Combination Of X-ray Photoelectron Spectroscopy Research Articles

Characterizing oxidation, thickness, and composition of metallic glass thin films with combined electron probe microanalysis and X-ray photoelectron spectroscopy

Metallic glass thin films (MGTFs) are a recently developed class of alloy coatings with potential applications ranging from biomedical devices to electrical components. Their tribological performance in service conditions is dictated by MGTF bulk composition but can be limited by the native oxide surface that inevitably forms upon exposure to atmosphere. Surface oxidation, thickness, and composition of ZrCuNiAl MGTFs were characterized using a combination of X-ray photoelectron microscopy (XPS) and electron probe microanalysis (EPMA). MGTF samples with nominal thicknesses of 50, 500, and 1500 nm were sputtered onto Si and SiN wafer substrates within a high vacuum deposition chamber and their amorphicity was confirmed by X-ray diffraction. XPS depth profiling identified the thin film composition and showed that the surface oxide was dominated by a mixed layer of mostly ZrO2, a little oxidized Al, and some metallic Zr. EPMA X-ray intensities were acquired as a function of beam energy to excite characteristic X-rays from different depths of the MGTFs and reconstructed using open-source thin film analysis software BadgerFilm, to determine the composition and thickness of sample layers. EPMA results constrain the composition to be Zr54Cu29Al10Ni7 within 0.7 at. % variation and total thicknesses to be 49, 470, and 1546 nm. Using the oxide composition identified from XPS depth profiling as an input for BadgerFilm analysis, EPMA results indicate the surface oxidation layer on each of the thin film samples was 6.5 ± 1.1 nm thick and uniform across a 0.25 mm region of the film.

Inhibition of atomic layer deposition of TiO2 by functionalizing silicon surface with 4-fluorophenylboronic acid

As the size of the components in electronic devices decreases, new approaches and chemical modification schemes are needed to produce nanometer-size features with bottom-up manufacturing. Organic monolayers can be used as effective resists to block the growth of materials on non-growth substrates in area-selective deposition methods. However, choosing the appropriate surface modification requires knowledge of the corresponding chemistry and also a detailed investigation of the behavior of the functionalized surface in realistic deposition schemes. This study aims to investigate the chemistry of boronic acids that can be used to prepare such non-growth areas on elemental semiconductors. 4-Fluorophenylboronic acid is used as a model to investigate the possibility to utilize the Si(100) surface functionalized with this compound as a non-growth substrate in a titanium dioxide (TiO2) deposition scheme based on sequential doses of tetrakis(dimethylamido)titanium and water. A combination of X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry allows for a better understanding of the process. The resulting surface is shown to be an effective non-growth area to TiO2 deposition when compared to currently used H-terminated silicon surfaces but to exhibit much higher stability in ambient conditions.

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers

Improving materials for energy conversion and storage devices is deeply connected with an optimization of their surfaces and surface modification is a promising strategy on the way to enhance modern energy technologies. This study shows that surface modification with ultra-thin oxide layers allows for a systematic tailoring of the surface dipole and the work function of mixed ionic and electronic conducting oxides, and it introduces the ionic potential of surface cations as a readily accessible descriptor for these effects. The combination of X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) illustrates that basic oxides with a lower ionic potential than the host material induce a positive surface charge and reduce the work function of the host material and vice versa. As a proof of concept that this strategy is widely applicable to tailor surface properties, we examined the effect of ultra-thin decoration layers on the oxygen exchange kinetics of pristine mixed conducting oxide thin films in very clean conditions by means of in-situ impedance spectroscopy during pulsed laser deposition (i-PLD). The study shows that basic decorations with a reduced surface work function lead to a substantial acceleration of the oxygen exchange on the surfaces of diverse materials.

Aromatic acids affect the performances of constructed rapid infiltration systems based on red mud and coke: Removal efficiency, electron transport, and metabolism

This study investigated the effect of coke and red mud as fillers in a constructed rapid infiltration system on the removal of three aromatic acids in wastewater. In addition, a combination of X-ray photoelectron spectroscopy (XPS) and metagenomics sequencing was used to explore the microbial communities and metabolic mechanisms. Results showed that the removal rates of chemical oxygen demand of the three columns containing phthalic acid (PA), benzoic acid (BA), and 1-naphthoic acid (1NA) were 83.59%, 92.52%, and 88.72%, and the removal rates of ammonia nitrogen were 37.33%, 40.83%, and 38.38% of, respectively. Meanwhile, the removal efficiency of three aromatic acids by the systems was BA > PA > 1NA. Proteobacteria and Actinobacteria were among the dominant bacterial groups in the columns. The highest relative abundance of Sphingopyxis was found in the column with 1NA, which provided a certain guarantee for the degradation of 1-naphthoic acid by this column. Compared to PA and 1NA, BA upregulated the abundance of the norB gene. The relative abundance of phoBR, a regulator of the. phosphoryl regulator response, was significantly down-regulated in the PA column, leading to a decrease in total phosphorus removal at the later stage. This study provides an economical and simple process for the treatment of wastewater containing aromatic acid. These promising results also indicate that red mud can be used as a resource in wastewater treatment.

In Situ Monitoring of Non-Thermal Plasma Cleaning of Surfactant Encapsulated Nanoparticles

Surfactants are widely used in the synthesis of nanoparticles, as they have a remarkable ability to direct their growth to obtain well-defined shapes and sizes. However, their post-synthesis removal is a challenge, and the methods used often result in morphological changes that defeat the purpose of the initial controlled growth. Moreover, after the removal of surfactants, the highly active surfaces of nanomaterials may undergo structural reconstruction by exposure to a different environment. Thus, ex situ characterization after air exposure may not reflect the effect of the cleaning methods. Here, combining X-ray photoelectron spectroscopy, in situ infrared reflection absorption spectroscopy, and environmental transmission electron microscopy measurements with CO probe experiments, we investigated different surfactant-removal methods to produce clean metallic Pt nanoparticles from surfactant-encapsulated ones. It was demonstrated that both ultraviolet-ozone (UV-ozone) treatment and room temperature O2 plasma treatment led to the formation of Pt oxides on the surface after the removal of the surfactant. On the other hand, when H2 was used for plasma treatment, both the Pt0 oxidation state and nanoparticle size distribution were preserved. In addition, H2 plasma treatment can reduce Pt oxides after O2-based treatments, resulting in metallic nanoparticles with clean surfaces. These findings provide a better understanding of the various options for surfactant removal from metal nanoparticles and point toward non-thermal plasmas as the best route if the integrity of the nanoparticle needs to be preserved.

In situ and ex situ quantification of nanoparticle fluxes in magnetron sputter inert gas condensation: A Cu nanoparticle case study

Magnetron sputter inert gas condensation was coupled with quadrupole mass spectrometry for the in situ characterization of a nanoparticle beam. The proposed method allows us to determine the size distribution and the mass flux of the nanoparticles. The measured quadrupole mass spectrometer grid current is converted into a nanoparticle flux and subsequently into a mass flux. Cu nanoparticles were deposited onto Si substrates using different filtering modes of the quadrupole mass spectrometer. Characterization was carried out using a combination of x-ray photoelectron spectroscopy and scanning electron microscopy. Quantitative analysis of the elemental composition of the Si surface revealed a Gaussian distribution of the deposited nanoparticles over the diameter of the rotating substrate holder with a good quantitative agreement with the predictions made from the in situ quantification method.

Structural and electronic properties of MoS2 and MoSe2 monolayers grown by chemical vapor deposition on Au(111).

The exceptional electronic and photonic properties of the monolayers of transition metal dichalcogenides including the spin-orbit splitting of the valence and conduction bands at the K points of the Brillouin zone make them promising for novel applications in electronics, photonics and optoelectronics. Scalable growth of these materials and understanding of their interaction with the substrate is crucial for these applications. Here we report the growth of MoS2 and MoSe2 monolayers on Au(111) by chemical vapor deposition at ambient pressure as well as the analysis of their structural and electronic properties down to the atomic scale. To this aim, we apply ultrahigh vacuum surface sensitive techniques including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray and angle-resolved ultraviolet photoelectron spectroscopy in combination with Raman spectroscopy at ambient conditions. We demonstrate the growth of high-quality epitaxial single crystalline MoS2 and MoSe2 monolayers on Au(111) and show the impact of annealing on the monolayer/substrate interaction. Thus, as-grown and moderately annealed (<100 °C) MoSe2 monolayers are decoupled from the substrate by excess Se atoms, whereas annealing at higher temperatures (>250 °C) results in their strong coupling with the substrate caused by desorption of the excess Se. The MoS2 monolayers are strongly coupled to the substrate and the interaction remains almost unchanged even after annealing up to 450 °C.

Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysis

Testing single crystalline epitaxial thin films as model systems for metal oxide electrocatalysts in the oxygen evolution reaction (OER) enables differentiating the OER descriptors such as crystal facet orientation, surface chemical composition, electronic structure and band bending at the interface to the electrolyte [1,2,3]. We designed single crystalline perovskite oxide bilayer structures to systematically tune the surface electronic structure and the band bending at the electrode/electrolyte interface to understand their role in the OER.The Co−O covalency in perovskite oxide cobaltites such as La1 − x SrxCoO3 is believed to impact the electrocatalytic activity during the OER. Additionally, space charge layers through band bending at the interface to the electrolyte may affect the electron transfer into the electrode, complicating the analysis and identification of true OER activity descriptors. Here, we separate the influence of covalency and band bending in hybrid epitaxial bilayer structures of highly OER-active La0.6Sr0.4CoO3 and undoped and less-active LaCoO3. Ultrathin LaCoO3 capping layers of 2−8 unit cells on La0.6Sr0.4CoO3 show intermediate OER activity between La0.6Sr0.4CoO3 and LaCoO3 evidently caused by the increased surface Co−O covalency compared to single LaCoO3 as detected by X-ray photoelectron spectroscopy. A Mott−Schottky analysis revealed low flat band potentials for different LaCoO3 capping layer thicknesses, indicating that no limiting extended space charge layer exists under OER conditions as all catalyst bilayer films exhibited hole accumulation at the surface [1].The combined X-ray photoelectron spectroscopy and Mott−Schottky analysis of atomically defined bilayer structures thus enables us to differentiate between the influence of the covalency and intrinsic space charge layers, which are indistinguishable in a single physical or electrochemical characterization. Our results emphasize the prominent role of transition metal oxygen covalency in perovskite electrocatalysts and introduce a bilayer approach to fine-tune the surface electronic structure [1].[1] L. Heymann, M. L. Weber, M. Wohlgemuth, M. Risch, R. Dittmann, C. Baeumer, F. Gunkel (2022) Separating the Effects of Band Bending and Covalency in Hybrid Perovskite Oxide Electrocatalyst Bilayers for Water Electrolysis, ACS Appl. Mater. Interfaces[2] M. Wohlgemuth, M. L. Weber, L. Heymann, C. Baeumer, F. Gunkel (2022) Activity-Stability Relationships in Oxide Electrocatalysts for Water Electrolysis, Front. Chem.[3] M. L. Weber, G. Lole, A. Kormanyos, A. Schwiers, L. Heymann, F. D. Speck, T. Meyer, R. Dittmann, S. Cherevko, C. Jooss, C. Baeumer, F. Gunkel, (2022) Atomistic Insights into Activation and Degradation of La0.6Sr0.4CoO3-δ Electrocatalysts under Oxygen Evolution Conditions Figure 1

Intriguing properties of graphite/polysiloxane composite-based pencil electrodes

Pencil leads can be considered well-defined and cheap graphite electrodes for a wide range of electrochemistry applications. These electrodes display many intriguing properties; however, the origin of these properties is not clear. Using various analytical approaches applied to two different commercially available Tombow (TO) and Staedtler (ST) pencils we reveal a causal relationship between the unique properties of pencils and their graphite/polysiloxane composite. We explore the impact of chloroform etching on chemical composition changes, thermal stability and electrochemical parameters of pencils. Using a combination of X-ray photoelectron spectroscopy (XPS) and gas chromatography-mass spectrometry (GC-MS/MS) various polydimethylsiloxanes in composites are revealed. The polysiloxane species leave into the chloroform solvent during the etching resulting in a significant decrease of their content within the electrodes. Differential scanning calorimetry (DSC) data, corroborated by gravimetric measurements, provide additional proof of the presence of composite structures in ST and TO pencils, showing glass transition temperatures at around 76 °C and 81 °C. The main difference between the TO and ST electrodes is the content and composition of the polysiloxanes within the graphite matrix. ST composites have significantly higher polymer content (∼ 30 %) with traces of Na and S impurities compared to TO ones (∼ 14 %) free of contaminations. Furthermore, mainly cyclic nanostructures appear in chloroform extracts of ST composites whereas rather chain-like clusters are liberated out of the TO counterparts. Complementary electrochemical experiments using cyclic voltammetry (CV), impedance spectroscopy (EIS) and the less known elimination voltammetry with linear scan (EVLS) reflect the performance superiority of TO electrodes with much lower polysiloxane content and free of impurities. High conductivity, low capacitive current along with favoured charge carrier transfer all promise a wide range of technological applications for the TO pencil material.

The Surface of Ionic Liquids in Water: From an Ionic Tug of War to a Quasi-Ordered Two-Dimensional Layer.

The sustainable development encompasses the search for new materials for energy storage, gas capture, separation, and solvents in industrial processes that can substitute conventional ones in an efficient and clean manner. Ionic liquids (ILs) emerged and have been advanced as alternative materials for such applications, but an obstacle is their hygroscopicity and the effects on their physical properties in the presence of humidity. Several industrial processes depend on the aqueous interfacial properties, and the main focus of this work is the water/IL interface. The behavior of the aqueous ionic liquids at the water-vacuum interface is representative for their water interfacial properties. Using X-ray photoelectron spectroscopy in combination with molecular dynamics simulations we investigate four aqueous IL systems, and provide molecular level insight on the interfacial behaviour of the ionic liquids, such as ion-pair formation, orientation and surface concentration. We find that ionic liquids containing a chloride anion have a lowered surface enrichment due to the low surface propensity of chloride. In contrast, the ionic liquids containing a bistriflimide anion are extremely surface-enriched due to cooperative surface propensity between the cations and anions, forming a two-dimensional ionic liquid on the water surface at low concentrations.

A combined first-principles calculations and X-ray photoelectron spectroscopy of Ce2T3X9 (T = Rh, Ru, Ir; X = Al, Ga): Possible strong topological insulator state in Ce2Ir3Al9

We calculated electronic structure of Ce2Rh3Ga9, Ce2Ru3Ga9, La2Ir3Al9 and Ce2Ir3Al9 compounds and we found that Ce2Ir3Al9 may exhibit strong topological insulator state according to Z2 index estimation based on parity algorithm and shape of band structure near Fermi level. The same algorithm shows strong topological insulator state for La2Ir3Al9 and Ce2Rh3Ga9 compounds, but their band structure near Fermi level is more like semimetallic one. Ce2Ru3Ga9 is a normal metal. Our calculations show no magnetic ordering for studied compounds. We also measured the XPS (X-ray Photoelectron Spectroscopy) spectra for these materials, and compared the valence band with simulated spectra, where good agreement was found. Core level states were also investigated and compared with Mulliken population analysis results. According to our measurements and calculations, the highest Ce valence is observed for Ce2Ir3Al9 whereas for Ce2Rh3Ga9 and Ce2Ru3Ga9 the Ce valence is smaller. Hybridization between conduction electrons and 4f states is very small, and for Ce2Ru3Ga9 essentially negligible.

N-heterocyclic carbenes – The design concept for densely packed and thermally ultra-stable aromatic self-assembled monolayers

Self-assembled monolayers (SAMs) of N-heterocyclic carbenes (NHCs) on metal substrates are currently one of the most promising systems in context of molecular-scale engineering of surfaces and interfaces, crucial for numerous applications. Interest in NHC SAMs is mainly driven by their assumingly higher thermal stability compared to thiolate SAMs most broadly used at the moment. Most of the NHC SAMs utilize imidazolium as an anchoring group for linking molecules to the metal substrate via carbene C atom. It is well established in the literature that standing up and stable NHC SAMs are built only when using bulky side groups attached to nitrogen heteroatoms in imidazolium moiety, which, however, leads to monolayers exhibiting much lower packing density compared to thiolate SAMs. Here, by combined X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and temperature-programmed secondary ion mass spectrometry analysis, we demonstrate that using NHCs with small methyl side groups in combination with simple, solution-based preparation leads to the formation of aromatic monolayers exhibiting at least doubled surface density, upright molecular orientation, and ultra-high thermal stability compared to the NHC SAMs reported before. These parameters are crucial for most applications, including, in particular, molecular and organic electronics, where aromatic SAMs serve either as a passive element for electrode engineering or as an active part of organic field effect transistors and novel molecular electronics devices.

Effect of Different In2O3(111) Surface Terminations on CO2 Adsorption.

In2O3-based catalysts have shown high activity and selectivity for CO2 hydrogenation to methanol; however, the origin of the high performance of In2O3 is still unclear. To elucidate the initial steps of CO2 hydrogenation over In2O3, we have combined X-ray photoelectron spectroscopy and density functional theory calculations to study the adsorption of CO2 on the In2O3(111) crystalline surface with different terminations, namely, the stoichiometric, reduced, and hydroxylated surface. The combined approach confirms that the reduction of the surface results in the formation of In adatoms and that water dissociates on the surface at room temperature. A comparison of the experimental spectra and the computed core-level shifts (using methanol and formic acid as benchmark molecules) suggests that CO2 adsorbs as a carbonate on all three surface terminations. We find that the adsorption of CO2 is hindered by hydroxyl groups on the hydroxylated surface.

Extending area selective deposition of ruthenium onto 3D SiO2-Si multilayer stacks

Recent trends in semiconductor process engineering have resulted in significant adoption of new materials and processes to enable new paradigms in device manufacturing. One such emerging process is area selective deposition where a material can be selectively deposited on an area of interest. In this work, we have demonstrated selective deposition of ruthenium (Ru) on amorphous (a-Si) and polycrystallized silicon (p-Si) to silicon dioxide (SiO2) on both 2D blanket films as well as 3D annealed SiO2–Si multilayer stacks. Amorphous Si once crystallized using high temperature annealing exhibits reduced surface hydrogen content (–Si–H), yet we observed Ru growth on p-Si films that were annealed under multiple conditions (800, 900, and 1000 °C). We have used a combination of Fourier transform-infrared spectroscopy and x-ray photoelectron spectroscopy (XPS) to show that both –Si–H and film crystallinity impact the selective growth of Ru. We have also demonstrated selective deposition of ∼10 nm Ru on p-Si layers and ∼0 nm Ru on SiO2 layers of the annealed 3D SiO2–Si multilayer stack. Additionally, by using a combination of XPS and transmission electron microscopy, we have demonstrated that Ru growth is higher on nongrowth surfaces in 2D substrates than on 3D stacks. Finally, we have shown that this process technology can be further advanced using a combination of selective and nonselective conformal atomic layer deposition processes to develop a novel 3D annealed SiO2–Si multilayer stack, thereby demonstrating a 3D device with low –H content p-Si films. This study can help us to realize new integration schemes for innovative 3D device structures.

A metal-free carbon catalyst for oxidative dehydrogenation of aryl cyclohexenes to produce biaryl compounds

A metal-free route based on a carbon catalyst to synthesize biphenyls through oxidative dehydrogenation (ODH) of phenyl cyclohexene has been investigated. Among the samples examined, an air-oxidized active carbon exhibits the best activity with a 9.1 × 10-2 h-1 rate constant, yielding 74% biphenyl in 28 h at 140 °C under five bar O2 in anisole. The apparent activation energy is measured as 54.5 kJ⋅mol-1. The extended reaction scope, consisting of 15 differently substituted phenyl cyclohexenes, shows the wide applicability of the proposed method. The catalyst's good recyclability over six runs suggests this ODH method as a promising route to access the biaryl compounds. In addition, the reaction mechanism is investigated with a combination of X-ray photoelectron spectroscopy, functional group blocking, and model compounds of carbon catalysts and is proposed to be based on the redox cycle of the quinoidic groups on the carbon surface. Additional experiments prove that the addition of the catalytic amount of acid (methanesulfonic acid) accelerates the reaction. In addition, Hammett plot examination suggests the formation of a carbonium intermediate, and its possible structure is outlined.

Thermo-Sensitive Microgel/Poly(ether sulfone) Composited Ultrafiltration Membranes.

Thermo-sensitive microgels known as PMO-MGs were synthesized via surfactant free emulsion polymerization, with poly(ethylene glycol) methacrylate (OEGMA475) and 2-(2-methoxyethoxy) ethyl methacrylate (MEO2MA) used as the monomers and N, N-methylene-bis-acrylamide used as the crosslinker. PMO-MGs are spherical in shape and have an average diameter of 323 ± 12 nm, as determined via transmission electron microscopy. PMO-MGs/poly (ether sulfone) (PES) composited ultrafiltration membranes were then successfully prepared via the non-solvent-induced phase separation (NIPS) method using a PMO-MG and PES mixed solution as the casting solution. The obtained membranes were systematically characterized via combined X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, Fourier transform infrared spectroscopy and contact angle goniometer techniques. It was found that the presence of PMO-MGs significantly improved the surface hydrophilicity and antifouling performance of the obtained membranes and the PMO-MGs mainly located on the channel surface of the membranes. At 20 °C, the pure water flux increased from 217.6 L·m-2·h-1 for pure PES membrane (M00) to 369.7 L·m-2·h-1 for PMO-MGs/PES composited membrane (M20) fabricated using the casting solution with 20-weight by percentage microgels. The incorporation of PMO-MGs also gave the composited membranes a thermo-sensitive character. When the temperature increased from 20 to 45 °C, the pure water flux of M20 membrane was enhanced from 369.7 to 618.7 L·m-2·h-1.

Three-dimensional N/O co-doped hard carbon anode enabled superior stabilities for sodium-ion batteries

Hard carbons (HCs) with low working potential have been considered one of the most promising anodes for sodium-ion batteries (SIBs), whereas the intrinsic poor rate performance and inferior cyclic stability hindered their practical application. Porosity designing and heteroatom doping are considered essential for high rate performance as well as durability by relieving volume expansion with Na-interaction and providing rapid Na+ diffusion paths. Herein, a three-dimensional N/O co-doped HCs (NOHCs) is synthesized as an anode for ultrastable SIBs. Combining X-ray photoelectron spectroscopy and transmission electron microscopy, we find that the content of pyrrolic-N is positively correlated with carbon interlayer distance, and the CO group could provide more active sites, thus superior reaction kinetics could be observed in NOHCs samples. In-situ Raman and ion diffusion kinetic analysis (GITT and CV) suggest that the integrated strategy of hetero doping and designed pore structure enables highly reversible electrochemical reactions and fast diffusion kinetics. Thus obtained NOHC-2 anode exhibits excellent capacity retention (69.8% after 15,000 cycles, 10.0 A g−1) and rate performance (160.2 mAh g−1 at 10.0 A g−1) with Na metal as the counter electrode. More importantly, the full cell composed of NOHCs anode and Prussian blue cathode delivers a high energy density of 97.3 Wh kg−1 with a power density of 985.7 W kg−1.

Combined electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy analysis of the passive films formed on 5083 aluminium alloy

A combined electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) approach showed that the corrosion behaviour of 5083 Al alloy was controlled by Mg dissolution at the Mg-rich intermetallic coarse particles (IMCs) that were defects of the passive film. It was thus shown that microstructures with high amount of Mg-rich IMCs were less resistant to corrosion. EIS experimental data were well superimposed with fitted ones calculated using a model proposed in the literature for pure magnesium. The model allowed to plot the resistivity profiles of the passive films, which highlighted their double-layer structure evidenced by XPS.

Influence of the Morphology on the Functionalization of Graphene Nanoplatelets Analyzed by Comparative Photoelectron Spectroscopy with Soft and Hard X‐Rays

AbstractSince its isolation, graphene has received growing attention from academia and industry due to its unique properties. However, the “what is my material” barrier hinders further commercialization. X‐ray photoelectron spectroscopy (XPS) is considered as a method of choice for the determination of the elemental and chemical composition. In this work the influence of the morphology of graphene particles on the XPS results is studied and investigated as a function of X‐ray energy, using conventional XPS with Al Kα radiation and hard X‐ray photoemission spectroscopy (HAXPES) using Cr Kα radiation. Thereby, the information depth is varied between 10 and 30 nm. For this purpose, two commercial powders containing graphene nanoplatelets with lateral dimensions of either ≈100 nm or in the micrometer range are compared. These larger ones exist as stack of graphene layers which is inspected with scanning electron microscopy. Both kinds of particles are then functionalized with either oxygen or fluorine. The size of the graphene particles is found to influence the degree of functionalization. Only the combination of XPS and HAXPES allows to detect the functionalization at the outermost surface of the particles or even of the stacks and to provide new insights into the functionalization process.

Characterization of Octyl Hydroxamic Acid as Inhibitor on Cu Chemical Mechanical Polishing

As an inhibitor for copper (Cu), Octyl hydroxamic acid (OHA) has been extensively studied through a combination of density functional theory (DFT) and experiments. Our findings indicate that using a concentration of 3 mM OHA as an inhibitor can lead to a remarkable removal rate (RR) and surface quality when the pH is at 10. Tafel analysis of potentiodynamic polarization plots was performed to demonstrate that OHA can lower the corrosion current. Further insight into the adsorption behavior of OHA on the Cu surface was obtained through a comprehensive study combining X-ray photoelectron spectroscopy (XPS), DFT calculations, and adsorption isotherm model analysis.