigate the blocking ability of plasma polymerized fluorocarbon layers against ALD-grown metal-oxide films. A considerable growth inhibition for ZnO has been observed on fluorocarbon coated Si(100) surfaces, while the same polymerized surface caused a relatively slow nucleation for HfO2 films. No growth selectivity was obtained for Al2O3 films, displaying almost the same nucleation behavior on Si and fluorocarbon surfaces. Thin film patterning has been demonstrated using this strategy by growing ZnO on lithographically patterned fluorocarbon/Si samples. High resolution SEM images and XPS line scan confirmed the successful patterning of ZnO up to a film thickness of ∼15 nm. © 2016 American Chemical Society.
Open Access
Bias in bonding behavior among boron, carbon, and nitrogen atoms in ion implanted a-BN, a-BC, and diamond like carbon films
(2011) Genisel, M. F.; Uddin, M. N.; Say, Z.; Kulakci, M.; Turan, R.; Gulseren, O.; Bengu, E.
In this study, we implanted Nþ and Nþ 2 ions into sputter deposited amorphous boron carbide (a-BC) and diamond like carbon (DLC) thin films in an effort to understand the chemical bonding involved and investigate possible phase separation routes in boron carbon nitride (BCN) films. In addition, we investigated the effect of implanted Cþ ions in sputter deposited amorphous boron nitride (a-BN) films. Implanted ion energies for all ion species were set at 40 KeV. Implanted films were then analyzed using x-ray photoelectron spectroscopy (XPS). The changes in the chemical composition and bonding chemistry due to ion-implantation were examined at different depths of the films using sequential ion-beam etching and high resolution XPS analysis cycles. A comparative analysis has been made with the results from sputter deposited BCN films suggesting that implanted nitrogen and carbon atoms behaved very similar to nitrogen and carbon atoms in sputter deposited BCN films. We found that implanted nitrogen atoms would prefer bonding to carbon atoms in the films only if there is no boron atom in the vicinity or after all available boron atoms have been saturated with nitrogen. Implanted carbon atoms also preferred to either bond with available boron atoms or, more likely bonded with other implanted carbon atoms. These results were also supported by ab-initio density functional theory calculations which indicated that carbon-carbon bonds were energetically preferable to carbon-boron and carbon-nitrogen bonds.
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
Characterization of denture acrylic resin surfaces modified by glow discharges
(Sage Publications, Inc., 1997) Süzer, Ş.; Özden, N.; Akaltan, F.; Akovali, G.
Resin samples prepared by compression molding using a poly (methyl methacrylate) (PMMA) denture base material were exposed to radio-frequency (rf) glow discharges to improve the wettability of the material. Fourier transform infrared (FT-IR) reflectance, X-ray photoelectron spectroscopy (XPS), and contact-angle measurements have been employed to characterize the changes introduced by the glow discharge plasma. FT-IR measurements cannot detect any modification. XPS reveals an increase in the O/C atomic ratio. Contact angles of the plasma-treated samples are always lower when compared with untreated ones. The increased O atomic concentration is attributed to formation of -COH groups on the surface during plasma treatment. The O/C atomic ratio decreases upon heating the samples in vacuum to 100 °C for 1-2 min and exposing the samples to liquid CH2Cl2 for 1-2 min. Exposure to distilled water for prolonged periods causes a slight decrease during the initial 1-20 days but levels off to a constant value up to a period of 60 days. Plasma treatment seems to offer a durable increase in the wettability for these materials left in air or distilled water.
Open Access
Charging / discharging of thin PS / PMMA films as probed by dynamic x-ray photoelectron spectroscopy
(2007) Sezen, H.; Ertas, G.; Dâna, A.; Süzer, Şefik
Polystyrene / polymethyl methacrylate (PS-PMMA) thin films were analyzed for detecting phase separation as well as probing their electrical responses by XPS. It was also shown that electrical parameters like resistance or capacitance can also be extracted using dynamical XPS measurements. A Kratos ES300 electron spectrometer was used for XPS measurements, and a nearby filament provided low-energy electrons for charge neutralization. The results show that under a positive stress, low-energy electrons are attracted to the sample and yield less positive charge on the sample, due to partial neutralization.
Open Access
Charging/discharging dynamics of CdS and CdSe films under photoillumination using dynamic x-ray photoelectron spectroscopy
(A I P Publishing LLC, 2010) Sezen, H.; Süzer, Şefik
Thin films of CdS and CdSe are deposited on HF-cleaned Si O2 /Si substrates containing ∼5 nm thermally grown silicon oxide. x-ray photoelectron spectroscopy (XPS) data of these films are collected in a dynamic mode, which is based on recording the spectrum under modulation with an electrical signal in the form of ±10 V square-wave pulses. Accordingly, all peaks are twined and shifted with respect to the grounded spectrum. The binding energy difference between the twinned peaks of a dielectric system has a strong dependence on the frequency of the electrical stimuli. Therefore, dynamic XPS provides a means to extract additional properties of dielectric materials, such as effective resistance and capacitance. In this work, the authors report a new advancement to the previous method, where they now probe a photodynamic process. For this reason, photoillumination is introduced as an additional form of stimulus and used to investigate the combined optical and electrical response of the photoconductive thin films of CdS and CdSe using dynamic XPS.
Open Access
Charging/discharging of Au (core)/silica (shell) nanoparticles as revealed by XPS
(American Chemical Society, 2005) Tunc, I.; Demirok, U. K.; Süzer, Şefik; Correa-Duatre, M. A.; Liz-Marzan, L. M.
By recording XPS spectra while applying external voltage stress to the sample rod, we can control the extent of charging developed on core-shell-type gold nanoparticles deposited on a copper substrate, in both steady-state and time-resolved fashions. The charging manifests itself as a shift in the measured binding energy of the corresponding XPS peak. Whereas the bare gold nanoparticles exhibit no measurable binding energy shift in the Au 4f peaks, both the Au 4f and the Si 2p peaks exhibit significant and highly correlated (in time and magnitude) shifts in the case of gold (core)/silica (shell) nanoparticles. Using the shift in the Au 4f peaks, the capacitance of the 15-nm gold (core)/6-nm silica (shell) nanoparticle/nanocapacitor is estimated as 60 aF. It is further estimated that, in the fully charged situation, only 1 in 1000 silicon dioxide units in the shell carries a positive charge during our XPS analysis. Our simple method of controlling the charging, by application of an external voltage stress during XPS analysis, enables us to detect, locate, and quantify the charges developed on surface structures in a completely noncontact fashion. © 2005 American Chemical Society.
Open Access
Chemically specific dynamic characterization of photovoltaic and photoconductivity effects of surface nanostructures
(American Chemical Society, 2010) Ekiz, O. Ö.; Mizrak, K.; Dâna, A.
We report characterization of photovoltaic and photoconductivity effects on nanostructured surfaces through light induced changes in the X-ray photoelectron spectra (XPS). The technique combines the chemical specificity of XPS and the power of surface photovoltage spectroscopy (SPV), with the addition of the ability to characterize photoconductivity under both static and dynamic optical excitation. A theoretical model that quantitatively describes the features of the observed spectra is presented. We demonstrate the applicability of the model on a multitude of sample systems, including homo- and heterojunction solar cells, CdS nanoparticles on metallic or semiconducting substrates, and carbon nanotube films on silicon substrates.
Open Access
Communication: Enhancement of dopant dependent x-ray photoelectron spectroscopy peak shifts of Si by surface photovoltage
(2011) Sezen, H.; Süzer, Şefik
Binding energies measured by x-ray photoelectron spectroscopy (XPS) are influenced by doping, since electrons are transferred to (p-type) and from (n-type) samples when they are introduced into the spectrometer, or brought into contact with each other (p-n junction). We show that the barely measurable Si2p binding energy difference between moderately doped n- and p-Si samples can be enhanced by photoillumination, due to reduction in surface band-bending, which otherwise screens this difference. Similar effects are also measured for samples containing oxide layers, since the band-bending at the buried oxide-Si interfaces is manifest as photovoltage shifts, although XPS does not probe the interface directly. The corresponding shift for the oxide layer of the p-Si is almost twice that of without the oxide, whereas no measurable shifts are observable for the oxide of the n-Si. These results are all related to band-bending effects and are vital in design and performance of photovoltaics and other related systems.
Open Access
Comparison of trimethylgallium and triethylgallium as "ga" source materials for the growth of ultrathin GaN films on Si (100) substrates via hollow-cathode plasma-assisted atomic layer deposition
(AVS Science and Technology Society, 2016-02) Alevli, M.; Haider A.; Kizir S.; Leghari, S. A.; Bıyıklı, Necmi
GaN films grown by hollow cathode plasma-assisted atomic layer deposition using trimethylgallium (TMG) and triethylgallium (TEG) as gallium precursors are compared. Optimized and saturated TMG/TEG pulse widths were used in order to study the effect of group-III precursors. The films were characterized by grazing incidence x-ray diffraction, atomic force microscopy, x-ray photoelectron spectroscopy, and spectroscopic ellipsometry. Refractive index follows the same trend of crystalline quality, mean grain, and crystallite sizes. GaN layers grown using TMG precursor exhibited improved structural and optical properties when compared to GaN films grown with TEG precursor.
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
Cyclodextrin functionalized poly(methyl methacrylate) (PMMA) electrospun nanofibers for organic vapors waste treatment
(Elsevier BV, 2010) Uyar, Tamer; Havelund, R.; Nur, Y.; Balan, A.; Hacaloglu, J.; Toppare, L.; Besenbacher, F.; Kingshott, P.
Poly(methyl methacrylate) (PMMA) nanofibers containing the inclusion complex forming betacyclodextrin (_-CD) were successfully produced by means of electrospinning in order to develop functional nanofibrous webs for organic vapor waste treatment. Electrospinning of uniform PMMA nanofibers containing different loadings of _-CD (10%, 25% and 50% (w/w)) was achieved. The surface sensitive spectroscopic techniques; X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) showed that some of the _-CD molecules are present on the surface of the PMMA nanofibers, which is essential for the trapping of organic vapors by inclusion complexation. Direct pyrolysis mass spectrometry (DP-MS) studies showed that PMMA nanowebs containing _-CD can entrap organic vapors such as aniline, styrene and toluene from the surroundings due to inclusion complexation with _-CD that is present on the fiber surface. Our study showed that electrospun nanowebs functionalized with cyclodextrinsmayhave the potential to be used as molecular filters and/or nanofilters for the treatment of organic vapor waste and air filtration purposes.
Open Access
Differential charging in SiO2/Si systems as determined by XPS
(American Chemical Society, 2004) Karadas, F.; Ertas, G.; Süzer, Şefik
The Si2p binding and the SiKLL kinetic energy difference between the SiO2 layer and Si substrate is shown to be influence by application of external voltage bias to the sample holder due to the differential charging as was already reported earlier (Ulgut, B.; Suzer, S. J. Phys. Chem. B 2003, 107, 2939). The cause of this bias induced (physical)-shift is now proven to be mostly due to partial neutralization by the stray electrons within the vacuum system by (i) introducing additional stray electrons via a filament and following their influence on the measured binding energy as a function of the applied voltage, (ii) measuring and Auger parameter. It is also shown that citrate-capped gold nanoclusters deposited on the SiO2/Si system experience differential charging similar to that of the oxide layer rather than the silicon substrate.
Open Access
Differential charging in x-ray photoelectron spectroscopy: a nuisance or a useful tool?
(American Chemical Society, 2003) Süzer, Şefik
We apply a negative bias to the sample while recording an XPS spectrum to enhance differential (positive) charging. The enhanced differential charging is due to the repulsion of stray electrons from the sample, which normally cause partial neutralization of the poorly conducting samples or regions accumulating positive charging, as a consequence of the photoelectron emission. This enhanced differential charging (obtained by negative biasing) is shown to have the ability to separate otherwise overlapping peaks of PDMS layer from that of the SiO2/Si substrate. Each layer experiences different charging that can be used to derive information related to dielectric properties of the layers, proximity of the atoms within composite multilayers, or both. Hence, differential charging in XPS, which is usually considered as a nuisance, is turned into a useful tool for extracting additional information from nanometer-size surface structures.
Open Access
Differentiation of domains in composite surface structures by charge-contrast x-ray photoelectron spectroscopy
(2007) Süzer, Şefik; Dâna, A.; Ertas, G.
An external bias is applied to two samples containing composite surface structures, while recording an XPS spectrum. Altering the polarity of the bias affects the extent of differential charging in domains that are chemically or electronically different to create a charge contrast. By utilizing this charge contrast, we show that two distinct silicon nitride and silicon oxynitride domains are present in one of the composite samples. Similarly, we use this technique to show that titanium oxide and silicon oxide domains exist as separate chemical entities in another composite sample. © 2007 American Chemical Society.
Open Access
Doping of 2-Cl-PANI/PVC films by exposure to UV, γ-rays and e-beams
(Elsevier Sequoia SA, Lausanne, Switzerland, 2000) Sevil, U. A.; Güven, O.; Birer, Ö.; Süzer, Ş.
2-Chloro-polyaniline (2-Cl-PANI) is chemically prepared in its non-conducting (Emeraldine Base, EB) form and dissolved together with polyvinylchloride (PVC) in THF for casting into thin (10-50 μm) composite films. The electrical conductivity of these films increases by more than four orders of magnitude (from 10-6 to 10-2 S/cm) when they are exposed to UV, γ-rays and e-beams. This is attributed to the dehydrochlorination (loss of HCl) of PVC by exposure to energetic particles and subsequent doping of the 2-Cl-PANI (i.e., conversion to Emeraldine Salt, ES) by the in-situ-created HCl. The doped films can also be returned to their undoped form by further exposure to NH3 vapours. The UV (or other particles)-induced doping/NH3 undoping cycles can be repeated several times until almost total dehydrochlorination of the PVC matrix. UV-Vis-NIR, Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopic (XPS) techniques are employed to follow the changes in the composite films upon doping by exposure to these energetic particles.
Open Access
Dynamical XPS measurements for probing photoinduced voltage changes
(2010) Sezen, H.; Süzer, Şefik
Photoillumination with 405 nm laser causes shifts in XPS peaks of n-Si(100), and CdS. To distinguish between surface photovoltage (SPV), and charging, dynamical measurements are performed, while sample is subjected to square wave pulses of ± 10.00 V amplitude, and 10-3-10 5 Hz frequency. For n-Si, Si2p peaks are twinned at + 10.00 and -10.00, yielding always 20.00 eV difference. Photoillumination shifts the twinned peaks to higher energies, but the difference is always 20.00 eV. However, for CdS, the measured binding difference of Cd3d peaks exhibits strong frequency dependence due to charging, which indicates that both fast SPV and slow charging effects are operative.
Open Access
Effect of reactor pressure on optical and electrical properties of InN films grown by high-pressure chemical vapor deposition
(Wiley - V C H Verlag GmbH & Co. KGaA, 2015) Alevli, M.; Gungor, N.; Alkis, S.; Ozgit Akgun, C.; Donmez, I.; Okyay, Ali Kemal; Gamage, S.; Senevirathna, I.; Dietz, N.; Bıyıklı, Necmi
The influences of reactor pressure on the stoichiometry, free carrier concentration, IR and Hall determined mobility, effective optical band edge, and optical phonon modes of HPCVD grown InN films have been analysed and are reported. The In 3d, and N 1s XPS spectra results revealed In-N and N-In bonding states as well as small concentrations of In-O and N-O bonds, respectively in all samples. InN layers grown at 1 bar were found to contain metallic indium, suggesting that the incorporation of nitrogen into the InN crystal structure was not efficient. The free carrier concentrations, as determined by Hall measurements, were found to decrease with increasing reactor pressure from 1.61×1021 to 8.87×1019 cm-3 and the room-temperature Hall mobility increased with reactor pressure from 21.01 to 155.18 cm2/Vs at 1 and 15 bar reactor pressures, respectively. IR reflectance spectra of all three (1, 8, and 15 bar) InN samples were modelled assuming two distinct layers of InN, having different free carrier concentration, IR mobility, and effective dielectric function values, related to a nucleation/interfacial region at the InN/sapphire, followed by a bulk InN layer. The effective optical band gap has been found to decrease from 1.19 to 0.95 eV with increasing reactor pressure. Improvement of the local structural quality with increasing reactor pressure has been further confirmed by Raman spectroscopy measurements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Open Access
Effect of substrate temperature and Ga source precursor on growth and material properties of GaN grown by hollow cathode plasma assisted atomic layer deposition
(IEEE, 2016) Haider, Ali; Kizir, Seda; Deminskyi, P.; Tsymbalenko, Oleksandr; Leghari, Shahid Ali; Bıyıklı, Necmi; Alevli, M.; Gungor, N.
GaN thin films grown by hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) at two different substrate temperatures (250 and 450 °C) are compared. Effect of two different Ga source materials named as trimethylgallium (TMG) and triethylgallium (TEG) on GaN growth and film quality is also investigated and reviewed. Films were characterized by X-ray photoelectron spectroscopy, spectroscopic ellipsometery, and grazing incidence X-ray diffraction. GaN film deposited by TMG revealed better structural, chemical, and optical properties in comparison with GaN film grown with TEG precursor. When compared on basis of different substrate temperature, GaN films grown at higher substrate temperature revealed better structural and optical properties.