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We studied the adsorption and reaction behavior of the ionic liquid (IL) 1,3-dimethylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C1C1Im][Tf2N]) on Cu(111) using non-contact atomic force microscopy (nc-AFM), scanning tunneling microscopy (STM), and angle-resolved X-ray photoelectron spectroscopy (ARXPS) in ultrahigh vacuum as a function of temperature, supported by density-functional theory (DFT) calculations. Our nc-AFM results for sub-monolayer IL films show that at 200 K, the IL self-assembles into highly ordered islands, with cations and anions arranged next to each other in a checkerboard–type phase. After extended annealing at 300 K, the structure transforms first to a hexagonal phase and then to a porous honeycomb phase. Simultaneously, many small, disordered islands are formed. Complementary ARXPS reveals no IL desorption until 300 K. However, a significant fraction of the IL is converted to a new species as deduced from new, strongly shifted peaks that develop in the XP spectra at around 275 K and grow with annealing time at 300 K. We correlate the remaining unshifted peaks to the ordered phases observed in nc-AFM and the shifted peaks to decomposition products, which appear as disordered islands in nc-AFM and STM. Upon further heating to 360 K, about 50% of the anions or their decomposition products desorb from the surface, while cation-related fragments mostly remain on the surface. From DFT, we obtain additional information on the structure of the ordered phases and the interaction of the IL with the substrate. [ABSTRACT FROM AUTHOR]

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C8C1Im][PF6] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG2)2Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C8C1Im][PF6] and the PEG chains of [(mPEG2)2Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C8C1Im][PF6] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy. [ABSTRACT FROM AUTHOR]

We investigated the surface tension and surface composition of various mixtures of the two ionic liquids (ILs) 1-methyl-3-octyl-imidazolium hexafluorophosphate [C8C1Im][PF6] and 1,3-bis(polyethylene glycol)imidazolium iodide [(mPEG2)2Im]I in the temperature range from 230 to 370 K under ultraclean vacuum conditions. The surface tension was measured using a newly developed apparatus, and the surface composition was determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). In the pure ILs, the alkyl chains of [C8C1Im][PF6] and the PEG chains of [(mPEG2)2Im]I are enriched at the IL/vacuum interface. In the mixtures, a strong selective surface enrichment of the alkyl chains occurs, which is most pronounced at low [C8C1Im][PF6] contents. For the surface tension, strong deviations from an ideal mixing behaviour take place. By applying a simple approach based on the surface composition of the mixtures as deduced from ARXPS, we are able to predict and reproduce the experimentally measured temperature-dependent surface tension values with astonishingly high accuracy.

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH 2 ) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level. [ABSTRACT FROM AUTHOR]

Angle-resolved X-ray photoelectron spectroscopy method was used to study self-sputtering effects of different n-type low-energy doping techniques, including conventional monoatomic 75As and 31P beam-line ion implants and AsH3 plasma doping (PLAD). It has been found that the self-sputtering effects of the beam-line implants correlate with the mass of ion species. As beam-line implant shows more serious self-sputtering effect than monoatomic P and B beam-line implants. Very low energy P implants show surface-swelling phenomena. PLAD process using AsH3 gas species has no sputtering effects but has slight deposition under current process condition. [ABSTRACT FROM AUTHOR]

Angle-resolved X-ray photoelectron spectroscopy method was used to study self-sputtering effects of different p-type (boron-based) low-energy doping techniques, including conventional monoatomic "B beam-line ion implant, molecular beamline ion implants, cluster B beam-line ion implant, and plasma doping (PLAD). It has been found that the self-sputtering effects of the beam-line implants correlate with the mass of ion species except for BF2 implant. Cluster B implant shows severe selfsputtering effect and surface roughness due to its very heavy and very large cluster ions. BF2 implant shows severe sputtering/etching effect but comparable roughness due to a combination of the physical sputtering and reactive ion etching. PLAD processes using B2H6 and BF3 gas species have no sputtering effects but have deposition under certain process conditions. [ABSTRACT FROM AUTHOR]

A newly developed surface analysis technique, which combines secondary ion mass spectrometry with angle-resolved X-ray photoelectron spectroscopy, was used to achieve more accurate results of the retained impurity doses and profiles for ultralow-energy implants, including conventional beamline implant and plasma immersion ion implantation (PIII). Using this method, it has been found that the B2H6 (diborane) PIII demonstrates thicker native oxide and much more B dose loss during rapid thermal processing and surface-cleaning treatments than conventional beamline ion implantation, due to the higher surface B concentration. In order to match the electrical parameters of the device, PIII must consider higher nominal dose to compensate the B loss. [ABSTRACT FROM AUTHOR]

An iterative algorithm is proposed to extract depth profiles based on Fick’s second law of diffusion in a multi-element system from data supplied by angle-resolved X-ray photoelectron spectroscopy (ARXPS). Parameters related to the concentration profiles are obtained by fitting the experimental angle-dependent relative photoelectron intensities to predictions from the algorithm. The use of relative instead of absolute photoelectron intensities eliminates error due to changes in absolute photoelectron intensities resulting from the change of system geometries in angle-resolved experiments. Simulations using an infinite source diffusion model have been conducted to study the influence of errors in the raw data and to demonstrate the robustness of the algorithm. The algorithm is tested based on preliminary experimental ARXPS data from a chemically treated polymer film. [Copyright &y& Elsevier]

The impact of the gate insulator process on interlayer (IL) hole traps in IL/high-K dual-layer p-MOSFET gate-stack is studied by physical and electrical measurements along with atomistic simulations. Processes that lead to higher concentrations of Hf and N in IL, measured by angle-resolved X-ray photoelectron spectroscopy, result in higher IL hole traps measured by flicker noise in prestress and verified by atomistic simulations. The influence of these process induced preexisting IL hole traps on parametric degradation of p-MOSFETs during Negative bias temperature instability (NBTI) stress is studied. The mechanism responsible for superior NBTI of thermal IL stack, having lower Hf and N content in the IL as compared with Chem-Ox IL stack, is explained. [ABSTRACT FROM PUBLISHER]

Abstract: High-density and similarly-sized Si nanodots were formed by annealing ultra-thin amorphous Si (a-Si) films deposited on SiO2/Si substrates in vacuum. Dependences of density and diameter of the Si nanodots on the a-Si film thickness and, annealing temperature and time were investigated by scanning electron microscopy. It is found that drastic increase (decrease) in the density (diameter) occurred at an a-Si thickness of 1 nm. By agglomeration of sub-nanometer thick a-Si films, a density larger than 1012 cm−2, an average diameter smaller than 5 nm, and a dispersion of diameter less than 15% were achieved. [Copyright &y& Elsevier]

For equimolar mixtures of ionic liquids with imidazolium-based cations of very different electronic structure, we observe very pronounced surface enrichment effects by angle-resolved X-ray photoelectron spectroscopy (XPS). For a mixture with the same anion, that is, 1-methyl-3-octylimidazolium hexafluorophosphate+1,3-di(methoxy)imidazolium hexafluorophosphate ([C 8 C 1 Im][PF 6 ]+[(MeO) 2 Im][PF 6 ]), we find a strong enrichment of the octyl chain-containing [C 8 C 1 Im] + cation and a corresponding depletion of the [(MeO) 2 Im] + cation in the topmost layer. For a mixture with different cations and anions, that is, [C 8 C 1 Im][Tf 2 N]+[(MeO) 2 Im][PF 6 ], we find both surface enrichment of the [C 8 C 1 Im] + cation and the [Tf 2 N] - (bis[(trifluoromethyl)sulfonyl]imide) anion, while [(MeO) 2 Im] + and [PF 6 ] - are depleted from the surface. We propose that the observed behavior in these mixtures is due to a lowering of the surface tension by the enriched components. Interestingly, we observe pronounced differences in the chemical shifts of the imidazolium ring signals of the [(MeO) 2 Im] + cations as compared to the non-functionalized cations. Calculations of the electronic structure and the intramolecular partial charge distribution of the cations contribute to interpreting these shifts for the two different cations., (© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)