Critical distance for secondary ion formation: Experimental SIMS measurements

We have performed direct experimental measurements of the critical distance for the secondary ion formation process. To this end, we compared the experimentally measured energy distribution of secondary Si⁻ ions with the theoretical energy distribution (Sigmund-Thompson relation) of secondary Si atoms. Our model states that the maxima positions of these two energy distributions differ by the Coulomb interaction potential between the outgoing ion (Si⁻ in our case) and a charge with the opposite polarity formed at the surface after electron transition between the outgoing Si atom and the surface. Quite a reasonable value was obtained for the critical distance, but with a large scatter in experimental data. The conclusion has been made that the experimental technique should be improved to get more precise values of the critical distance, which is of high importance for practical purposes.     

Effect of primary oxygen ion implantation on SIMS depth profiling in glasses

The influence of the primary oxygen ion implantation on SIMS in-depth profiles in halide and chalcogenide glasses was examined. Various behaviours of particular profiles were generally explained in terms of the chemical affinity of analysed reactants and modifications of the glass structure induced by primary ions.     

Measurement and modeling of work function changes during low energy cesium sputtering

In this paper, a H-terminated silicon wafer was bombarded by low energy cesium ions during ToF-SIMS analysis and work function variations of the target were measured for different analysis conditions. This measurement was performed by measuring the shift of the secondary ions energy distributions with a reflectron type analyzer. At first, the silicon’s work function change was found to be −2.3 eV during 500 eV Cs⁺ bombardment at 45°. This effect is due to the creation of a dipolar layer at the surface of the silicon by the implanted cesium. Then the work function variation was measured at 300 eV for varying cesium surface concentrations. The work function was found to decrease monotonously with the increasing cesium surface concentration, as during cesium adsorption experiments. The results were modeled following three different approaches and the value of the effective polarizability α of cesium was found to be equal to 1.9 × 10⁻³⁹ C m²/V. Finally, the effect of the bombardment energy on the work function variation was studied for beams with energies ranging from 250 to 2000 eV. The effective polarizability of cesium was found to increase with increasing Cs beam energy.     

The effect of carbon contamination and argon ion sputtering on the work function of chlorinated indium tin oxide

The work function of indium tin oxide (ITO) was increased by treating ITO with dichlorobenzene with UV light. Carbon contamination of the Cl-ITO was measured using X-ray Photoelectron Spectroscopy (XPS) and argon ion sputtering was used to remove the carbon from the surface. It was found that the carbon contamination from residual dichlorobenzene significantly lowered the work function of the ITO and after argon ion sputtering the work function increased to 5.8 eV. It was found that chlorination of ITO occurs after more than 6 min of UV exposure. Further sputtering of ITO resulted in the removal of the functionalized chlorine, the introduction of argon ion contaminants on the ITO decreases its work function.     

SIMS analysis of residual gas elements with a Cameca IMS-6f ion microprobe

In this paper, we present experimental data for SIMS analysis of residual gas elements (RGEs) with a Cameca IMS-6f ion microprobe. We considered a simple experimental technique, which provides an effective separation of the secondary ions, sputtered from the bulk of a target, and from the molecules, adsorbed on the analyzed surface from the residual atmosphere. The technique needs the sputtering yield of one monolayer (ML) per second to be applied. The method improves (in more than one order of magnitude) the detection limit for RGEs in SIMS analysis, and simultaneously, provides information about the residual atmosphere at the sample surface and in the main chamber of the experimental instrument. The method provides a calibration method for an ion gauge, and can be used for SIMS analysis with a gas (O₂) flooding.     

Formulation for XPS spectral change of oxides by ion bombardment as a function of sputtering time

XPS measurement revealed that the original state of TiO₂ was changed to Ti₂O₃ and TiO by ion bombardment. TiO₂ decreased and Ti₂O₃ increased at the initial stage. TiO increased at a later stage than Ti₂O₃. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO₂ to Ti₂O₃ and from Ti₂O₃ to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO₂ to Ti₂O₃ is about ten times larger than that from Ti₂O₃ to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment.     

Optical characterization and laser damage of fused silica optics after ion beam sputtering

The sputtering process of fused silica bombarded by Ar ion beam is simulated with the SRIM software. The effects of ion beam energy and incident angle on sputtering yield and surface damage are computed. Since ion beam sputtering will result in defects in fused silica, such as E′ color centers and other lattice defects and probably Argon bubbles, the optimized sputtering energy is selected below 1 keV so that the projected range of Ar ions is less than 10 Å. The experimental results show that the scratches in subsurface of fused silica can be smoothed obviously and better surface can be obtained as the optimized parameters are used for ion beam sputtering. The laser induced damage threshold of fused silica increases by about 18% after ion beam sputtering.     

Variations of work function and corrosion behaviors of deformed copper surfaces

Surface work function (WF) and the corrosion behavior of copper under influence of plastic strain were investigated using experimental and computational approaches. It was observed that both the corrosion potential (Ecorr) and the WF decreased while the corrosion rate increased with an increase in plastic strain, indicating that the strained surface layer became more electrochemically active. Ecorr and WF eventually became stable when the plastic strain reached a certain level. However, the corrosion rate continuously increased. It was demonstrated that this continuous increase in corrosion rate could be dominated by the dislocation density rather than the corrosion potential. The study has shown that the WF is closely related to the corrosion potential and could thus be a sensitive parameter for investigating mechanisms responsible for corrosive wear. The investigation of the effects of plastic deformation on the corrosion behavior would help to fundamentally understand the synergism of wear and corrosion.     

Dynamics of water adsorption on TiO2 monitored by work function spectroscopy

Water adsorption dynamics on two TiO₂ (1 1 0) rutile surfaces at room temperature has been investigated using the work function (WF) change as a function of time. The first surface was prepared in a standard way using sputtering/annealing cycles, whereas the second one was long term annealed at 620 K in moderate vacuum conditions (the residual gas pressure of about 1 × 10⁻⁷ mbar) and cleaned afterwards. The WF change show striking difference as compared to those obtained for highly reduced TiO₂ (1 1 0) rutile or the (2 × 1) reconstructed surfaces. For the first kind of surface we show that the observed adsorption dynamics can be qualitatively explained by the present understanding of the water adsorption on non-reconstructed TiO₂ (1 1 0) rutile surface according to which the bridging oxygen vacancies and Ti rows are the main adsorption sites. Although generally similar to the former results, water adsorption dynamics on the second kind of the surface has an additional feature that can be only explained by a new adsorption site, which we suggest to be due to (2 × 1) reconstructed regions coexisting with the non-reconstructed TiO₂ (1 1 0) surface.     

Characterization of drug-eluting stent (DES) materials with cluster secondary ion mass spectrometry (SIMS)

Secondary ion mass spectrometry (SIMS) employing an SF₅⁺ polyatomic primary ion source was utilized to analyze several materials commonly used in drug-eluting stents (DES). Poly(ethylene-co-vinyl acetate) (PEVA), poly(lactic-co-glycolic acid) (PLGA) and various poly(urethanes) were successfully depth profiled using SF₅⁺ bombardment. The resultant molecular depth profiles obtained from these polymeric films showed very little degradation in molecular signal as a function of increasing SF₅⁺ primary ion dose when experiments were performed at low temperatures (signal was maintained for doses up to ∼5 × 10¹⁵ ions/cm²). Temperature was determined to be an important parameter in both the success of the depth profiles and the mass spectral analysis of the polymers. In addition to the pristine polymer films, paclitaxel (drug released in Taxus™ stent) containing PLGA films were also characterized, where it was confirmed that both drug and polymer signals could be monitored as a function of depth at lower paclitaxel concentrations (10 wt%).     

Self-assembly growth and electron work function of copper phthalocyanine films on indium tin oxide glass

Organic semiconductor materials are becoming a promising subject of not only scientific interest but also potential applications in the field of new energy resources. In this study, the copper phthalocyanine (CuPc) films as an excellent organic semiconductor were self-assembly grown on indium tin oxide glass by electrodeposition, the structural and electronic properties were investigated using various techniques. The results demonstrated that ordered α-form crystalline CuPc films were obtained. The decrease of electron work function of CuPc films with the increase of film thickness was found, which was obviously dependent on the surface morphology. The understanding of these behaviors of CuPc films will be significant for designing related photoelectric devices.     

Quantitative study of oxygen enhancement of sputtered ion yields. I. Argon ion bombardment of a silicon surface with O2 flood

A novel quantification approach is applied to determine in situ the amount of surface oxygen within the sputtered particle escape depth during steady-state sputter depth profiling of silicon under simultaneous oxygenation with an oxygen flood gas or with an oxygen primary ion beam. Quantification is achieved by comparing the secondary ion intensities of ¹⁶O that is adsorbed or implanted at the Si surface with the measured peak intensities of a calibrated ¹⁸O ion implant used as a reference standard. Sputtered ion yields can thereby be related to surface oxygen levels. In the present work the dependences of the partial silicon sputter yield Y and of the positive and negative secondary ion useful yields UY(X^±) (X = B, O, Al, Si, P) on the oxygen/silicon ratio, O/Si, in the sputtered flux are studied for ⁴⁰Ar⁺ bombardment of Si with simultaneous O₂ flooding. The silicon sputter yield is found to decrease with increasing flood pressure and O/Si ratio by up to a factor of 3. Both positive and negative secondary ion yields are enhanced by the presence of oxygen at the silicon surface. The useful ion yield of Si⁺ scales non-linearly with the atom fraction of surface oxygen; this behavior is shown to invalidate models that suggest that Si⁺ ion yield enhancement is dominated either by isolated oxygen atoms or by formation of SiO₂ precipitates. In contrast a microscopic statistical model that assumes that local Si⁺ ion formation depends only on the number of oxygen atoms coordinated to the Si atom to be ejected fits the ion yield data quantitatively.     

Work function, valence band and secondary ion intensity variations noted during the initial stages of SIMS depth profiling of Si and SiO2 by Cs

Work function, valence band and ²⁸Si⁻ secondary ion intensity variations from various Si substrates sputtered by 1 keV Cs⁺ at 60° were measured. Oxide free Si wafers and native oxide terminated wafers did not reveal any appreciable valence band variations close to the Fermi edge. Their work functions however, decreased substantially with an exponential trend noted between this and Si⁻ secondary ion intensities from the O free Si wafer. This is consistent with the electron tunneling model which assumes a resonance charge transfer process. Native oxide terminated wafers exhibited deviations from this exponential trend, while Si wafers with thicker oxides revealed the growth of sub-band features in the valence band spectra on sputtering with Cs⁺. These features, may partially, if not fully, explain the Cs⁺ induced enhancement effect noted on SiO₂ substrates where work function based models are not applicable.     

Dependence of electron work function of Al-Mg alloys on surface structures and relative humidity

In many fields the determination of electronic structures of a solid material is a prerequisite in order to investigate its physical/chemical properties as well as related applications. The effect of surface structures and ambient environment on the electronic behavior is of both fundamental and practical significance. In this study, the electron work function (EWF) of Al-Mg alloys is investigated using a scanning Kelvin probe. The results show that the EWF decreases with the increase of surface smoothness, whereas surface oxidation layers would result in the increase of the EWF. Furthermore EWF is strongly dependent on the relative humidity, especially when the relative humidity is higher than 70%, implying that considerable care should be takenon such dependence in order to gain a meaningful parameter for the characterization of surface behavior.     

Molecular level alignment and work function change of dimethyl-disulfide physisorbed thin films on Au(1 1 1)

The formation and the electronic properties of a dimethyl-disulfide (DMDS) thin film adsorbed at low temperature on the Au(1 1 1) surface has been studied by means of Ultraviolet Photoemission Spectroscopy. The dependence of the binding energy of the molecular states as a function of coverage has been analyzed and compared to the corresponding work function change. A deviation from the expected rule for the molecular level alignment is observed and attributed to the differences between local and average work function. The effect of a buffer thiolated monolayer, obtained by dosing DMDS at room temperature, on the evolution of the interface electronic properties is also analyzed and discussed.     

Comparison of implantation and diffusion behavior of Ti, Sb and N in ion-implanted single crystal and polycrystalline ZnO: A SIMS study

Implantation and diffusion behavior of Sb, Ti and N in ZnO single crystal and sputter deposited thin films were studied through secondary ion mass spectrometric studies on ion-implanted and thermally annealed samples. Sb was implanted and Ti and N were co-implanted into ZnO single crystals and polycrystalline thin films on Si substrates at room temperature. The implanted samples were then annealed at 800 °C. Depth profiles of implant distributions before and after annealing were examined by Secondary Ion Mass Spectrometry (SIMS). As expected, implant range is sensitive to the mass of the dopants; and the dopant distribution is broadened as implanted elements migrate deeper into the film on thermal annealing. While diffusion of N in the ZnO thin film is not significant, Ti tends to diffuse deeper into the sample during annealing. For Ti and N co-implanted single crystal, annealing induced diffusion causes more redistribution of the lighter N than Ti. In general, implanted dopants diffuse more easily in thin films compared to the single crystal due to the presence of grain boundaries in the latter.     

Effects of electron beam irradiation on the friction and work function of the wrinkled graphene

The ability to control the tribological and electrical properties of graphene is critical to the fabrication of micro- and nanoelectromechanical systems (MEMS/NEMS) devices. Due to its high energy, electron beam irradiation has been widely used to adjust the local electrical properties of the graphene, such as inducing local defects or n-type doping. However, whether electron beam irradiation can affect the local tribological properties of wrinkled graphene has not been investigated yet. In this research, we demonstrated that the lateral force signal and the work function of the wrinkled monolayer graphene were affected by the electron beam irradiation.By using Kelvin-probe force microscopy (KPFM) and Raman spectroscopy, we measured the local electrical properties of the wrinkled monolayer graphene and confirmed that the electron-beam exposed area was changed as n-doped graphene. We compared the lateral force signal with surface potential data and concluded that the n-type doping induced by electron beam affected the tribological characteristics. Characterization of the electron-beam exposed wrinkled graphene provides a physical insight that the electrical and tribological characteristics of wrinkled graphene are correlated.     

The work function reduction of the Pt field emitter

We have carried out the field emission experiments to measure the temperature dependence of the work function of Pt field emitter and found that the work function steeply decreases more than 2 eV by annealing at relatively low temperature above about 500 K in ultra high vacuum. The maximum reduction of the work function was 2.59 eV. The reduced work function was restored the original value of Pt clean surface by applying high voltage of only 20% of Pt evaporation field. The experimental results are tentatively interpreted in terms of the formation of complex cyanides on the emitter shank during the electrochemical etching in KCN solution and the surface diffusion of potassium atoms formed by the thermal decomposition of the complex cyanides to the emitter cap.     

Surface work function of chemically derived graphene: A first-principles study

Using first-principles calculations within the framework of density-functional theory, we systematically study the modulation effect of chemical decoration including hydrogenation, fluorination, and oxidization on the surface work function of graphene. The chemical decoration is effective approach to modulate the surface work function, which expands the space to design diverse nano-devices based on graphene. Moreover, we also find some un-expectation chemically decorated cases which do not follow the traditional rule of “electronegative (electropositive) adsorbates, which increase (decrease) the work function of the surface”. Such a phenomenon is mainly derived from the charge redistribution induced by the bonding process between adsorbates and carbon atoms along with the chemical decoration.