Characterizing SIMS transient effects apparent in matrix secondary ion signals from silicon under 1 keV Cs impact

The low energy Si₂⁻, Si₃⁻ and Si₄⁻ secondary ion signals resulting from Cs⁺ impact on Si appear to scale with the Cs uptake noted over the SIMS transient region in a manner consistent with the electron tunneling model. These populations, particularly Si₃⁻ and Si₄⁻ also exhibit a relative insensitivity to the presence of O (shown once sputter rate variations are accounted for). Profiles that more closely match the expected Si concentration gradient from a native oxide terminated Si wafer present within the SIMS transient region can also be obtained by simply dividing the Si₃⁻ or Si₄⁻ secondary ion intensities by the Si₂⁻ intensities. This suggests a possible alternative route for reducing transient effects present in the negative secondary ion populations from Si wafers.     

Properties of the SiO2/SiC interface investigated by angle resolved studies of the Si 2p and Si 1s levels and the Si KLL Auger transitions

Angle resolved photoemission studies of the Si 2p and Si 1s core levels and the Si KL_2,3L_2,3 Auger transitions from SiO₂/SiC samples are reported. Most samples investigated were grown in situ on initially clean and well ordered √3×√3 reconstructed 4H-SiC(0 0 0 1) surfaces but some samples were grown ex situ using a standard dry oxidation procedure. The results presented cover samples with total oxide thicknesses from about 5 to 118 Å. The angle resolved data show that two oxidation states only, Si⁺¹ and Si⁺⁴, are required to explain and model recorded Si 2p, Si 1s and Si KLL spectra.The intensity variations observed in the core level components versus electron emission angle are found to be well described by a layer attenuation model for all samples when assuming a sub-oxide (Si₂O) at the interface with a thickness ranging from 2.5 to 4 Å. We conclude that the sub-oxide is located at the interface and that the thickness of this layer does not increase much when the total oxide thickness is increased from about 5 to 118 Å.The SiO₂ chemical shift is found to be larger in the Si 1s level than in the Si 2p level and to depend on the thickness of the oxide layer. The SiO₂ shift is found to be fairly constant for oxides less than about 10 Å thick, to increase by 0.5 eV when increasing the oxide thickness to around 25 Å and then to be fairly constant for thicker oxides. An even more pronounced dependence is observed in the Si KLL transitions where a relative energy shift of 0.9 eV is determined.The relative final state relaxation energy ΔR(2p) is determined from the modified Auger parameter. This yields a value of ΔR(2p)=−1.7 eV and implies, for SiO₂/SiC, a “true” chemical shift in the Si 2p level of only ≈0.4 eV for oxide layers of up to 10 Å thick.     

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.     

Formation of Sim and SimCn clusters by C60 sputtering of Si

The secondary ion mass spectrum of silicon sputtered by high energy C₆₀⁺ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Si_m⁺ (1 ≤ m ≤ 15) and various Si_mC_n⁺ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Si_m⁺ clusters up to Si₇⁺ are significant (between 0.1 and 0.6 of the Si⁺ yield) with even numbered clusters Si₄⁺ and Si₆⁺ having the highest probability of formation. The abundances of cluster ions between Si₈⁺ and Si₁₁⁺ are still significant (>1% relative to Si⁺) but drop by a factor of ∼100 between Si₁₁⁺ and Si₁₃⁺. The probability of formation of clusters Si₁₃⁺-Si₁₅⁺ is approximately constant at ∼5 × 10⁻⁴ relative to Si⁺ and rising a little for Si₁₅⁺, but clusters beyond Si₁₅ are not detected (Si_m≥16⁺/Si⁺ < 1 × 10⁻⁴). The probability of formation of Si_m⁺ and Si_mC_n⁺ clusters depends only very weakly on the C₆₀⁺ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Si_m⁺ and Si_mC_n⁺ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C₆₀⁺ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Si_m⁺ clusters produced during C₆₀⁺ sputtering of silica (SiO₂) and various silicate minerals. The abundances for clusters heavier than Si₂⁺ are very small compared to the case where Si is the target.The data reported here suggest that Si_m⁺ and Si_mC_n⁺ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.     

Influence of the chemisorption state on the charge distribution of low energy Si scattered from I adatoms

The ion fractions of 5 keV Si⁺ ions singly scattered from iodine adatoms adsorbed on Al(1 0 0), Si(1 1 1) and pre-oxidized Si(1 1 1) were measured with time-of-flight spectroscopy. A considerable ion yield was observed, which did not change significantly with exit angle or I coverage. The mechanism of ion formation is assigned to valence electron resonant charge transfer (RCT) assisted by promotion of the Si ionization level. The yields are smaller than those of Si scattered from Cs adatoms, however, which suggests that electron tunneling from the occupied chemisorption states of the I adatom provides an additional neutralization channel.     

Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.     

Epitaxial SiC formation induced by medium energy ions on Si(1 1 1) at room temperature

In the search for silicon technology compatible substrate for III-nitride epitaxy, we present a proof-of-concept for forming epitaxial SiC layer on Si(1 1 1). A C/Si interface formed by ion sputtering is exposed to 100-1500 eV Ar⁺ ions, inducing a chemical reaction to form SiC, as observed by core-level X-ray photoelectron spectroscopy (XPS). Angle dependent XPS studies shows forward scattering feature that manifest the epitaxial SiC layer formation, while the valence band depicts the metal to insulator phase change.     

Cesium redeposition artifacts during low energy ToF-SIMS depth profiling

H-terminated Si samples were preloaded with Cs by performing ToF-SIMS depth profiles (250 eV Cs⁺, 15 keV Ga⁺) until the steady state was reached both with and without a bias of +40 V applied to the ion extraction electrode. Xe⁺ depth profiles (350 eV Xe⁺, 15 keV Ga⁺) were obtained inside and around the Cs craters with and without applying the 40 V bias. The results indicate that the maximum of the Cs⁺ signal of the Xe⁺ depth profiles shifts to the surface if no bias is applied, either during the Cs⁺ sputtering or during the Xe⁺ sputtering (i.e., the profiles are broadest with both biases (Cs⁺ and Xe⁺) on and narrowest and closest to the surface if both biases are off). This effect can be explained by the electric field, caused by the bias, deflecting the sputtered low energy Cs⁺ ions back to the surface.     

Initial stage of nitridation on Si(1 0 0) surface using low-energy nitrogen ion implantation

The initial stage of the thermal nitridation on Si (1 0 0)-2 × 1 surface with the low-energy nitrogen ion (200 eV) implantation was studied by photoemission spectroscopy (PES). The formation of nitride was shown the different characteristics depending on the annealing temperature. The disordered surface at room temperature was changed to 2 × 1 periodicity with the low-energy electron diffraction (LEED) as increasing the nitridation temperature. By decomposition of Si 2p spectrum, we can identify the three subnitrides (Si¹⁺, Si²⁺, and Si³⁺). By changing the take-off angle of the Si 2p, we can increase surface sensitivity and estimate that Si¹⁺, Si²⁺ and Si³⁺ are the interface states.     

Interaction of cesium with charged oxide under UV irradiation imaged by photoemission electron microscopy

We report the first observation of electron transfer from charged SiO₂/Si(1 0 0) by ion-implantation via internal photoemission from Si by photoemission electron microscopy (PEEM) for the purpose of the microscopic control of promotion of catalyst by electron transfer from oxide support. The contrast of the PEEM image varies with the amount and kind of the implanted ion and the deposition of Cs through the formation of electrical double layer consisting of Cs⁺ and trapped electrons at trapping centers created by the implantation. It is then firmly established that oxide charging can be microscopically tuned by ion-implantation.     

The effect of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface

We have studied the effects of controlled ion bombardment on the electronic structure of the Si(0 0 1) surface. The surface was exposed to various doses of Ar⁺ ions accelerated towards the surface at 500 eV. X-ray photoelectron spectroscopy (XPS) spectra of the irradiated H-terminated Si(0 0 1) surface reveal the appearance of peaks that are associated with the presence of cleaved Si bonds. Ultraviolet photoelectron spectroscopy (UPS) spectra of the irradiated Si(0 0 1)2 × 1 surface show that the dimer dangling-bond surface state decays monotonically with increasing dose. These results, coupled with previous scanning tunneling microscopy (STM) studies, indicate that the breaking of dimers, and possibly the creation of adatom-like defects, during ion irradiation are responsible for the changes in the electronic structure of the valence band for this surface.     

Characterization of ion species of silicon oxide films using positive and negative secondary ion mass spectra

Secondary ion species of silicon oxide films have been investigated using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Characterization of thermally grown SiO₂ films on silicon has been performed. A diagram showing secondary ion spectra of SiO₂ films in both positive and negative polarities indicates the pattern of change in polarities and intensities of ion species from SiO⁺ to Si₅O₁₁⁻. The ions mostly change from positive to negative polarity between Si_nO_2n−1 and Si_nO_2n. Ion peaks with the strongest intensities in the respective cluster ions correspond to the Si_nO_2n+1 negative ion. Intensities of ion species of Si_nO_2n+2 appear negligibly small. Ion species of Si₃O⁺, Si₃O₂⁺ and Si₃O₃⁺ have been found at the interface between silicon and SiO₂ films. The intensity patterns of these ion species compared to those of SiO₂ films indicate that most of these species are not emitted from the SiO₂ films, but likely from the SiO structures.     

Photoemission studies of pulsed-RF plasma nitrided ultra-thin SiON dielectric layers

Results are presented of a photoemission study of the electronic structure of SiON layers formed by a pulsed-RF decoupled plasma nitration (DPN) of ultra-thin SiO₂ grown base layers approximately 1.0 nm thick. The optical thickness of these device grade nitrided dielectric layers was in the range 1.4-1.6 nm. X-ray photoelectron spectroscopy (XPS) studies indicate that the nitrogen is incorporated in a single chemical environment at concentration levels in the range 15-17%. Angle resolved XPS measurements show that the nitrogen is distributed through the layer, with the binding energy of the N 1s peak at 398.3 eV which is indicative of a Si₃N₄-like chemical species in an oxide environment. High resolution core level photoemission studies of the spin orbit stripped Si 2p⁴⁺ peak revealed full width half maximum values in the range 1.4-1.55 eV, which are significantly larger than the 1.15 eV value reported for SiO₂ layers. Synchrotron radiation photoemission studies of the valence band spectra enable the valence band off-set at the Si/SON interface to be evaluated as 2.3 eV and to infer a conduction band off-set of 2.1 eV.     

XPS study of silicon surface after ultra-low-energy ion implantation

Ultra-low-energy ion implantation of silicon with a hydrogen-terminated (0 0 1) surface was carried out using a mass-separated ³¹P⁺ ion beam. The ion energy was 30 eV, the displacement energy of silicon, and the ion doses were 6 × 10¹³ ions/cm². Annealing after the implantation was not carried out. The effects of ion implantation on the surface electrical state of silicon were investigated using X-ray photoelectron spectroscopy (XPS). The Si 2p peak position using XPS depends on the doping conditions because the Fermi level of the hydrogen-terminated silicon surface is unpinned. The Si 2p peak position of the specimen after ion implantation at a vacuum pressure of 3 × 10⁻⁷ Pa was shifted to the higher energy region. It suggested the possibility of phosphorus doping in silicon without annealing. In the case of ion implantation at 5 × 10⁻⁵ Pa, the Si 2p peak position was not shifted, and the peak was broadened because of the damage by the fast neutrals. Ultra-low-energy ion doping can be achieved at ultra-high-vacuum conditions.     

Ion-bombardment induced morphology change of device related SiGe multilayer heterostructures

Ion assisted molecular beam epitaxy bears the potential to tune morphological and structural parameters of semiconductor heterolayers for opto- and nanoelectronic applications. The morphology evolution and the degree of relaxation are influenced by the ion beam parameters and the strain of the heteroepitaxial film. In this work, the morphology of silicon germanium (SiGe) layers due to Si⁺-ion beam treatment during growth is investigated by atomic force microscopy (AFM) as a function of ion energy and ion flux density. Ion energies range from 100 eV to 1000 eV. The AFM measurements are used to determine the roughness distribution across the wafers. A regular pattern of SiGe crystallites is found, where the damage due to low ion energy Si⁺-ion bombardment is medium and the degree of relaxation, determined by Raman spectroscopy, is below 25%.     

Secondary ion emission from Si bombarded with large Ar cluster ions under UHV conditions

Si was bombarded with size-selected 40 keV Ar cluster ions and positive secondary ions were measured using the time-of-flight technique under high and ultra-high vacuum (HV and UHV respectively) conditions. Si⁺ ions were main species detected under the incidence of 40 keV Ar cluster ions, and the yields of Si cluster ions such as Si₄⁺ were also extremely high under both conditions. On the other hand, oxidized secondary ions such as SiO⁺ were detected with high intensity only under the HV condition. The yield ratios of oxidized ions decreased in UHV to less than 1% of their values in HV. The effect of residual gas pressure on Si cluster ion yields is relatively low compared to oxidized ions, and the UHV condition is required to obtain accurate secondary ion yields.     

Exact compositional analysis of SiGe alloys by matrix effect compensated MCs+-SIMS

SiGe alloy, owing to its high electron and hole mobility, has potential applications in high-speed microelectronic device technology. The optimization of such technology requires the precise determination of Ge concentration in the full range of composition and the understanding and control of the Ge–Si interdiffusion phenomenon. The most appropriate analytical technique with highest detection sensitivity (～subparts per billion) for measuring elemental concentration is secondary ion mass spectrometry (SIMS). However, strong compositional dependence of secondary ion yield, i.e. “matrix effect,” has always made SIMS quantification extremely difficult. A procedure for the accurate quantification of Ge concentration in molecular beam epitaxy (MBE)-grown Si_1?x Ge _x (0<x<0.72) alloys based on MCs⁺-SIMS approach has been proposed. The “matrix effect” is shown to be completely suppressed for all Ge concentrations irrespective of impact Cs⁺ ion energies. The novel methodology has successfully been applied for direct quantitative composition analysis of Si/Ge multilayer structure.     

Valence band studies of the formation of ultrathin pure silicon nitride films on Si(1 0 0)

The growth of ultrathin films of Si₃N₄ directly on Si surfaces is studied with valence band photoemission. The information from these studies about the growth mechanism and the changes of the electronic structure is enhanced by the use of various photon energies with synchrotron radiation. The silicon nitride films are grown isothermally on the Si(1 0 0) and Si(1 1 1) surfaces by reactions with atomic N. The atomic nitrogen is produced by using a remote, microwave excited nitrogen plasma. The growth under these conditions was earlier shown to be self limiting. The details in the valence band spectra are identified and resolved with numerical methods, and followed systematically during the growth. Thus the identification of Si surface states, Si-nitride interface states and bulk nitride states becomes possible. The previously obtained separation between amorphous and crystalline growth occurring around 500 °C is further supported in the present studies.     

4d core hole formation in silver and its role in Ag secondary ion formation/survival

The low energy mono-atomic secondary ion intensities of Ag⁻ over the transient regions from Ag under 1-5 keV Cs⁺ primary ion impact are compared. These energies are used since they appear to be above and below the collisional excitation threshold for 4d core hole formation. The lack of any work function dependence in both suggests that (a) Ag⁻ forms via resonance charge transfer of electrons from the broad 5s-5p band to Ag atoms bearing 4d core holes (Auger is disregarded for energetic reasons), and that (b) the route via which 4d core holes are formed, whether it be via collective oscillations or collisional excitation, is of minimal importance. The similarity in X-ray induced plasmon loss features from clean and Cs implanted Ag confers with these results.     

Uranium passivation by C implantation: A photoemission and secondary ion mass spectrometry study

Implantation of 33 keV C⁺ ions into polycrystalline U²³⁸ with a dose of 4.3 × 10¹⁷ cm⁻² produces a physically and chemically modified surface layer that prevents further air oxidation and corrosion. X-ray photoelectron spectroscopy and secondary ion mass spectrometry were used to investigate the surface chemistry and electronic structure of this C⁺ ion implanted polycrystalline uranium and a non-implanted region of the sample, both regions exposed to air for more than a year. In addition, scanning electron microscopy was used to examine and compare the surface morphology of the two regions. The U 4f, O 1s and C 1s core-level and valence band spectra clearly indicate carbide formation in the modified surface layer. The time-of-flight secondary ion mass spectrometry depth profiling results reveal an oxy-carbide surface layer over an approximately 200 nm thick UC layer with little or no residual oxidation at the carbide layer/U metal transitional interface.