Angle-resolved X-ray Photoelectron Spectroscopy Analysis Research Articles

Surface analysis and interface properties of 2-aminobenzimidazole corrosion inhibitor for brass in chloride solution.

This work presents a corrosion study of 2-aminobenzimidazole (ABI) as a corrosion inhibitor for brass in chloride solution. Electrochemical, field emission scanning electron microscopy, atomic force microscopy, and contact angle measurements showed that ABI mitigates brass corrosion after short-, medium-, and long-term immersion periods. Next, a detailed surface analysis of the ABI adsorbed on the brass surface was performed using attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) techniques. XPS imaging was performed in association with principal component analysis to determine the different phases on the surface. In order to describe the in-depth composition of the ABI surface, an angle-resolved XPS analysis was performed. This analysis was further supported by gas cluster ion beam sputtering to gradually remove the ABI surface layer, and XPS analysis was performed after each sputtering cycle. Finally, TOF-SIMS analyses showed the formation of Cu/Cu2-ABI and Zn-ABI compounds, the 2D distribution of ABI-related compounds, and their thermal stability on the brass surface. Graphical abstract.

Formation of Horizontally and Vertically Oriented MoS2 and MoSe2 Films Using Cracked Small S- and Se-Molecules and Its Applications for Transparent a-Si:H Thin Film Photovoltaic Devices

Molybdenum dichalcogenide films (MoX2, X=S, Se) were fabricated on 6-inch wafers by a breakthrough technique utilizing cracked small X-molecules. Uniformly deposited Mo-metal films were sulfurized or selenized by reactive chalcogen (Xa, a= 1- 2) small molecules, and MoX2 film was approximately 3 times thicker than the Mo metal precursor. The behavior of reaction chamber pressure according to the cracking temperature indicated that one large molecule could crack into 4 – 5 small particles in experimental condition used in this work. The formation of protrusions was also effectively inhibited to obtain MoX2 films of a device quality. First, I will explain how effectively large chalcogen molecules (normally X8) were cracked, and the cracking effect on the film quality. By controlling the cracking temperature separately, we could lower the growth temperature down to 400 oC or lower. The effect of cracking and X-source evaporation temperatures on the film quality will be also presented. The film quality was dependent on the deposition technique of Mo metal films. The films were characterized using x-ray photoelectron spectroscopy (XPS), Raman scattering, atomic force microscopy (AFM), and transmission electron microscopy (TEM). Cross sectional high resolution TEM image, energy-dispersive x-ray spectroscopy, and angle-resolved XPS analysis of 6 nm-thick MoS2 sulfurized at 570 oC showed that the film has well-aligned layer-by-layer crystalline structure and the composition and chemical states were uniform through depth. Normally, layer-by-layer grown MoX2 films on very flat surfaces are studied for device applications as reported in earlier works. But, practical devices require the growth of semiconductor films on rough and/or patterned surfaces. Then, we studied the formation of a few nm-thick and a few tens nm-thick MoX2 films on rough surfaces, and found that the MoX2 films could be successfully grown on a very rough substrate (root mean square roughness = 38 nm) using the method introduced in this work. When MoX2 films were grown by chalcogenizing Mo, the crystalline orientation of MoX2 films depended on the thickness of Mo films. When the Mo film is thinner than 5 nm, we could obtain layer-by-layer structured, i.e., MoX2 films. We had reported the successful application of the horizontally grown MoX2 film to the field effect transistors in the previous work [1]. Contrarily, when the Mo film was 5 nm or thicker, the formed MoX2 films had vertically oriented crystalline structure. It is because the stress due to 3 times volume expansion should be released by changing the crystalline orientation from planar layer-by-layered to vertically oriented structures. In this work, we utilized the vertically oriented MoX2 films as an interlayer between the semiconductor layer and the electrode. By adopting the MoX2 interlayer in amorphous silicon (a-Si:H) thin film photovoltaic devices having the inverted structure, we could obtain greatly improved cell performances. In the substrate type photovoltaic cells, the shunt resistance increased from 10 kΩ (no MoSe2) to 18 kΩ (with MoSe2) and the open circuit voltage increased from 0.717 V to 0.785 V. The a-Si:H photovoltaic cell having 26 % visible light transmittance on a glass substrate showed the conversion efficiency of 7.7 % under blue light irradiation of 7 mW/cm2. In conclusion, the horizontally and vertically oriented MoX2 films of high crystallinity were formed by chalcogenizing Mo metal films using reactive cracked small X-molecules, and the use of MoX2 film as an interlayer greatly improved the performance of a-Si:H thin film photovoltaic devices. The growth method introduced in this work would be one of the most promising methods to obtain uniform and high quality metal dichalcogenide films on a large substrate. The most important advantage of this method is that it can be easily applied to other metal chalcogenide materials. [1] Jung, K. H.; Yun, S. J.; Choi, Y.; Cho, J. H.; Lim, J. W.; Chai, H.-J.; Cho, D.-H.; Chung, Y.-D.; Kim, G. Nanoscale 2018, 10, 15213-15221.

(Invited) Interface Control of Advanced Electronic Devices - High-k/Metal Gate System and Magnetic Tunneling Junction

With the scaling of electronic devices, interface control of the constituent materials has become more and more important. Several key issues and related topics are taken up and reviewed with respect to logic and memory devices. The key issues are interface control in high-k/metal gate system for logic application and magnetic tunneling junction for memory application. High-k/Metal Gate System [1] In accordance with the requirement of CMOS scaling, replacement of thermally grown SiO2 gate dielectric with other dielectric materials with higher dielectric constant (k) has become imperative to reduce the equivalent oxide thickness (EOT) to achieve higher drivability of FET. Key factors on Hf-based high-k/metal gate (HK/MG) CMOS technology based on conventional gate first process for low operational power application are overviewed. Work-function (WF) tuning derived from ionic property of high-k material, process cost, EOT scaling with low gate leakage current are issues to be overcome. Among them, the key issue is how to control the atomic distribution in the Hf-based HK/MG system, which is absolutely requisite for WF tuning and EOT scaling. Interpretation of effective work-function (WF): For conventional gate first process, due to the interfacial reaction, the Fermi level is pinned and the WF increases with decreasing the EOT. In addition to this, due to the fixed charge in the high-k dielectric, the WF is also modulated, hence the effective WF (eWF) changes. The effect of the fixed charge is rather complicated due to an oxygen vacancy behavior in HK. Consequently, the eWF results in the “roll-off” behavior caused by the (+) charge induced by the oxygen vacancy. When the oxygen increases, i.e., (-) charge increases in the HK, the obtained WF tends to roll-up. In contrast, it tends to roll-off for more (+) charge induced by oxygen vacancy, Vo 2+in the HK. Formation process of Hf-based high-k (HK): Generally, HK is deposited by metal-organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD), however, HK dielectric formation by oxidizing a preliminarily sputtered metallic-Hf is reasonable approach for fabricating the HK gate stack in a very pure form with less water content across the wafer. And in a very important thing, by controlling the oxidation time, this process can provide precise thickness control of the interfacial layer (IL) including “zero IL” with excellent uniformity. Magnetic Tunneling Junction A magnetic tunnel junction (MTJ) for spin-transfer-torque (STT) switching is a promising building block of non-volatile working memory embedded in very large scale integrated circuits (VLSIs) because of its potential to reduce a power consumption by replacing the conventional volatile cache memories. Among many materials, a CoFeB/MgO/CoFeB stack structure has attracted much attention as a candidate of MTJ embedded in VLSIs because of its high tunnel magnetoresistance (TMR) ratio caused by a perpendicular magnetic easy axis. And what is better, this MTJ has a potential for high integration into VLSIs down to a junction size of 1X nm regime. To improve the MTJ performance, crystal structure of the CoFeB/MgO interface is a crucial issue as well as B behavior during the process treatment. Redox reaction: As an example of the interfacial reaction, a redox reaction was observed at the surface of Ta/CoFeB/MgO/CoFeB MTJ stack after annealing up to 400℃ for 1 h in vacuum, by angle-resolved X-ray photoelectron spectroscopy (XPS). For 1nm-thick tantalum capping layer of the as-deposited stack sample, both the tantalum layer and the surface of the CoFeB layer underneath the tantalum layer were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra with respect to as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms was found to occur at the surface of the CoFeB layer. This reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were found to be reduced by boron atoms that diffused toward the surface of the top CoFeB layer. By means of naturally oxidized surface of the CoFeB layer formed on SiO2, the redox reaction behavior after annealing was confirmed by angle-resolved XPS analysis[2]. This redox reaction is thermodynamically reasonable according to the Ellingham diagram. (This work is supported by Industrial Affiliation on the STT-MRAM program in CIES Consortium and ACCEL project under JST.) [1] M. Niwa (2013), Chapter 4, High Permittivity Gate Dielectric Materials, Edited by S. Karr, Springer Series in Advanced Microelectronics 43 , pp. 191-234. [2] S. Sato et al., Appl. Phys. Lett. 196, 142407 (2015).

Investigation of TiN thin film oxidation depending on the substrate temperature at vacuum break

Due to the reduction of the thickness of the layers used in the advanced technology nodes, there is a growing importance of the surface phenomena in the definition of the general properties of the materials. One of the least controlled and understood phenomenon is the oxidation of metals after deposition, at the vacuum break. In this study, the influence of the sample temperature at vacuum break on the oxidation level of TiN deposited by metalorganic chemical vapor deposition is investigated. TiN resistivity appears to be lower for samples which underwent vacuum break at high temperature. Using X-ray photoelectron spectrometry analysis, this change is correlated to the higher oxidation of the TiN layer. Moreover, angle resolved XPS analysis reveals that higher is the temperature at the vacuum break, higher is the surface oxidation of the sample. This surface oxidation is in turn limiting the diffusion of oxygen in the volume of the layer. Additionally, evolution of TiN layers resistivity was monitored in time and it shows that resistivity increases until a plateau is reached after about 10 days, with the lowest temperature at vacuum break resulting in the highest increase, i.e., the resistivity of the sample released to atmosphere at high temperature increased by a factor 1.7 whereas the resistivity of the sample cooled down under vacuum temperature increased by a factor 2.7.

Microstructural Analysis of Multi-phase Ultra-Thin Oxide Overgrowth on Al–Mg Alloy by High Resolution Transmission Electron Microscopy

High-resolution transmission electron microscopy analyses are carried out to understand the microstructure of the ultra-thin oxide-film grown on a (native) amorphous Al2O3-coated Al-0.8 at.% Mg alloy substrate at T = 600 K for t = 2 h and at pO2 of 1 × 10−2 Pa. This oxide-film is found to be non-uniformly thick with thicknesses varying from 1.50 to 4.60 nm. Occasionally, this oxide is found to diffuse into the Al–Mg alloy substrate, forming oxide thicknesses up to 10.5 nm. Overall, this oxide-film is found to consist of a mixed amorphous, (poly) crystalline and an intermediate amorphous-to-crystalline transition regions, with crystalline regions consisting mostly of MgO and the diffused oxide regions into the Al–Mg alloy substrate coated with γ-Al2O3. These observations are then compared with the experimental results obtained using angle-resolved X-ray Photoelectron Spectroscopy analysis and thermodynamic predictions for the growth of an ultra-thin oxide-film due to dry, thermal oxidation of Al–Mg alloy substrates.

Layer by layer electroless deposition: An efficient route for preparing adhesion-enhanced metallic coatings on plastic surfaces

A layer by layer (LbL) electroless deposition method is presented to fabricate adhesion-enhanced metallic coatings on plastic surfaces. This method relies on procedures of modifying the polymeric substrates to form surface-bonded active groups. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) were used to characterize the Ag surfaces. Formation mechanism of Ag films via this plating technology has been primarily investigated in detail. In order to explore component structure of Ag coatings, the spray-assisted LbL process has been designed as various spray passes in air or N2 atmosphere, with angle resolved XPS analysis. Standard cross-cut test and 90° peel test results confirmed the high adhesion at the interface of metallic coatings and plastic substrates, owing to the chemical covalent bonding that can be introduced for other coatings on different kinds of materials. In addition, inspiring by the prepared ornamental coatings and Cu films, this LbL method provides an efficient, simple and fast process to prepare metallic coatings on plastic surfaces and it is believed that such technique may open a new approach to expand the methodology of fabricating decorative coatings and surface metallization of polymer materials.

High-selectivity electrochemical non-enzymatic sensors based on graphene/Pd nanocomposites functionalized with designated ionic liquids

Nano-sized Pd particles are uniformly dispersed on graphene nanosheets (GNSs) using a supercritical-fluid-assisted deposition technique to increase the electrochemical sensing properties. The incorporation of different kinds of ionic liquid (IL) can increase the electrode sensing current toward different analytes. Butylmethylpyrrolidinium–bis(trifluoromethanesulfonyl)imide (BMP–TFSI) IL is beneficial for glucose detection, whereas the electrode with butylmethylpyrrolidinium–dicyanamide (BMP–DCA) IL shows high sensitivity toward ascorbic acid (AA). The selective detection of glucose or AA from their mixture is for the first time demonstrated using a non-enzymatic electrode with the aid of an IL. Angle-resolved X-ray photoelectron spectroscopy analyses indicate that GNSs can create an aligned cation/anion orientation in the adsorbed IL film, with the anions preferentially occupying the topmost surface. As a result, the electrode sensitivity and selectivity are mainly determined by the IL constituent anions.

Evidence of a reduction reaction of oxidized iron/cobalt by boron atoms diffused toward naturally oxidized surface of CoFeB layer during annealing

We have investigated the redox reaction on the surface of Ta/CoFeB/MgO/CoFeB magnetic tunnel junction stack samples after annealing at 300, 350, and 400 °C for 1 h using angle-resolved X-ray photoelectron spectroscopy for precise analysis of the chemical bonding states. At a capping tantalum layer thickness of 1 nm, both the capping tantalum layer and the surface of the underneath CoFeB layer in the as-deposited stack sample were naturally oxidized. By comparison of the Co 2p and Fe 2p spectra among the as-deposited and annealed samples, reduction of the naturally oxidized cobalt and iron atoms occurred on the surface of the CoFeB layer. The reduction reaction was more significant at higher annealing temperature. Oxidized cobalt and iron were reduced by boron atoms that diffused toward the surface of the top CoFeB layer. A single CoFeB layer was prepared on SiO2, and a confirmatory evidence of the redox reaction with boron diffusion was obtained by angle-resolved X-ray photoelectron spectroscopy analysis of the naturally oxidized surface of the CoFeB single layer after annealing. The redox reaction is theoretically reasonable based on the Ellingham diagram.

Study of the Anchoring Process of Tethered Unsymmetrical Zn-Phthalocyanines on TiO2 Nanostructured Thin Films

Thin nanoporous TiO2 layers, deposited by dc reactive sputtering, have been functionalized with a novel unsymmetrical Zn(II) phthalocyanine (ZnPc-II) bearing a push–pull system, properly designed for application in dye sensitized solar cells. The anchoring process has been studied by combining visible absorption (vis), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) in order to investigate the molecular assembly during the early stage of the sensitizing process. The vis and XPS measurements indicate that the ZnPc-II surface density (dsurf, molecules/cm2) and its binding geometry are strongly affected by the concentration of the grafting solutions. It has been observed that the ZnPc-II surface density monotonically increases by increasing the solution concentration up to a saturation of dsurf ∼ 1.0 × 1013 molecules/cm2. Angle resolved XPS analyses indicate that at low molecular surface density a strong interaction between the ZnPc-II aromatic macrocycle and the TiO2 surface occurs...

Protein adsorption and covalent bonding to silicon nitride surfaces modified with organo-silanes: Comparison using AFM, angle-resolved XPS and multivariate ToF-SIMS analysis

Organo-silanes provide a suitable interface between the silicon-based transducers of various biosensing devices and the sensing proteins, immobilized through physical adsorption, as for (3-aminopropyl)triethoxysilane (APTES), or covalent binding, e.g. via protein amine groups to (3-glycidoxypropyl)trimethoxysilane (GOPS) modified surface. Immobilization of rabbit gamma globulins (RgG) to silicon nitride surfaces, modified either with APTES or GOPS, was examined as a function of incubation time using atomic force microscopy (AFM), angle-resolved X-ray photoelectron spectroscopy (ARXPS) and time of flight secondary ion mass spectrometry (ToF-SIMS). Multivariate technique of principal component analysis was applied to ToF-SIMS spectra in order to enhance sensitivity of immobilized RgG detection. Principal component regression shows a linear relationship with surface density determined rigorously from ARXPS following an organic bilayer approach, allowing for protein coverage quantification by ToF-SIMS. Taking it overall the surface immobilized amount of RgG is higher and develops faster on the surfaces silanized with APTES rather than with GOPS. Similar, although less distinct, difference is observed between the two surface types concerning the temporal evolution of average AFM height. The average height of protein overlayer correlates well with ARXPS and ToF-SIMS data expressed in terms of protein surface density. However, determined linear regression coefficients are distinctively higher for the surfaces modified with epoxy- rather than amino-silane, suggesting different surface density and conformation of the proteins immobilized through to covalent binding and physical adsorption.

Derivatization of Free Radicals in an Isopropanol Plasma Polymer Film: The First Step toward Polymer Grafting

Plasma-polymerized films (PPF) synthesized by plasma-enhanced chemical vapor deposition (PECVD) find increasing applications in biomedicine and differ in many ways from conventional polymers. One of the most specific properties of the PPF is the high reactivity of its free-radical-rich surface, arising from the deposition mechanism. Although generally considered as a disadvantage leading to the aging of the PPF, reactivity of the plasma-treated polymers and PPF surfaces can be beneficially employed, for example, for grafting of a specific chemical functionality or short polymer chains. The quantitative evaluation of the surface radical density of the PPF is thus considered as the necessary preparatory step toward any subsequent grafting reaction. In the present study, the surface radical density of an isopropanol-based PPF was quantitatively determined by a combination of NO chemical derivatization and X-ray photoelectron spectroscopy (XPS). Once the derivatization conditions were optimized, the radical density, derived from at % N determined by XPS, was evaluated as a function of the deposition power. It was found out that the surface density of free radicals presents a maximum for the deposition power of 200 W (~2.3 × 10(14) spin/cm(2)) and it stabilizes (~2.1 × 10(14) spin/cm(2)) with further power increase. XPS findings were supported by in situ FTIR measurements that provided additional information about the degree of plasma fragmentation denoting fragmentation saturation for a deposition power of 200 W. By fitting the N1s peak it was possible to identify primary, secondary and ternary radicals and to study their respective evolutions with different deposition conditions. Angle-resolved XPS analysis allowed the in-depth distribution of radicals to be addressed, revealing that on the top surface, primary, and secondary radicals are dominating, whereas more tertiary radicals are present in the subsurface region. Finally, some preliminary chemical grafting experiments have allowed the relevance of derivatization results to be cross-checked.

Angle-Resolved XPS Analysis and Characterization of Monolayer and Multilayer Silane Films for DNA Coupling to Silica

We measure silane density and Sulfo-EMCS cross-linker coupling efficiency on aminosilane films by high-resolution X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements. We then characterize DNA immobilization and hybridization on these films by (32)P-radiometry. We find that the silane film structure controls the efficiency of the subsequent steps toward DNA hybridization. A self-limited silane monolayer produced from 3-aminopropyldimethylethoxysilane (APDMES) provides a silane surface density of ~3 nm(-2). Thin (1 h deposition) and thick (19 h deposition) multilayer films are generated from 3-aminopropyltriethoxysilane (APTES), resulting in surfaces with increased roughness compared to the APDMES monolayer. Increased silane surface density is estimated for the 19 h APTES film, due to a ∼32% increase in surface area compared to the APDMES monolayer. High cross-linker coupling efficiencies are measured for all three silane films. DNA immobilization densities are similar for the APDMES monolayer and 1 h APTES. However, the DNA immobilization density is double for the 19 h APTES, suggesting that increased surface area allows for a higher probe attachment. The APDMES monolayer has the lowest DNA target density and hybridization efficiency. This is attributed to the steric hindrance as the random packing limit is approached for DNA double helices (dsDNA, diameter ≥ 2 nm) on a plane. The heterogeneity and roughness of the APTES films reduce this steric hindrance and allow for tighter packing of DNA double helices, resulting in higher hybridization densities and efficiencies. The low steric hindrance of the thin, one to two layer APTES film provides the highest hybridization efficiency of nearly 88%, with 0.21 dsDNA/nm(2). The XPS data also reveal water on the cross-linker-treated surface that is implicated in device aging.

Resolving overlapping peaks in ARXPS data: The effect of noise and fitting method

Peak-fitting of X-ray photoelectron spectroscopy (XPS) data can be very sensitive to noise when the difference on the binding energy among the peaks is smaller than the width of the peaks. This sensitivity depends on the fitting algorithm. Angle-resolved XPS (ARXPS) analysis offers the opportunity of employing the combined information contained in the data at the various angles to reduce the sensitivity to noise. The assumption of shared peak parameters (center and width) among the spectra for the different angles, and how it is introduced into the analysis, plays a basic role. Sequential fitting is the usual practice in ARXPS data peak-fitting. It consist on first estimating the center and width of the peaks from the data acquired at one of the angles, and then using those parameters as a starting approximation for fitting the data for each of the rest of the angles. An improvement of this method consists of averaging the centers and widths of the peaks obtained at the different angles, and then employing these values to assess the areas of the peaks for each angle. Another strategy for using the combined information is by assessing the peak parameters from the sum of the experimental data. The complete use of the combined information contained in the data-set is optimized by the simultaneous fitting method. It consists of the assessment of the center and width of the peaks by fitting the data at all the angles simultaneously. Computer-generated data was employed to compare the sensitivity with respect to noise between the sequential, averaged-sequential, sum, and simultaneous fitting methods. It is shown that the latter is significantly more robust and could provide reliable results even for noisy data and small peak separation. The fundamentals for the robustness of the simultaneous method are discussed, as well as the possibility of fitting many parameters at the same time. As an added feature of ARXPS, it was found that the estimation of the error intervals on the peak parameters is done remarkably more precisely by employing XPS data at various angles.

Adlayers of Dimannoside Thiols on Gold: Surface Chemical Analysis

Carbohydrate films on gold based on dimannoside thiols (DMT) were prepared, and a complementary surface chemical analysis was performed in detail by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), near-edge X-ray absorption fine structure (NEXAFS), FT-IR, and contact angle measurements in order to verify formation of ω-carbohydrate-functionalized alkylthiol films. XPS (C 1s, O 1s, and S 2p) reveals information on carbohydrate specific alkoxy (C-O) and acetal moieties (O-C-O) as well as thiolate species attached to gold. Angle-resolved synchrotron XPS was used for chemical speciation at ultimate surface sensitivity. Angle-resolved XPS analysis suggests the presence of an excess top layer composed of unbound sulfur components combined with alkyl moieties. Further support for DMT attachment on Au is given by ToF-SIMS and FT-IR analysis. Carbon and oxygen K-edge NEXAFS spectra were interpreted by applying the building block model supported by comparison to data of 1-undecanethiol, poly(vinyl alcohol), and polyoxymethylene. No linear dichroism effect was observed in the angle-resolved C K-edge NEXAFS.

Studies on the effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped 2-perfluorooctylethyl methacrylate films

The effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped with various numbers of units of 2-perfluorooctylethyl methacrylate (FMA) (PnAMA-ec-PFMA) were investigated by differential scanning calorimetry, angle-resolved XPS analysis, contact angle measurements, and X-ray diffraction (XRD). The results show that with similar numbers of FMA units at the polymer chain end the extent of fluorine segregation (Q) increased with increasing the number of carbon atoms in the side n-alkyl chains of poly(n-alkyl methacrylate). The surface fluorine content within 5nm deep of the film of poly(n-octadecyl methacrylate) end-capped with one FMA unit (PODMA160-ec-PFMA1.0) was 208-fold higher than that of the bulk level. These observed differences in Q values were found due to the aggregate structure of the end-capped polymers in the solution, the flexibility, and the crystallinity of the n-alkyl side chains. When the nonfluorinated block was completely amorphous, the molecular aggregate structure of the end-capped polymers in the solution played an important role in the surface segregation of the fluorinated moieties on the resulting film. However, when the nonfluorinated block was crystalline, crystallinity would enhance greatly the segregation of the fluorinated moieties.

Preparation and XPS study of X-ray photochromic transparent BiOI/nylon11 composite film

Nylon11 film immersed in BiI3–ethanol solution was used for in situ generation of transparent BiOI/nylon11 X-ray photochromic composite materials via integration of the hydrolyzate (BiOI) of BiI3 into nylon11. The obtained BiOI/nylon11 composite film shows a reversible photochromic effect, changing the color from orange-red to brownish black under soft X-ray irradiation and back to orange-red after air exposure. X-ray photoelectron spectroscopy (XPS) results show that the oxidation state of Bi atoms in BiOI/nylon11 composite film does not change before and after changing the color. Angle-resolved XPS analysis reveals that BiOI in nylon11 film is well distributed within an infiltration depth of about 10 nm. The source of the X-ray photochromic effect for transparent BiOI/nylon11 composite film may be related to oxygen as well as the interaction between BiOI and the amide groups. The oxygen AT% in the composite film decreases with increasing X-ray irradiation time. The present method for preparing transparent BiOI/nylon11 X-ray photochromic composite materials is facile and low cost. The X-ray photochromic effect has potential applications in some technology fields. For example, it can be used to create temporary patterning in a colored composite material surface.

XPS for non-destructive depth profiling and 3D imaging of surface nanostructures

Depth profiling of nanostructures is of high importance both technologically and fundamentally. Therefore, many different methods have been developed for determination of the depth distribution of atoms, for example ion beam (e.g. O(2)(+) , Ar(+)) sputtering, low-damage C(60) cluster ion sputtering for depth profiling of organic materials, water droplet cluster ion beam depth profiling, ion-probing techniques (Rutherford backscattering spectroscopy (RBS), secondary-ion mass spectroscopy (SIMS) and glow-discharge optical emission spectroscopy (GDOES)), X-ray microanalysis using the electron probe variation technique combined with Monte Carlo calculations, angle-resolved XPS (ARXPS), and X-ray photoelectron spectroscopy (XPS) peak-shape analysis. Each of the depth profiling techniques has its own advantages and disadvantages. However, in many cases, non-destructive techniques are preferred; these include ARXPS and XPS peak-shape analysis. The former together with parallel factor analysis is suitable for giving an overall understanding of chemistry and morphology with depth. It works very well for flat surfaces but it fails for rough or nanostructured surfaces because of the shadowing effect. In the latter method shadowing effects can be avoided because only a single spectrum is used in the analysis and this may be taken at near normal emission angle. It is a rather robust means of determining atom depth distributions on the nanoscale both for large-area XPS analysis and for imaging. We critically discuss some of the techniques mentioned above and show that both ARXPS imaging and, particularly, XPS peak-shape analysis for 3D imaging of nanostructures are very promising techniques and open a gateway for visualizing nanostructures.

Studies on the Adsorption Property and Structure of Polyamine-Ended Poly(ethylene glycol) Derivatives on a Gold Surface by Surface Plasmon Resonance and Angle-Resolved X-ray Photoelectron Spectroscopy

The adsorption properties and structure of polyamine-ended poly(ethylene glycol) (PEG) derivatives on a flat gold surface were studied by means of surface plasmon resonance (SPR) and X-ray photoelectron spectroscopy (XPS) using PEG(5k)-block-poly[2-(N,N-dimethylamino)ethyl methacrylate](7.5k) [PEG-b-PAMA(5k/7.5k)] and pentaethylenhexamine-ended PEG(5k) [N6-PEG(5k)], which had 48 and 6 amino groups at the omega-end, respectively. The SPR analysis showed that the amount of PEG-b-PAMA(5k/7.5k) adsorbed onto the gold surface was not affected by the change in pH, and the desorption of this copolymer from the surface was not observed upon the addition of a solution at high salt concentration. The angle-resolved XPS (ARXPS) analysis revealed the structure of the PEG-b-PAMA polymer layer constructed on the gold surface: the PAMA segments were concentrated and located at the interface between the PEG layer and the gold surface. On the other hand, in the case of the PEG-graft-PAMA copolymer (PAMA-g-PEG)-modified gold surface, both the PAMA and the PEG segments homogeneously migrated to all regions of the constructed copolymer layer. The adsorbed amounts of N6-PEG(5k) under different pH conditions were constant and 2-3 times higher than those caused by the adsorption of single amino group-terminated PEG(5k) [PEG-NH(2)(5k)] and hydroxyl group-terminated PEG(5k) [PEG-OH(5k)]. The N6-PEG(5k)-modified gold surface showed a higher nonfouling property toward the adsorption of bovine serum albumin compared with the bare and the N6-modified gold surface. These results indicate that polyamine-ended PEGs were strongly immobilized onto the gold surface by polyamine anchors, even though electrostatic interaction between the polyamine and the gold substrate was not the dominant factor in this adsorption event. Furthermore, the formation of an almost complete phase-separated PEG/polyamine layer on the gold surface by polyamine-ended PEGs was strongly suggested.

Etch Characteristics of ZrO2 Thin Films in High Density Plasma

In this work, we investigated the etching characteristics of ZrO2 thin film and the selectivity of ZrO2 thin film to Si in the HBr/CF4 high density plasma (HDP) system. The maximum etch rate of 70.8 nm/min for ZrO2 thin film was obtained at HBr (75%)/CF4 (25%) gas mixing ratio. At the same time, the etch rate was measured as functions of the etching parameters such as HDP source power, bias power and temperature. The angle-resolved X-ray photoelectron spectroscopy analysis showed an efficient destruction of the oxide bonds by the ion bombardment as well as an accumulation of low volatile reaction products on the etched surface. Based on these data, the ion-assisted chemical reaction was proposed as the main etch mechanism of ZrO2 for the CF4-containing plasmas.

Analysis of weakly bonded oxygen in HfO2/SiO2/Si stacks by using HRBS and ARXPS

We have used transmission electron microscopy, high-resolution Rutherford backscattering spectrometry (HRBS), and angle-resolved X-ray photoelectron spectroscopy (ARXPS) to investigate the interfacial oxidized states of hafnium oxide/silicon oxide/Si gate oxide stacks. The atomic concentrations and profiles of HRBS analysis are similar before and after annealing; however, ARXPS shows a clear difference in bond status. These results imply that weakly bonded oxygen atoms existed in the stacks alongside the suboxides. In the as-deposited layers, dioxides are found at the interfaces and suboxides in the layers whereas after annealing suboxides are found at the interfaces and dioxides are found in the layers because of redistribution of bonds during annealing. The combination of HRBS and ARXPS analyses indicated that the main oxidized states transformed from the suboxides to the dioxides with no obvious quantitative difference in the content of oxygen atoms, suggesting that reactions of the weakly bonded oxygen atoms occurred with the suboxides within the layers.