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Delayed atomic layer deposition (ALD) of ZnO, i.e., area selective (AS)-ALD, was successfully achieved on silicon wafers (SiSiO2) terminated with tris(dimethylamino)methylsilane (TDMAMS). This resist molecule was deposited in a home-built, near-atmospheric pressure, flow-through, gas-phase reactor. TDMAMS had previously been shown to react with SiSiO2 in a single cycle/reaction and to drastically reduce the number of silanols that remain at the surface. ZnO was deposited in a commercial ALD system using dimethylzinc (DMZ) as the zinc precursor and H2O as the coreactant. Deposition of TDMAMS was confirmed by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and wetting. ALD of ZnO, including its selectivity on TDMAMS-terminated SiSiO2 (SiSiO2TDMAMS), was confirmed by in situ multi-wavelength ellipsometry, ex situ SE, XPS, and/or high-sensitivity/low-energy ion scattering (HS-LEIS). The thermal stability of the TDMAMS resist layer, which is an important parameter for AS-ALD, was investigated by heating SiSiO2TDMAMS in air and nitrogen at 330 °C. ALD of ZnO takes place more readily on SiSiO2TDMAMS heated in the air than in N2, suggesting greater damage to the surface heated in the air. To better understand the in situ ALD of ZnO on SiSiO2TDMAMS and modified (thermally stressed) forms of it, the ellipsometry results were plotted as the normalized growth per cycle. Even one short pulse of TDMAMS effectively passivates SiSiO2. TDMAMS can be a useful, small-molecule inhibitor of ALD of ZnO on SiSiO2 surfaces.

Delayed atomic layer deposition (ALD) of ZnO, i.e., area selective (AS)-ALD, was successfully achieved on silicon wafers (Si/SiO2) terminated with tris(dimethylamino)methylsilane (TDMAMS). This resist molecule was deposited in a home-built, near atmospheric pressure, flow-through , gas-phase reactor. TDMAMS has been shown to react with Si/SiO2 in a single cycle/reaction and to drastically reduce the number of silanols that remain at the surface. ZnO was deposited in a commercial ALD system using dimethylzinc (DMZ) as the zinc precursor and H2O as the coreactant. Deposition of TDMAMS was confirmed by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), and wetting. ALD of ZnO, including its selectivity on TDMAMS – terminated Si/SiO2 (Si/SiO2/TDMAMS), was confirmed by in situ ellipsometry, ex situ SE, XPS, and/or high sensitivity – low energy ion scattering (HS-LEIS). The thermal stability of the TDMAMS resist layer, which is an important parameter for AS-ALD, was investigated by heating Si/SiO2/TDMAMS in air and nitrogen at 330 ºC. ALD of ZnO takes place more readily on Si/SiO2/TDMAMS heated in the air than in N2, suggesting greater damage to the surface heated in the air. To better understand the in situ ALD of ZnO, the data were also plotted as the normalized growth per cycle and to show the selectivity. Even one, short pulse of TDMAMS effectively passivates Si/SiO2. TDMAMS can be an effective small molecule inhibitor of ALD of ZnO on Si/SiO2 surfaces.

Due to significant advances in instrumentation, many previously specialized techniques have become “routine” in user facilities. However, detailed knowledge held by experts has often not been relayed to general users, so they often rely on entry-level information, basic principles, and comparison with literature results for data analysis. As a result, major errors in the data analysis of multiple surface and material analysis techniques, including in x-ray photoelectron spectroscopy (XPS), have been appearing in the scientific literature. Representative examples of serious errors in XPS data analysis are shown in this work. We suggest that surface and material analysis, and perhaps even science in general, are in a state of “pre-crisis.” We use two (logistic) models from population biology to suggest that bad analyses self-correct if they remain below a critical number. However, beyond a threshold, the literature can become useless because of the perpetuation of faulty analyses and concomitant loss of its self-correcting ability. XPS is used by scientists in many communities because of the power of the technique and high-quality instrumentation that is commercially available. Those who make new surfaces and materials face unique challenges because of the large number of surface and material analytical techniques that are often needed to characterize their materials. Graduate students and post-docs are often provided with only minimal instruction on using surface and material characterization methods. High fees for instruments may affect both the quality and the quantity of the data people collect. The Prisoner's Dilemma is a model from game theory that describes situations with reward structures that encourage uncooperative behavior and lead to suboptimal outcomes. However, the outcomes of Prisoner's Dilemma are not inevitable—their consequences change if their reward structures change. The current system does not appear to incentivize detailed learning of surface and material characterization techniques and careful material characterization. Prisoner's dilemmas appear to lead to other undesirable consequences in science. The concerns raised in this work suggest that many manuscripts are incompletely reviewed at present. The different stakeholders in this problem, including authors, research advisers, subject matter experts, reviewers, scientists who notice examples of faulty data analysis, editors, journals and publishers, funding agencies, scientific societies, leaders at universities and research centers, and instrument vendors, can improve the current situation. This work provides specific recommendations for each of these stakeholders. For example, we believe that authors are primarily responsible for the correctness of their work, not reviewers or editors; we question the wisdom of listing the names of the editor and reviewers on a paper; we are grateful for the significant contributions that have been made by subject matter experts to produce standards and tutorial information; the high cost of instrument time at some institutions may limit student access and result in suboptimal analyses; staff scientists often need to be better recognized for their intellectual contributions to studies; publishers may wish to allow selective reviewing of specific sections of papers related to material characterization; the reviewing at some open access journals may be inadequate; while it had its shortcomings, the pre-open access model of publishing incentivized the production and publication of high-quality work; audits of the products (scientific papers) of funding agencies may be necessary; collaboration needs to be encouraged to a greater extent at some institutions; and instrument vendors should not suggest to potential customers that surface characterization, e.g., by XPS, is trivial or simple.

Surface silanols (SiOH) are important moieties on glass surfaces. Here we present a tag-and-count approach for determining surface silanol densities, which consists of tagging surface silanols with Zn via atomic layer deposition (ALD) followed by detection of the zinc by high sensitivity-low energy ion scattering (HS-LEIS). Shards of fused silica were hydroxylated with aqueous hydrofluoric acid (HF) and then heated to 200, 500, 700, or 900 °C. These heat treatments increasingly condense and remove surface silanols. The samples then underwent one ALD cycle with dimethylzinc (DMZ) or diethylzinc (DEZ) followed by water. As expected, fused silica surfaces heated to higher temperatures showed lower Zn coverages. When fused silica surfaces treated at 200 °C were exposed to DMZ for two different dose times, the same sub-monolayer quantity of Zn was obtained by X-ray photoelectron spectroscopy (XPS). Surface cleaning/preparation immediately before HS-LEIS, including atomic oxygen treatment and annealing, played a critical role in these efforts. Surfaces treated with DMZ generally showed slightly higher Zn signals by LEIS. Using this methodology, a value of 4.59 OH/nm2 was found for fully hydroxylated fused silica. Both this result and those obtained at 500, 700, and 900 °C are in very good agreement with literature values.

Low-energy ion scattering (LEIS) probes the atomic composition of the outer surface. Well-defined reference samples are used for the quantitation. For elements like fluorine and calcium, it is not easy to find suitable, clean, and homogeneous references, since fluorine is a gas and calcium is a very reactive metal. In contrast to surface analytic techniques such as XPS, the extreme surface sensitivity of LEIS makes it difficult to use stable compounds like CaF2 as reference, since these compounds are not homogeneous at the atomic scale. With LEIS, CaF2 is not expected to show an atomic ratio F/Ca = 2.0. Thus, before CaF2 can be used as reference, its atomic surface concentrations have to be determined. Here, 3-keV He+ scattering by a LiF(001) single crystal, an evaporated layer of Ca, and a Cu foil are used as basic references. High-purity CaF2 is available in two forms: a single crystal and a powder. For a practical reference, powders are preferred, since if bulk impurities segregate to the surface, they will be dispersed over a large surface area. It is found that both CaF2 (111) and powder have similar F/Ca atomic ratios. This confirms the F termination for both samples. For the powder, the F and Ca signals are reduced by 0.77 ± 0.03 in comparison with those for the single crystal. The atomic sensitivity factors and relative sensitivity factors have been determined for F, Ca, and Cu.

We present self-assembly routes of metamagnetic FeRh nanoisland arrays using sputter deposition processing. Controlling the growth parameters and epitaxy allows tuning the size and shape of the FeRh nanoislands. While the phase transition between antiferromagnetic and ferromagnetic order is largely suppressed in nanoislands formed on oxide substrates via thermodynamic nucleation, we find that metamagnetism is largely preserved in nanomagnet arrays formed through solid-state dewetting. This behavior is strongly dependent on the resulting crystal faceting of the nanoislands, which is characteristic of each assembly route. Comparing the calculated surface energies for each magnetic phase of the nanoislands reveals that metamagnetism can be suppressed or allowed by specific geometrical configurations of the facets. Furthermore, we find that the spatial confinement leads to very pronounced supercooling and the absence of phase separation in the nanoislands. Finally, the supported nanomagnets are chemically etched away from the substrates to inspect the phase transition properties of self-standing nanoparticles. We demonstrate that solid-state dewetting is a feasible and scalable way to obtain supported and free-standing FeRh nanomagnets with preserved metamagnetism., Comment: 28 pages, 7 figures, 1 table

Rapid pressure-less sintering of nanoparticle yttria-stabilized zirconia (YSZ) can result in the formation of a gradient structure characterized by an airtight layer at the surface and interconnected porosity inside the sintered compact. This structure constrains a sample from further shrinkage and limits its final density. In this study, we rapidly sintered green bodies prepared from four commercially available YSZ powder grades, all with a particle size of 60 nm, but with different chemical compositions. We have shown that all powders contained residual chlorine which is responsible for the above mentioned core-shell structure of rapidly sintered samples rather than low thermal conductivity of zirconia. The only sample without this gradient structure was prepared from the powder grade with an increased amount of binder that helped to reduce the chlorine content during binder burnout. The ultimate way for elimination of negative chlorine effect was annealing the sample at 1000 °C prior to rapid sintering.

Low energy ion scattering (LEIS) is an extremely surface sensitive technique that can quantitatively analyze the outermost atomic layer of a material. In LEIS and high sensitivity-low energy ion scattering (HS-LEIS), straightforward quantitation is available using reference and/or standard materials. Here, we present the HS-LEIS spectra of zinc obtained with 3 keV 4He+ and 4 keV 20Ne+ projectile ions. Zinc is an important material with a wide range of applications. Thus, these spectra should be useful standards/references for future applications. A high purity zinc foil was used for these measurements after the removal of the oxide layer. As a reference for the instrumental sensitivity, the spectra for Cu from a high purity foil are also included with this submission. Atomic sensitivity and relative sensitivity factors for Zn and Cu are reported.

The powder of CaF2 has been proposed as a practical reference for the quantitation of Ca and F in low energy ion scattering (LEIS) analysis. It is chemically inert, easy to clean, and inexpensive. LEIS is extremely surface sensitive. Thus, in contrast to surface analytic techniques such as x-ray photoelectron spectroscopy and secondary ion mass spectroscopy, the surface termination of a sample is clearly reflected in the LEIS results. It is, thus, unlikely that in LEIS, the F/Ca ratio for CaF2 is 2.0. This paper supports the reliability of the CaF2 powder reference by evaluating the calcium and fluorine atomic surface concentrations, roughness factor and shows that the surface termination of the powder is the same as that of CaF2(111). The CaF2 samples are treated by annealing at 725 K and measured at 625 K. The presented spectra are practically free of contamination. Ion scattering by LiF (001), an evaporated Ca layer, and a Cu foil are used as basic references for Ca and F. The atomic sensitivity factors and the relative sensitivity factors have been determined for F, Ca, and Cu (3 keV He+, 145 degrees). The F/Ca atomic ratio is found to be the same (2.3 +/- 0.1) for CaF2(111) and its powder. For the powder, the Ca and F signals are reduced by a factor of 0.77 +/- 0.03 in comparison with those for the single crystal.

Iron oxides are among the most abundant compounds on Earth and have consequently been studied and used extensively in industrial processes. Despite these efforts, concrete understanding of some of their surface phase structures has remained elusive, in particular the oxidized ${\alpha}-Fe_2O_3(0001)$ hematite surface. We detail an optimized recipe to produce this phase over the entire hematite surface and study the geometrical parameters and composition of its complex structure by means of atomically resolved microscopy, electron diffraction and surface-sensitive spectroscopies. We conclude that the oxidized ${\alpha}-Fe_2O_3(0001)$ surface is terminated by a two-dimensional iron oxide with structure, lattice parameters, and orientation different from the bulk substrate. Using total-energy density functional theory for simulation of a large-scale atomic model, we identify the structure of the surface layer as antiferromagnetic, conductive $1T-FeO_2$ attached on half-metal terminated bulk. The model succeeds in reproducing the characteristic modulations observed in the atomically resolved images and electron diffraction patterns.

A combination of dynamic secondary ion mass spectroscopy (DSIMS) and time-of-flight low-energy ion scattering (TOF-LEIS) has been applied to acquire a composition depth profile of MoSi multilayers. During the sequential Ar+ sputtering secondary ions were monitored while in-between the sputtering cycles the TOF-LEIS spectra of scattered He neutrals were acquired. All the measured TOF-LEIS spectra versus sputtering time were displayed in one bitmap from which the depth profiles for different scattering depths were derived and analyzed. Analyzing the TOF-LEIS spectra of He particles scattered from the areas below the layer altered by ion-beam mixing led to an improvement of the depth resolution. In this way the resolution limits due to mixing phenomena can be overcome. Finally, the direct comparison of the DSIMS and TOF-LEIS depth profiles was carried out.

A classical dynamics simulation of the low energy He+ ion scattering on a Cu(100) surface was carried out for a more detailed explanation of LEIS azimuthal scans with respect to a previous work. The Thomas-Fermi–Moliere screened potential was used in the calculations to describe interatomic repulsive interactions. A stopping power and thermal vibrations of target atoms were involved as well. The results of the simulations were compared with the experiment and thus the correction factors of interatomic scans found. The main features of the calculated azimuthal scans N(Φ) are discussed and the relevant parts compared. Additionally, ion blocking effects were studied by the analysis of N Φ , β distribution of ions backscattered into the whole half-space above the Cu(100) surface. This gave us a more transparent view into the low energy ion scattering processes on this periodic surface.

Angle-resolved XPS depth profiling is a useful method in surface and ultrathin film research. However, it is useful to test various modeled structures in order to get information on its ability to recognize individual sublayers and to find its resolution limits. In this paper, a model consisting of ultrathin films with sharp interfaces has been proposed and the relative intensities of XPS lines as a function of the detection angle calculated. In addition, this method has been improved by the incorporation of an attenuation of the photoelectron signal already in the layer of its origin. Using the signal obtained from the simulation of electron spectra for surface-analysis-based simulations as an experimental one, genetic algorithms have been used for reproducing the profiles, especially for finding its first estimates. In this way, it was possible to find the pros and cons of the angle-resolved XPS method in the depth profiling of Co, C and SiO2 ultrathin layers on Si substrates. Copyright © 2010 John Wiley & Sons, Ltd.

Low energy ion scattering (LEIS) is used to characterize Ga layers deposited onto Si(1 1 1)-(7 × 7) substrates at different deposition temperatures. The Ga/Si system exhibits a pronounced 3D island growth and thus is a suitable object to investigate the relation between LEIS-peak shapes and the morphology of thin films. It is shown that up to a certain critical depth (a few MLs) the single scattering component can be used as a measure of the number of surface Ga atoms per unit area. If a higher amount of Ga is deposited, the single scattering model is not valid anymore and multiple scattering becomes significant. The Ga peak starts to be asymmetric with a well developed multiple scattering component. Such a component can be utilized for the observation of the morphology of the layers. It was found that the more intensive the 3D growth of adsorbed Ga atoms on the Si(1 1 1) substrate, the more pronounced is the multiple scattering yield for a given amount of Ga.

In the paper the design and application of a time-of-∞ight low energy ion scattering instrument built into an UHV complex deposition and analytical apparatus is described. A special attention is aimed at demonstrating the ability of time-of-∞ight low energy ion scattering to analyse near-to-surface layers of thin fllms prepared both ex situ and in situ. It is shown that the broadening of peaks in time-of-∞ight low energy ion scattering spectra can be attributed to multiple scattering and inelastic losses of ions in deeper layers. As a result of that, the peak width of ultrathin fllms depends on their thickness.

Low-energy ion scattering (LEIS) is known for its extreme surface sensitivity, as it yields a quantitative analysis of the outermost surface as well as highly resolved in-depth information for ultrathin surface layers. Hence, it could have been generally considered to be a suitable technique for the analysis of graphene samples. However, due to the low scattering cross section for light elements such as carbon, LEIS has not become a common technique for the characterization of graphene. In the present study we use a high-sensitivity LEIS instrument with parallel energy analysis for the characterization of CVD graphene transferred to thermal silica/silicon substrates. Thanks to its high sensitivity and the exceptional depth resolution typical of LEIS, the graphene layer closure was verified, and different kinds of contaminants were detected, quantified, and localized within the graphene structure. Utilizing the extraordinarily strong neutralization of helium by carbon atoms in graphene, LEIS experiments performed at several primary ion energies permit us to distinguish carbon in graphene from that in nongraphitic forms (e.g., the remains of a resist). Furthermore, metal impurities such as Fe, Sn, and Na located at the graphene-silica interface (intercalated) are detected, and the coverages of Fe and Sn are determined. Hence, high-resolution LEIS is capable of both checking the purity of graphene surfaces and detecting impurities incorporated into graphene layers or their interfaces. Thus, it is a suitable method for monitoring the quality of the whole fabrication process of graphene, including its transfer on various substrates.

In the paper the ability of TOF-LEIS to monitor the growth of ultrathin Ga layers in situ is presented. The FWHM of the Ga peaks in the TOF-LEIS spectra showed a linear dependence on Ga coverage. The analysis of the Ga growth on two Si(1 1 1) substrates cleaned in two distinct ways (chemical etching and UHV thermal flashing) revealed changes in the Si peak evolution caused by different growth modes taking place on these two substrates. This has been proved by ex situ AFM measurements as well.

Low energy ion scattering (LEIS) is a well known technique for quantitative composition and structure analysis. Two different detection methods can be used in a LEIS experiment, i.e. an electrostatic analyzer or a time-of-flight (TOF) spectrometer. Both techniques have specific advantages. Nevertheless, the time-of-flight technique surpasses usual electrostatic analyzers used in LEIS in terms of energy resolution. The possibility to measure ions and neutrals, and the better energy resolution permit to study neutralization or charge exchange processes in much more detail. Here we present a TOF–LEIS setup with an energy resolution of better than 0.4% for 3 keV He ions and report experimental results for 3 keV He ions backscattered from a polycrystalline Cu target. The resulting ion spectrum shows interesting inherent features, which are analyzed. Possible causes for the appearance of these features are discussed.

In the paper the application of a complex UHV apparatus for in-situ investigation of low-temperature Ga–N ultra-thin film synthesis by thermal Ga atoms and hyperthermal nitrogen ions is presented. It was found by XPS that the highest content of GaN bonds was present in the layers grown on a ‘nitrogen-rich’ substrate at enhanced substrate temperature (400 °C). ‘Nitrogen-rich’ Si surfaces grew from hyperthermal nitrogen ions on substrates contaminated by oxygen (‘native’ and chemically etched Si). The ‘gallium-rich’ substrate possessed smaller number of GaN bonds. Higher content of GaO bonds was found on Si substrates covered by native oxide and chemically etched silicon. Due to low nitrogen ion currents the thickness of the films was small (

A six-lens-entrance ion optics and its retractable vacuum housing for ion beam analytical instrument was designed. Based on an electrostatic energy analyser and mass spectrometer the instrument will allow us to carry out in situ monitoring of ion beam deposition (IBD) processes and relevant technologies via SIMS, low energy ion scattering (LEIS) and energy analysis of charge-exchange ions. To optimize the entrance optics, the computer code SIMION 4.0 was used.

Cobalt-cemented hard metals present an example of samples with a complicated matrix consisting of components differing in chemical and physical properties and with extremely low volatility of all components. The purpose of this study was to compare particle formation of a set of real samples with similar matrices but different content of major components. The laser ablation process was studied using a Q-switched quintupled (213 nm) nanosecond Nd:YAG laser. Five samples of Co-cemented tungsten carbides, actually WC-TiC-(Ta,Nb)C-Co with a varied content of main constituents, were selected as representatives of a family of 15 miscellaneous tungsten carbide hard metal products. Physical and chemical properties vary over this specimen selection and therefore the effect on particle size formation and distribution was expected. The size distributions by number of ablated particles in different size ranges were measured using an optical aerosol spectrometer. The results proved the relationship between particle formation and sample composition. The structure of laser generated particles and the properties of ablation-craters were additionally studied by scanning electron microscopy (SEM). Spherical particles in the diameter range of 0.25–2 μm and μm-sized agglomerates composed of primary nano-particles were observed. The W and Co content in the aerosol particles was determined by energy dispersive X-ray spectroscopy (EDS). The volumes of ablation craters were measured by an optical profilometer. The laser ablation study of selected Co-cemented tungsten carbide hard metals indicates a similar total volume of formed particles with composition-dependent particle-size distributions.