Loss of Oxygen Atoms on Well-Oxidized Cobalt by Heterogeneous Surface Recombination.

Calorimetry is a commonly used method in plasma characterization, but the accuracy of the method is tied to the accuracy of the recombination coefficient, which in turn depends on a number of surface effects. Surface effects also govern the kinetics in advanced methods such as atomic layer oxidation of inorganic materials and functionalization of organic materials. The flux of the reactive oxygen atoms for the controlled oxidation of such materials depends on the recombination coefficient of materials placed into the reaction chamber, which in turn depends on the surface morphology, temperature, and pressure in the processing chamber. The recombination coefficient of a well-oxidized cobalt surface was studied systematically in a range of temperatures from 300 to 800 K and pressures from 40 to 200 Pa. The coefficient increased monotonously with decreasing pressure and increasing temperature. The lowest value was about 0.05, and the highest was about 0.30. These values were measured for cobalt foils previously oxidized with oxygen plasma at the temperature of 1300 K. The oxidation caused a rich morphology with an average roughness as deduced from atomic force images of 0.9 µm. The results were compared with literature data, and the discrepancy between results reported by different authors was explained by taking into account the peculiarities of their experimental conditions.

AFM Study of Roughness Development during ToF-SIMS Depth Profiling of Multilayers with a Cs+ Ion Beam in a H2 Atmosphere.

The influence of H2 flooding on the development of surface roughness during time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profiling was studied to evaluate the different aspects of a H2 atmosphere in comparison to an ultrahigh vacuum (UHV) environment. Multilayer samples, consisting of different combinations of metal, metal oxide, and alloy layers of different elements, were bombarded with 1 and 2 keV Cs+ ion beams in UHV and a H2 atmosphere of 7 × 10-7 mbar. The surface roughness Sa was measured with atomic force microscopy (AFM) on the initial surface and in the craters formed while sputtering, either in the middle of the layers or at the interfaces. We found that the roughness after Cs+ sputtering depends on the chemical composition/structure of the individual layers, and it increases with the sputtering depth. However, the increase in the roughness was, in specific cases, approximately a few tens of percent lower when sputtering in the H2 atmosphere compared to the UHV. In the other cases, the average surface roughness was generally still lower when H2 flooding was applied, but the differences were statistically insignificant. Additionally, we observed that for the initially rough surfaces with an Sa of about 5 nm, sputtering with the 1 keV Cs+ beam might have a smoothing effect, thereby reducing the initial roughness. Our observations also indicate that Cs+ sputtering with ion energies of 1 and 2 keV has a similar effect on roughness development, except for the cases with initially very smooth samples. The results show the beneficial effect of H2 flooding on surface roughness development during the ToF-SIMS depth profiling in addition to a reduction of the matrix effect and an improved identification of thin layers.

Depth profiling of Cr-ITO dual-layer sample with secondary ion mass spectrometry using MeV ions in the low energy region.

This work explores the possibility of depth profiling of inorganic materials with Megaelectron Volt Secondary Ion Mass Spectrometry using low energy primary ions (LE MeV SIMS), specifically 555 keV Cu2+, while etching the surface with 1 keV Ar+ ions. This is demonstrated on a dual-layer sample consisting of 50 nm Cr layer deposited on 150 nm In2O5Sn (ITO) glass. These materials proved to have sufficient secondary ion yield in previous studies using copper ions with energies of several hundred keV. LE MeV SIMS and keV SIMS depth profiles of Cr-ITO dual-layer are compared and corroborated by atomic force microscopy (AFM) and time-of-flight elastic recoil detection analysis (TOF-ERDA). The results show the potential of LE MeV SIMS depth profiling of inorganic multilayer systems in accelerator facilities equipped with MeV SIMS setup and a fairly simple sputtering source.

ToF-SIMS Depth Profiling of Metal, Metal Oxide, and Alloy Multilayers in Atmospheres of H2, C2H2, CO, and O2.

The influence of the flooding gas during ToF-SIMS depth profiling was studied to reduce the matrix effect and improve the quality of the depth profiles. The profiles were measured on three multilayered samples prepared by PVD. They were composed of metal, metal oxide, and alloy layers. Dual-beam depth profiling was performed with 1 keV Cs+ and 1 keV O2+ sputter beams and analyzed with a Bi+ primary beam. The novelty of this work was the application of H2, C2H2, CO, and O2 atmospheres during SIMS depth profiling. Negative cluster secondary ions, formed from sputtered metals/metal oxides and the flooding gases, were analyzed. A systematic comparison and evaluation of the ToF-SIMS depth profiles were performed regarding the matrix effect, ionization probability, chemical sensitivity, sputtering rate, and depth resolution. We found that depth profiling in the C2H2, CO, and O2 atmospheres has some advantages over UHV depth profiling, but it still lacks some of the information needed for an unambiguous determination of multilayered structures. The ToF-SIMS depth profiles were significantly improved during H2 flooding in terms of matrix-effect reduction. The structures of all the samples were clearly resolved while measuring the intensity of the MnHm-, MnOm-, MnOmH-, and Mn- cluster secondary ions. A further decrease in the matrix effect was obtained by normalization of the measured signals. The use of H2 is proposed for the depth profiling of metal/metal oxide multilayers and alloys.

The Oleofobization of Paper via Plasma Treatment.

Cellulose is a promising biomass material suitable for high volume applications. Its potential lies in sustainability, which is becoming one of the leading trends in industry. However, there are certain drawbacks of cellulose materials which limit their use, especially their high wettability and low barrier properties, which can be overcome by applying thin coatings. Plasma technologies present a high potential for deposition of thin environmentally friendly and recyclable coatings. In this paper, two different plasma reactors were used for coating two types of cellulose-based substrates with hexamethyldisiloxane (HMDSO). The changes in surface characteristics were measured by atomic force microscopy (AFM), scanning electron microscopy (SEM), surface free energy and contact angles measurements, X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectrometry (SIMS). Successful oleofobization was observed for an industrial scale reactor where pure HMDSO was used in the absence of oxygen.

Defluorination of Polytetrafluoroethylene Surface by Hydrogen Plasma.

Defluorination of polytetrafluoroethylene (PTFE) surface film is a suitable technique for tailoring its surface properties. The influence of discharge parameters on the surface chemistry was investigated systematically using radio-frequency inductively coupled H2 plasma sustained in the E- and H-modes at various powers, pressures and treatment times. The surface finish was probed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The measurements of water contact angles (WCA) showed increased wettability of the pristine PTFE; however, they did not reveal remarkable modification in the surface chemistry of the samples treated at various discharge parameters. By contrast, the combination of XPS and ToF-SIMS, however, revealed important differences in the surface chemistry between the E- and H-modes. A well-expressed minimum in the fluorine to carbon ratio F/C as low as 0.2 was observed at the treatment time as short as 1 s when plasma was in the H-mode. More gradual surface chemistry was observed when plasma was in the E-mode, and the minimal achievable F/C ratio was about 0.6. The results were explained by the synergistic effects of hydrogen atoms and vacuum ultraviolet radiation.