Browsing by Author "Baykara, M. Z."

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Open Access
Advanced atomic force microscopy techniques
(Beilstein - Institut zur Foerderung der Chemischen Wissenschaften, 2012-12-21) Glatzel, T.; Holscher, H.; Schimmel, T.; Baykara, M. Z.; Schwarz, U. D.; Garcia, R.
Although its conceptual approach is as simple as the technique used in record players already introduced in the 19th century, the invention of the atomic force microscope (AFM) in 1986 by Binnig, Quate, and Gerber was a milestone for nanotechnology. The scanning tunneling microscope (STM), introduced some years earlier, had already achieved atomic resolution, but is limited to conductive surfaces. Since its operational principle is based on the detection of the forces acting between tip and sample, this restriction does not exist for the AFM. Consequently, atomic force microscopy quickly became the standard tool for nanometer-scale imaging of all types of surfaces in all environments. True atomic resolution was first achieved in the 1990s. The most convincing results, however, were restricted to the so-called noncontact mode in vacuum for a long time, but recent technical developments overcame this limitation, and atomic-resolution imaging is now also a standard in liquids. Beyond pushing the resolution limit to the picometer range, the invention of the AFM triggered the development of a growing number of new scanning probe methods and approaches, ranging from an expansion of the properties that can be mapped to the active manipulation of surfaces and small particles. Practically every month, reports on the growing capabilities of AFMs appear. Nearly every physical effect that influences the tip–sample interaction has been used to improve existing modes and to develop new ones. For example, many recently presented techniques include the excitation of higher cantilever oscillation modes; it is amazing in how many ways the shaking of a simple cantilever can improve our knowledge about the tip–sample interaction. Another direction is high-speed atomic force microscopy, which is one of the eminent challenges that need to be solved in order to allow the in situ observation of biological processes. Data acquisition times have already reached the millisecond range, enabling the visualization of the dynamic behavior of biological molecules and cells. Other recent accomplishments include imaging of organic molecules with unprecedented resolution, full three-dimensional mapping of surface force fields, and the imaging and discrimination of individual chemical bonds. The development of advanced techniques is the focus of this Thematic Series, following the Thematic Series “Scanning probe microscopy and related techniques” edited by Ernst Meyer and the Thematic Series “Noncontact atomic force microscopy” edited by Udo Schwarz. The articles that are part of the series demonstrate that, despite its 25 years of history, the AFM is still far from reaching its limits, and today’s developments are far-reaching. As the number of research groups utilizing advanced atomic force microscopy techniques increases with each passing year, the technical improvements, data-acquisition approaches, analysis procedures, user friendliness, and application areas of the technique further diversify. With this Thematic Series, it is our intention to stimulate these improvements. We thank all authors for contributing their excellent work to this series. Furthermore, we acknowledge all referees for their promptly provided reports keeping the publication times short and attractive for contributors. Finally, we are grateful to the open access policy of the Beilstein Journal of Nanotechnology providing the ground for unrestricted discussions on advanced atomic force microscopy techniques. Thilo Glatzel, Hendrik Hölscher, Thomas Schimmel, Mehmet Z. Baykara, Udo D. Schwarz and Ricardo Garcia December 2012
Open Access
Analysis of amplitude modulation atomic force microscopy in aqueous salt solutions
(Elsevier, 2014-11-01) Karayaylali, P.; Baykara, M. Z.
We present a numerical analysis of amplitude modulation atomic force microscopy in aqueous salt solutions, by considering the interaction of the microscope tip with a model sample surface consisting of a hard substrate and soft biological material through Hertz and electrostatic double layer forces. Despite the significant improvements reported in the literature concerning contact-mode atomic force microscopy measurements of biological material due to electrostatic interactions in aqueous solutions, our results reveal that only modest gains of similar to 15% in imaging contrast at high amplitude setpoints are expected under typical experimental conditions for amplitude modulation atomic force microscopy, together with relatively unaffected sample indentation and maximum tip-sample interaction values.
Open Access
Artifacts related to tip asymmetry in high-resolution atomic force microscopy and scanning tunneling microscopy measurements of graphitic surfaces
(American Institute of Physics Inc., 2015) Uluutku, B.; Baykara, M. Z.
The effect of tip asymmetry on atomic-resolution scanning tunneling microscopy and atomic force microscopy measurements of graphitic surfaces has been investigated via numerical simulations. Employing a three-dimensional, crystalline, metallic tip apex and a two-layer thick graphene sample as a model system, basic calculations of the tip-sample interaction have revealed a significant effect of tip asymmetry on obtained results, including artificial modulation of site-specific chemical interaction forces and spatial distortion of observed features. Related artifacts are shown to be enhanced for tips with low lateral stiffness values. Our results emphasize that potentially erroneous interpretations of atomic-scale surface properties via imaging and spectroscopy measurements can be caused or enhanced by tip asymmetry.
Open Access
Atom-specific forces and defect identification on surface-oxidized Cu ( 100 ) with combined 3D-AFM and STM measurements
(American Physical Society, 2013) Baykara, M. Z.; Todorović, M.; Mönig, H.; Schwendemann, T. C.; Ünverdi, Ö.; Rodrigo, L.; Altman, E. I.; Pérez, R.; Schwarz, U. D.
The influence of defects on the local structural, electronic, and chemical properties of a surface oxide on Cu(100) were investigated using atomic resolution three-dimensional force mapping combined with tunneling current measurements and ab initio density functional theory. Results reveal that the maximum attractive force between tip and sample occurs above the oxygen atoms; theory indicates that the tip, in this case, terminates in a Cu atom. Meanwhile, simultaneously acquired tunneling current images emphasize the positions of Cu atoms, thereby, providing species-selective contrast in the two complementary data channels. One immediate outcome is that defects due to the displacement of surface copper are exposed in the current maps, even though force maps only reflect a well-ordered oxygen sublattice. The exact nature of the defects is confirmed by the simulations, which also reveal that the arrangement of the oxygen atoms is not disrupted by the copper displacement. In addition, the experimental force maps uncover a position-dependent modulation of the attractive forces between the surface oxygen and the copper-terminated tips, which is found to reflect the surface's inhomogeneous chemical and structural environment. As a consequence, the demonstrated method has the potential to directly probe how defects affect surface chemical interactions. © 2013 American Physical Society.
Open Access
Effect of lateral tip stiffness on atomic-resolution force field spectroscopy
(American Vacuum Society, 2013) Uluutku, B.; Baykara, M. Z.
Atomic force microscopy is being increasingly used to measure atomic-resolution force fields on sample surfaces, making correct interpretation of resulting data critically important. In addition to asymmetry, elastic deformations undergone by the microscope tip are thought to affect measurements. In this study, simple analytical potentials and a model tip apex were used to theoretically analyze how lateral tip stiffness affects force spectroscopy on the surface of NaCl(001). The results suggest that lateral deformations experienced by the tip lead to certain distortions in measured force spectra, the degree of which depends on lateral tip stiffness. © 2013 American Vacuum Society.
Open Access
Effect of roughness on the layer-dependent friction of few-layer graphene
(American Physical Society, 2017-09) Ye, Z.; Balkanci, A.; Martini, A.; Baykara, M. Z.
Friction on few-layer graphene is known to exhibit unique layer dependence where friction measured via atomic force microscopy (AFM) on the nanometer scale is generally observed to decrease with increasing number of layers. However, this trend is not always observed for AFM probe tips with different sizes and for graphene on different substrates. Within this context, the precise role played by the interface, in particular, the size of the contact and substrate roughness, in the layer dependence of friction on graphene is not yet completely understood. Here, we probe the origins of the roughness dependence of layer-dependent friction on graphene by a combination of AFM measurements and molecular dynamics (MD) simulations. In the experiments, friction is observed to monotonically decrease with increasing number of graphene layers for tips with various apex radii, while the roughness of the sample surface is observed to decrease. In the simulations, two opposite layer-dependence trends for friction are observed on few-layer graphene on substrates with different roughness values. The underlying mechanisms are investigated using atomistic details obtained from the simulations, where the different friction trends are found to originate from an interplay between surface roughness, the trajectory of the tip, and the number of atoms in contact. Finally, the effect of topographical correlation length on the layer dependence of friction on graphene is discussed.
Open Access
Exploring atomic-scale lateral forces in the attractive regime: a case study on graphite (0001)
(Institute of Physics Publishing, 2012) Baykara, M. Z.; Schwendemann, T. C.; Albers, B. J.; Pilet, N.; Mönig, H.; Altman, E. I.; Schwarz, U. D.
A non-contact atomic force microscopy-based method has been used to map the static lateral forces exerted on an atomically sharp Pt/Ir probe tip by a graphite surface. With measurements carried out at low temperatures and in the attractive regime, where the atomic sharpness of the tip can be maintained over extended time periods, the method allows the quantification and directional analysis of lateral forces with piconewton and picometer resolution as a function of both the in-plane tip position and the vertical tip-sample distance, without limitations due to a finite contact area or to stick-slip-related sudden jumps of tip apex atoms. After reviewing the measurement principle, the data obtained in this case study are utilized to illustrate the unique insight that the method offers. In particular, the local lateral forces that are expected to determine frictional resistance in the attractive regime are found to depend linearly on the normal force for small tip-sample distances. © 2012 IOP Publishing Ltd.
Open Access
Genetically-tunable mechanical properties of bacterial functional amyloid nanofibers
(American Chemical Society, 2017) Abdelwahab, M. T.; Kalyoncu, E.; Onur, T.; Baykara, M. Z.; Seker U.O.S.
Bacterial biofilms are highly ordered, complex, dynamic material systems including cells, carbohydrates, and proteins. They are known to be resistant against chemical, physical, and biological disturbances. These superior properties make them promising candidates for next generation biomaterials. Here we investigated the morphological and mechanical properties (in terms of Young’s modulus) of genetically-engineered bacterial amyloid nanofibers of Escherichia coli (E. coli) by imaging and force spectroscopy conducted via atomic force microscopy (AFM). In particular, we tuned the expression and biochemical properties of the major and minor biofilm proteins of E. coli (CsgA and CsgB, respectively). Using appropriate mutants, amyloid nanofibers constituting biofilm backbones are formed with different combinations of CsgA and CsgB, as well as the optional addition of tagging sequences. AFM imaging and force spectroscopy are used to probe the morphology and measure the Young’s moduli of biofilm protein nanofibers as a function of protein composition. The obtained results reveal that genetically-controlled secretion of biofilm protein components may lead to the rational tuning of Young’s moduli of biofilms as promising candidates at the bionano interface.
Open Access
Nanoscale tribology of graphene grown by chemical vapor deposition and transferred onto silicon oxide substrates
(Cambridge University Press, 2016) Demirbaş, T.; Baykara, M. Z.
We present a comprehensive nanoscale tribological characterization of single-layer graphene grown by chemical vapor deposition (CVD) and transferred onto silicon oxide (SiO2) substrates. Specifically, the nanotribological properties of graphene samples are studied via atomic force microscopy (AFM) under ambient conditions using calibrated probes, by measuring the evolution of friction force with increasing normal load. The effect of using different probes and post-transfer cleaning procedures on frictional behavior is evaluated. A new method of quantifying lubrication performance based on measured friction coefficient ratios of graphene and SiO2 is introduced. A comparison of lubrication properties with mechanically-exfoliated graphene is performed. Results indicate that CVD-grown graphene constitutes a very good solid lubricant on SiO2, reducing friction coefficients by ∼ 90% for all investigated samples. Finally, the effect of wrinkles associated with CVD-grown graphene on measured friction values is quantitatively analyzed, with results revealing a substantial increase in friction on these structural defects.
Open Access
Noncontact atomic force microscopy II
(Beilstein-Institut Zur Forderung der Chemischen Wissenschaften, 2014) Baykara, M. Z.; Schwarz, U. D.
Open Access
Noncontact atomic force microscopy III
(Beilstein-Institut Zur Forderung der Chemischen Wissenschaften, 2016-06) Baykara, M. Z.; Schwarz, U. D.
Open Access
Noncontact atomic force microscopy: an emerging tool for fundamental catalysis research
(American Chemical Society, 2015) Altman, E. I.; Baykara, M. Z.; Schwarz, U. D.
ConspectusAlthough atomic force microscopy (AFM) was rapidly adopted as a routine surface imaging apparatus after its introduction in 1986, it has not been widely used in catalysis research. The reason is that common AFM operating modes do not provide the atomic resolution required to follow catalytic processes; rather the more complex noncontact (NC) mode is needed. Thus, scanning tunneling microscopy has been the principal tool for atomic scale catalysis research. In this Account, recent developments in NC-AFM will be presented that offer significant advantages for gaining a complete atomic level view of catalysis.The main advantage of NC-AFM is that the image contrast is due to the very short-range chemical forces that are of interest in catalysis. This motivated our development of 3D-AFM, a method that yields quantitative atomic resolution images of the potential energy surfaces that govern how molecules approach, stick, diffuse, and rebound from surfaces. A variation of 3D-AFM allows the determination of forces required to push atoms and molecules on surfaces, from which diffusion barriers and variations in adsorption strength may be obtained. Pushing molecules towards each other provides access to intermolecular interaction between reaction partners. Following reaction, NC-AFM with CO-terminated tips yields textbook images of intramolecular structure that can be used to identify reaction intermediates and products.Because NC-AFM and STM contrast mechanisms are distinct, combining the two methods can produce unique insight. It is demonstrated for surface-oxidized Cu(100) that simultaneous 3D-AFM/STM yields resolution of both the Cu and O atoms. Moreover, atomic defects in the Cu sublattice lead to variations in the reactivity of the neighboring O atoms. It is shown that NC-AFM also allows a straightforward imaging of work function variations which has been used to identify defect charge states on catalytic surfaces and to map charge transfer within an individual molecule.These advances highlight the potential for NC-AFM-based methods to become the cornerstone upon which a quantitative atomic scale view of each step of a catalytic process may be gained. Realizing this potential will rely on two breakthroughs: (1) development of robust methods for tip functionalization and (2) simplification of NC-AFM instrumentation and control schemes. Quartz force sensors may offer paths forward in both cases. They allow any material with an atomic asperity to be used as a tip, opening the door to a wide range of surface functionalization chemistry. In addition, they do not suffer from the instabilities that motivated the initial adoption of complex control strategies that are still used today.
Open Access
Nonuniform friction-area dependency for antimony oxide surfaces sliding on graphite
(American Physical Society, 2013) Ritter, C.; Baykara, M. Z.; Stegemann, B.; Heyde, M.; Rademann, K.; Schroers, J.; Schwarz, U. D.
We present frictional measurements involving controlled lateral manipulation of antimony nanoparticles on graphite featuring atomically smooth particle-substrate interfaces via tapping- and contact-mode atomic force microscopy. As expected from earlier studies, the power required for lateral manipulation as well as the frictional forces recorded during the manipulation events exhibit a linear dependence on the contact area over a wide size range from 2000 nm2 to 120 000 nm2. However, we observe a significant and abrupt increase in frictional force and dissipated power per contact area at a value of about 20 000 nm2, coinciding with a phase transition from amorphous to crystalline within the antimony particles. Our results suggest that variations in the structural arrangement and stoichiometry of antimony oxide at the interface between the particles and the substrate may be responsible for the observed effect. © 2013 American Physical Society.
Open Access
Probing three-dimensional surface force fields with atomic resolution: measurement strategies, limitations, and artifact reduction
(Beilstein - Institut zur Foerderung der Chemischen Wissenschaften, 2012) Baykara, M. Z.; Dagdeviren, O. E.; Schwendemann, T. C.; Mönig, H.; Altman, E. I.; Schwarz, U. D.
Noncontact atomic force microscopy (NC-AFM) is being increasingly used to measure the interaction force between an atomically sharp probe tip and surfaces of interest, as a function of the three spatial dimensions, with picometer and piconewton accuracy. Since the results of such measurements may be affected by piezo nonlinearities, thermal and electronic drift, tip asymmetries, and elastic deformation of the tip apex, these effects need to be considered during image interpretation. In this paper, we analyze their impact on the acquired data, compare different methods to record atomic-resolution surface force fields, and determine the approaches that suffer the least from the associated artifacts. The related discussion underscores the idea that since force fields recorded by using NC-AFM always reflect the properties of both the sample and the probe tip, efforts to reduce unwanted effects of the tip on recorded data are indispensable for the extraction of detailed information about the atomicscale properties of the surface. © 2012 Baykara et al.
Open Access
Self-assembled molecular films of alkanethiols on graphene for heavy metal sensing
(American Chemical Society, 2018) Afsharimani, N.; Uluutku, B.; Saygin, V.; Baykara, M. Z.
We report a comparative study involving the formation of self-assembled molecular films by two types of alkanethiols (1-octadecanethiol and 1-dodecanethiol) on graphene grown via chemical vapor deposition, for heavy metal sensing applications. Scanning tunneling microscopy measurements confirm that the alkanethiol molecules can form localized, ordered molecular films on single-layer graphene despite the presence of structural and chemical irregularities. To test and compare the sensory characteristics associated with graphene functionalized by 1-octadecanethiol and 1-dodecanethiol, graphene-based field effect transistors are fabricated via photolithography on silicon dioxide substrates. Devices based on graphene functionalized with 1-octadecanethiol are successfully employed to demonstrate the detection of mercury and lead ions at the 10 ppm level via Dirac point shifts, with a notable difference in response associated with the use of different heavy metal ions. On the other hand, devices based on graphene functionalized with 1-dodecanethiol exhibit p-type character, before and/or after exposure to heavy metal ions, complicating their use in heavy metal sensing in a straightforward fashion via Dirac point shifts.
Open Access
Simultaneous measurement of multiple independent atomic-scale interactions using scanning probe microscopy: data interpretation and the effect of cross-talk
(American Chemical Society, 2015) Baykara, M. Z.; Todorović, M.; Mönig, H.; Schwendemann, T. C.; Rodrigo, L.; Altman, E. I.; Pérez, R.; Schwarz, U. D.
In high-resolution scanning probe microscopy, it is becoming increasingly common to simultaneously record multiple channels representing different tip-sample interactions to collect complementary information about the sample surface. A popular choice involves simultaneous scanning tunneling microscopy (STM) and noncontact atomic force microscopy (NC-AFM) measurements, which are thought to reflect the chemical and electronic properties of the sample surface. With surface-oxidized Cu(100) as an example, we investigate whether atomic-scale information on chemical interactions can be reliably extracted from frequency shift maps obtained while using the tunneling current as the feedback parameter. Ab initio calculations of interaction forces between specific tip apexes and the surface are utilized to compare experiments with theoretical expectations. The examination reveals that constant-current operation may induce a noticeable influence of topography-feedback-induced cross-talk on the frequency shift data, resulting in misleading interpretations of local chemical interactions on the surface. Consequently, the need to apply methods such as 3D-AFM is emphasized when accurate conclusions about both the local charge density near the Fermi level, as provided by the STM channel, and the site-specific strength of tip-sample interactions (NC-AFM channel) are desired. We conclude by generalizing to the case where multiple atomic-scale interactions are being probed while only one of them is kept constant.
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
Three-dimensional interaction force and tunneling current spectroscopy of point defects on rutile TiO2(110)
(American Institute of Physics Inc., 2016) Baykara, M. Z.; Mönig, H.; Schwendemann, T. C.; Ünverdi, Ö.; Altman, E. I.; Schwarz, U. D.
The extent to which point defects affect the local chemical reactivity and electronic properties of an oxide surface was evaluated with picometer resolution in all three spatial dimensions using simultaneous atomic force/scanning tunneling microscopy measurements performed on the (110) face of rutile TiO2. Oxygen atoms were imaged as protrusions in both data channels, corresponding to a rarely observed imaging mode for this prototypical metal oxide surface. Three-dimensional spectroscopy of interaction forces and tunneling currents was performed on individual surface and subsurface defects as a function of tip-sample distance. An interstitial defect assigned to a subsurface hydrogen atom is found to have a distinct effect on the local density of electronic states on the surface, but no detectable influence on the tip-sample interaction force. Meanwhile, spectroscopic data acquired on an oxygen vacancy highlight the role of the probe tip in chemical reactivity measurements.
Open Access
Tribological interaction between polytetrafluoroethylene and silicon oxide surfaces
(AIP Publishing LLC, 2014) Uçar, A.; Çopuroğlu, M.; Baykara, M. Z.; Arıkan, Orhan; Süzer, Şefik
We investigated the tribological interaction between polytetrafluoroethylene (PTFE) and silicon oxide surfaces. A simple rig was designed to bring about a friction between the surfaces via sliding a piece of PTFE on a thermally oxidized silicon wafer specimen. A very mild inclination (∼0.5°) along the sliding motion was also employed in order to monitor the tribological interaction in a gradual manner as a function of increasing contact force. Additionally, some patterns were sketched on the silicon oxide surface using the PTFE tip to investigate changes produced in the hydrophobicity of the surface, where the approximate water contact angle was 45° before the transfer. The nature of the transferred materials was characterized by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XPS results revealed that PTFE was faithfully transferred onto the silicon oxide surface upon even at the slightest contact and SEM images demonstrated that stable morphological changes could be imparted onto the surface. The minimum apparent contact pressure to realize the PTFE transfer is estimated as 5 kPa, much lower than reported previously. Stability of the patterns imparted towards many chemical washing processes lead us to postulate that the interaction is most likely to be chemical. Contact angle measurements, which were carried out to characterize and monitor the hydrophobicity of the silicon oxide surface, showed that upon PTFE transfer the hydrophobicity of the SiO2 surface could be significantly enhanced, which might also depend upon the pattern sketched onto the surface. Contact angle values above 100° were obtained.
Open Access
Understanding scanning tunneling microscopy contrast mechanisms on metal oxides: a case study
(American Chemical Society, 2013) Mönig, H.; Todorović, M.; Baykara, M. Z.; Schwendemann, T. C.; Rodrigo, L.; Altman, E. I.; Pérez, R.; Schwarz, U. D.
A comprehensive analysis of contrast formation mechanisms in scanning tunneling microscopy (STM) experiments on a metal oxide surface is presented with the oxygen-induced (2√2×√2)R45 missing row reconstruction of the Cu(100) surface as a model system. Density functional theory and electronic transport calculations were combined to simulate the STM imaging behavior of pure and oxygen-contaminated metal tips with structurally and chemically different apexes while systematically varying bias voltage and tip-sample distance. The resulting multiparameter database of computed images was used to conduct an extensive comparison with experimental data. Excellent agreement was attained for a large number of cases, suggesting that the assumed model tips reproduce most of the commonly encountered contrast-determining effects. Specifically, we find that depending on the bias voltage polarity, copper-terminated tips allow selective imaging of two structurally distinct surface Cu sites, while oxygen-terminated tips show complex contrasts with pronounced asymmetry and tip-sample distance dependence. Considering the structural and chemical stability of the tips reveals that the copper-terminated apexes tend to react with surface oxygen at small tip-sample distances. In contrast, oxygen-terminated tips are considerably more stable, allowing exclusive surface oxygen imaging at small tip-sample distances. Our results provide a conclusive understanding of fundamental STM imaging mechanisms, thereby providing guidelines for experimentalists to achieve chemically selective imaging by properly selecting imaging parameters. © 2013 American Chemical Society.