Temporal evolution on SiO2 surface under low energy Ar+-ion bombardment: roles of sputtering, mass redistribution, and shadowing.

Self-organized pattern evolution on SiO2 surface under low energy Ar-ion irradiation has been investigated extensively at varied ion energies, angles of ion incidence, and ion flux. Our investigations reveal an instability on SiO2 surface in an angular window of 40° ̶ 70° and for a comprehensive range of Ar-ion energies (200-1000 eV). Different topographical features, viz. ripples, mounds, and elongated nanostructures evolve on the surface, depending upon the angle of incidence and ion fluence. The results are compiled in the form of a parametric phase diagram (ion energy versus angle of incidence) which summarizes the pattern formation on SiO2 surface. To understand the evolution of observed patterns, we have carried out theoretical estimation, taking into account the synergetic roles of ion induced curvature-dependent sputter erosion and prompt atomic redistribution. It is shown that irradiation-induced mass redistribution of target atoms plays a crucial role in determining the critical angle of ion incidence for pattern formation on SiO2 under the present experimental conditions, whereas the contribution of curvature-dependent sputtering needs to be considered to understand the existence of the angular window of pattern formation. In addition, ion-beam shadowing by surface features are shown to play a dominant role in the formation of mounds and elongated structures at higher ion fluences.

Ion-beam modification of 2-D materials - single implant atom analysis via annular dark-field electron microscopy.

Functionalisation of two-dimensional (2-D) materials via low energy ion implantation could open possibilities for fabrication of devices based on such materials. Nanoscale patterning and/or electronically doping can thus be achieved, compatible with large scale integrated semiconductor technologies. Using atomic resolution High Angle Annular Dark Field (HAADF) scanning transmission electron microscopy supported by image simulation, we show that sites and chemical nature of individual implants/ dopants in graphene, as well as impurities in hBN, can uniquely and directly be identified on grounds of their position and their image intensity in accordance with predictions from Z-contrast theories. Dopants in graphene (e.g., N) are predominantly substitutional. In other 2-Ds, e.g. dichalcogenides, the situation is more complicated since implants can be embedded in different layers and substitute for different elements. Possible configurations of Se-implants in MoS2 are discussed and image contrast calculations performed. Implants substituting for S in the top or bottom layer can undoubtedly be identified. We show, for the first time, using HAADF contrast measurement that successful Se-integration into MoS2 can be achieved via ion implantation, and we demonstrate the possibility of HAADF image contrast measurements for identifying impurities and dopants introduced into in 2-Ds.

Determination of gradient elastic tensors: stress and strain dependencies of electric field gradients in cubic and hexagonal systems.

We present ab-initio calculations of the independent components of gradient elastic tensors, so-called gradient elastic constants, which relate electric field gradient tensors to stress or strain tensors. The constants of cubic and hexagonal metals, MAX phases, and zinc oxide were determined within the framework of density functional theory by using the augmented plane waves plus local orbitals method implemented in the WIEN2k code. Comparison with experimental gradient elastic constants and electric field gradients' stress dependencies suggest an accuracy of about 30% of the calculated constants, independent of the probe that detects the field gradient being self- or foreign-atom. Changes in the electric field gradient take place by strain-induced asymmetric occupations of the p and d states in the valence region for all investigated materials. Volume and structural dependencies of the electric field gradient can directly be determined from this fundamental approach and are, for hexagonal closed packed metals, consistent with vanishing electric field gradients around ideal close packing and volume dependencies larger than one. The concept of these calculations is applicable in any hyperfine interaction method and, thus, can be used to gain information about intrinsic strains in systems where the experimental gradient elastic constants are inaccessible.

Stopping power of liquid water for carbon ions in the energy range between 1 MeV and 6 MeV.

The stopping power of liquid water was measured for the first time for carbon ions in the energy range between 1 and 6 MeV using the inverted Doppler shift attenuation method. The feasibility study carried out within the scope of the present work shows that this method is well suited for the quantification of the controversial condensed phased effect in the stopping power for heavy ions in the intermediate energy range. The preliminary results of this work indicate that the stopping power of water for carbon ions with energies prevailing in the Bragg-peak region is significantly lower than that of water vapor. In view of the relatively high uncertainty of the present results, a new experiment with uncertainties less than the predicted difference between the stopping powers of both water phases is planned.

Perturbed angular correlation studies of uniaxial compressive stressed zinc, titanium, rutile, Ti2AlN, and Nb2AlC.

We use the perturbed angular correlation method with (111)In-(111)Cd probe atoms to in situ study the changes in the electric field gradient at room temperature of polycrystalline Ti(2)AlN and Nb(2)AlC, titanium and zinc, and rutile samples, as a function of cyclic uniaxial compressive loads. The load dependence of the quadrupole coupling constant νQ was found to be large in titanium and zinc but small in Ti(2)AlN, Nb(2)AlC and rutile. Reversible and irreversible increases in the electric field gradient distribution widths were found under load and after releasing the load, respectively. Annihilation of dislocations, as well as elastic deformation, are considered to contribute to the reversible behavior. The irreversible response must be caused by a permanent increase in dislocation and point defect densities. The deformation induced broadening of the electric field gradient can be recovered by post-annealing of the deformed sample.

Designing self-organized nanopatterns on Si by ion irradiation and metal co-deposition.

Dot and ripple nanopatterns on Si surfaces with defined symmetry and characteristic dot spacings of 50-70 nm were created by 1 keV Ar ion irradiation at normal incidence and simultaneous co-deposition of Fe atoms at grazing incidence. Fe was continuously supplied from different sputter targets surrounding the Si substrate, leading to a steady-state Fe content in the near-surface region of the substrates. The pattern formation is self-organized, most probably caused by ion-induced phase separation. Patterns were analyzed with atomic force microscopy and the Fe content in the irradiated layer was measured with Rutherford backscattering. The symmetries of the produced patterns are isotropic, four-fold symmetric, three-fold symmetric and various types of two-fold symmetric patterns, depending on the geometrical arrangement of the sputter targets. Pattern formation was studied for a steady-state coverage of Fe between 0.5 and 3.3 × 10(15) Fe cm(-2). The threshold coverage for the onset of pattern formation is about 0.5-1 × 10(15) Fe cm(-2). The coherence length of the patterns is comparable to the average dot spacing. Nevertheless, the autocorrelation analysis reveals a residual long-range periodicity of some patterns. The dot spacing can be adjusted between about 20 nm and several hundred nm depending on the ion species and ion energy.

Ion implantation of graphene-toward IC compatible technologies.

Doping of graphene via low energy ion implantation could open possibilities for fabrication of nanometer-scale patterned graphene-based devices as well as for graphene functionalization compatible with large-scale integrated semiconductor technology. Using advanced electron microscopy/spectroscopy methods, we show for the first time directly that graphene can be doped with B and N via ion implantation and that the retention is in good agreement with predictions from calculation-based literature values. Atomic resolution high-angle dark field imaging (HAADF) combined with single-atom electron energy loss (EEL) spectroscopy reveals that for sufficiently low implantation energies ions are predominantly substitutionally incorporated into the graphene lattice with a very small fraction residing in defect-related sites.

Electric field gradients at (111)In/(111)Cd probe atoms on A-sites in 211-MAX phases.

The method of perturbed angular correlation (PAC) was applied to selected MAX phases with 211 stoichiometry. Radioactive (111)In ions were implanted in order to measure the electric field gradients (EFG) in the key compounds Ti(2)InC and Zr(2)InC to determine the strength and symmetry of the EFG at the In-site. Further PAC studies in the In-free MAX phases Ti(2)AlN, Nb(2)AlC, Nb(2)AsC and Cr(2)GeC were performed to confirm that the In probes occupy the A-site as well. The strength of the EFG, with a quadrupole coupling constant ν(Q) between 250 and 300 MHz in these phases, is quite similar to the ones found in Ti(2)InC with ν(Q) = 292(1) MHz and in Zr(2)InC with ν(Q) = 344(1) MHz, respectively. Different annealing behavior was observed whereas in all cases a linear decrease of ν(Q) with increasing measuring temperatures was found. The experimental results are also in excellent agreement with those predicted by ab initio calculations using the APW+lo method implemented in the WIEN2k code. This study shows in an exceptional manner that (111)In → (111)Cd atoms are suitable probes to investigate the local surrounding at the A-site in 211-MAX phases.

Comparison of high pressure liquid chromatographic and chemical methods for vitamin D3 concentrates. II. Collaborative study.

A collaborative study was carried out which compared the official chemical method, 43.B14-43.B24, the official rat bioassay, 43.165, and the high pressure liquid chromatographic method for vitamin D3 resin, vitamin D3 resin in oil, and dry concentrate. A total of 340 samples were distributed to 17 collaborators for analysis. Five laboratories performed both the chemical and HPLC methods on 5 sets of blind duplicates. A 2-way analysis of variance comparing both methods for each sample showed a significant (P less than 0.01) difference between methods only for Sample 5. When the 2 methods were compared over all the samples, no significant (P less than 0.05) difference was found. Except for Sample 5, there were no differences in the repeatability of the methods. Per cent recoveries on Sample 3, which contained exactly 0.200 X 10(6) IU/g, showed 98.2% for the chemical method and 100.6% for the HPLC method for the 5 laboratories that performed both methods. The assay results of the HPLC and chemical methods are in good agreement with those found by the biological assay on Samples 1-4, but not for Sample 5. Evidence indicates that Sample 5 degraded partially to isotachysterol, and while the HPLC method yielded a reasonable value on this material, the chemical method erroneously showed full potency. An amendment is included for the collaboratively studied HPLC method which detects and eliminates 5,6-trans-vitamin D3, a possible interferant.

High-pressure liquid chromatographic determination of vitamin D3 in resins, oils, dry concentrates, and dry concentrates containing vitamin A.

A high-pressur liquid chromatographic (HPLC) procedure has been developed for the determination of vitamin D3 in resins, oils, dry concentrates, and dry concentrates containing vitamin A. Specificity of the method for vitamin D3 in the presence of isomers and other related constituents was shown by ultimate recovery of the vitamin D3 and the individual constituents and their characterization by other methods such as ultraviolet spectrophotometry. Precision and accuracy are within 2%, and as many as 20 determinations may be completed in a working day. Excellent agreement with the official AOAC biological assay was found. A comparison of the response of isomers of vitamin D3 by the HPLC method vs. other instrumental and chemical procedures shows HPLC to be the most specific method for determining the bioactive isomers.