Image contrast enhancement in field-emission scanning electron microscopy of single-walled carbon nanotubes

The image contrast enhancement in scanning electron microscopy of single-walled carbon nanotubes (SWNTs) on SiO₂ surfaces was experimentally investigated using a field-emission scanning electron microscope (FESEM) using a wide range of primary electron (PE) voltages. SWNT images of different contrasts were obtained at different PE voltages. Image contrast enhancement of SWNTs was investigated by charging SiO₂ surfaces at different PE voltages. The phenomena are ascribed to the surface potential difference and charge injection between SWNTs and SiO₂ substrates induced by the electron-beam irradiation.     

Laser-induced oxidation of the Si(111) surface

Pulsed laser induced oxidation of clean Si(111) surfaces has been studied by Auger electron spectroscopy and electron energy loss spectroscopy. The short duration time of the pulse has allowed a precise investigation of the first stages of the oxidation. About 1–2 oxide monolayers first grow in less than 10 s. Their stoichiometry evolves from SiO_x towards SiO₂ with increasing beam energy densities. Once this superficial layer has formed, no evolution is seen with further irradiation, suggesting that oxygen diffusion during the pulse duration cannot sustain the oxide growth.     

SiO2 surface defect centers studied by AES

A theoretical model is proposed on how a Si dangling bond associated with an oxygen vacancy on a SiO₂ surface (E_s′ center) should be observed by Auger electron spectroscopy (AES). The Auger electron distribution N_A(E) for the L₂₃VV transition band is calculated for a stoichiometric SiO₂ surface, and for a SiO_x surface containing Si-(e^?O₃) coordinations. The latter is characterized by an additional L₂₃VD transition band, where D is the energy level of the unpaired electron e^?. The theoretical N_A(E) spectra are compared with experimental N(E) spectra for a pristine, and for an electron radiation damaged quartz surface. Agreement with the theoretical model is obtained if D is assumed to lie ≈2 eV below the conduction band edge. This result shows that AES is uniquely useful in revealing the absolute energy level of localized, occupied surface defect states. As the L₂₃VD transition band (main peak at 86 eV) cannot unambiguously be distinguished from a SiSi₄ coordination L₂₃VV spectrum (main peak at 88 eV), supporting evidence is presented as to why we exclude a SiSi₄ coordination for our particular experimental example. Application of the Si-(e^?O₃) model to the interpretation of SiO₂Si interface Auger spectra is also discussed.     

Décomposition thermique du monoxide de carbone sur une surface de molybdène: Formation de couches superficielles de carbone et de carbure

We have investigated the decomposition of carbon monoxide on polycrystalline and (001), (110) monocrystalline molybdenum surfaces. This study was performed by massspectrometry, for thermal desorption studies, Auger electron spectrometry (AES), low energy electron diffraction (LEED) and photoelectron spectroscopy (ESCA). By heating the clean Mo surface in CO or by heating the Mo surface covered with CO, the dissociation of chemisorbed CO leads to a build-up of carbon layer which inhibits the subsequent adsorption. Two distinct types of fine structure are associated with the KLL line of carbon Auger spectra. If the Mo surface is heated at a temperature between 300 and 1500 K, the Auger peak is characteristic of a “graphite layer”. If the Mo surface is heated at a temperature up to 2000 K, the Auger peak is characteristic of a “carbure” layer. This “carbure layer” give rise to a surstructure which agrees with a Mo₂C surface layer and was also investigated by ESCA. Chemical shifts of (1s) C and (3d) Mo photoemission bands were observed and attributed to the bounding between Mo and C atoms in the Mo₂C layer.     

Long range enhancement of boron diffusivity by phosphorus diffusion

The effect of electron and ion beam irradiation on the Si_{L vv} Auger spectra of SiO₂, Si₃N₄ and Si-oxynitride films was measured by the relative intensity of the 92 eV signal, characteristic for the formation of “free” silicon during irradiation. While in Si-oxynitride (O/N = 0.37) the beam effects were almost negligible, some damage was found in Si₃N₄, but SiO₂ appeared to be extremely sensitive for electron and ion beam irradiation. By low energy electron loss spectroscopy (ELS) of ion bombarded SiO₂ and Si₃N₄ films new electron states due to broken Si-O and Si-N bonds could be determined within the band gap of the insulators. The measured energy losses were interpreted by means of electron energy level schemes of the amorphous films.     

Surface EXAFS via differential electron yield

Surface‐sensitive analysis via extended X‐ray absorption fine‐structure (EXAFS) spectroscopy is demonstrated using a thickness‐defined SiO₂ (12.4 nm)/Si sample. The proposed method exploits the differential electron yield (DEY) method wherein Auger electrons escaping from a sample surface are detected by an electron analyzer. The DEY method removes local intensity changes in the EXAFS spectra caused by photoelectrons crossing the Auger peak during X‐ray energy sweeps, enabling EXAFS analysis through Fourier transformation of wide‐energy‐range spectral oscillations. The Si K‐edge DEY X‐ray absorption near‐edge structure (XANES) spectrum appears to comprise high amounts of SiO₂ and low Si content, suggesting an analysis depth, as expressed using the inelastic mean free path of electrons in general electron spectroscopy, of approximately 4.2 nm. The first nearest neighbor (Si—O) distance derived from the Fourier transform of the Si K‐edge DEY‐EXAFS oscillation is 1.63 Å. This value is within the reported values of bulk SiO₂, showing that DEY can be used to detect a surface layer of 12.4 nm thickness with an analysis depth of approximately 4.2 nm and enable `surface EXAFS' analysis using Fourier transformation.     

Surface energy modification by electron beam

We observe a pronounced variation of wettability properties in solid state materials induced by a low-energy electron beam. The phenomenon occurs in several stages characterized by various mechanisms. We show that for low electron doses the irradiation leads to decrease in the wetting of a dielectric surface due to induced surface electric potential. The higher electron charge leads to formation of a chemical monolayer on material’s surface. It has been found that the electron irradiation strongly modifies the surface free energy of SiO₂ by decreasing its total surface free energy value, almost twice. However, electron-induced variations of dispersive and polar components of the surface free energy are quite different and depend of incident electron charge.     

Band bending variation of the Si(111) surface during its thermal oxidation

During the thermal oxidation of Si(111) surfaces performed under ultra high vacuum conditions and investigated with various surface techniques such as Auger electron spectroscopy, low energy electron diffraction, ultra violet and X-ray induced photoemission spectroscopy, the Si 2p core level binding energy was measured and provided directly the band bending variation of the Si surface. A net interface charge then could be deduced. This is an elegant in situ method to have access to the electrical characteristics of the SiSiO₂ interface during its formation.     

The positive charging effect of dielectric films irradiated by a focused electron beam

Space charge and surface potential profiles are investigated with numerical simulation for dielectric films of SiO₂ positively charged by a focused electron beam. By combining the Monte Carlo method and the finite difference method, the simulation is preformed with a newly developed comprehensive two-dimensional model including electron scattering, charge transport and trapping. Results show that the space charge is distributed positively, like a semi-ellipsoid, within a high-density region of electrons and holes, but negatively outside the region due to electron diffusion along the radial and beam incident directions. Simultaneously, peak positions of the positive and negative space charge densities shift outwards or downwards with electron beam irradiation. The surface potential, along the radial direction, has a nearly flat-top around the center, abruptly decreases to negative values outside the high-density region and finally increases to zero gradually. Influences of electron beam and film parameters on the surface potential profile in the equilibrium state are also shown and analyzed. Furthermore, the variation of secondary electron signal of a large-scale integration sample positively charged in scanning electron microscopic observation is simulated and validated by experiment.     

Observing the effect of water vapor on post-irradiated surface morphology of SiO2 and Si3N4 insulators by atomic force microscopy

In this work, we investigated the effect of water-vapor treatment on the surface morphology of SiO₂ and Si₃N₄ insulators before and after Co⁶⁰ gamma-ray irradiation by using the atomic force microscopy (AFM) operated under non-contact mode. Before irradiation, no apparent surface morphology change was found in SiO₂ samples even they were water vapor treated. However, bright spots were found on post-irradiated water-vapor-treated SiO₂ sample surfaces but not on those without water-vapor treatment. We attributed the bright spots to the negative charge accumulation in the oxide due to charge balancing between hydroxyl (OH⁻) ions adsorbed on SiO₂ surface and electron-hole pairs (ehps) generated during irradiation since they can be annealed out after low temperature annealing process. On the contrary, no bright spots were observed on post-irradiated Si₃N₄ samples with and without water-vapor treatment. This result confirms that Si₃N₄ is a better water-resist passivation layer than SiO₂ layer.     

Mechanisms for oxygen adsorption on the Si(110) surface studied by Auger electron spectroscopy

Oxygen adsorption on the Si(110) surface has been studied by Auger electron spectroscopy. For a clean annealed surface chemisorption occurs, with an initial sticking probability of ～6 × 10^?3. In this case the oxygen o_kll signal saturates and no formation of SiO₂ can be detected from an analysis of the Si L_2,3VV lineshape. With electron impact on the surface during oxygen exposure much larger quantities are adsorbed with the formation of an SiO₂ surface layer. This increased reactivity towards oxygen is due to either a direct effect of the electron beam or to a combined action of the beam with residual CO during oxygen inlet, which creates reactive carbon centers on the surface. Thus in the presence of an electron beam on the surface separate exosures to CO showed adsorption of C and O. For this surface subsequent exposure in the absence of the electron beam resulted in additional oxygen adsorption and formation of SiO₂. No adsorption of CO could be detected without electron impact. The changes in surface chemistry with adsorption are detectable from the Si L_2,3VV Auger spectrum. Assignments can be made of two main features in the spectra, relating to surface and bulk contributions to the density of states in the valence band.     

Degradation of Y2SiO5:Ce phosphor powders

The degradation of the cathodoluminescence (CL) intensity of cerium-doped yttrium silicate (Y₂SiO₅:Ce) phosphor powders was investigated for possible application in low voltage field emission displays (FEDs). Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and CL spectroscopy were used to monitor changes in the surface chemical composition and luminous efficiency of commercially available Y₂SiO₅:Ce phosphor powders. The degradation of the CL intensity for the powders is consistent with a well-known electron-stimulated surface chemical reaction (ESSCR) model. It was shown with XPS and CL that the electron stimulated reaction led to the formation of a luminescent silicon dioxide (SiO₂) layer on the surface of the Y₂SiO₅:Ce phosphor powder. XPS also indicated that the Ce concentration in the surface layer increased during the degradation process and the formation of CeO₂ and CeH₃ were also part of the degradation process. The CL intensity first decreased until about 300 C cm⁻² and then increased due to an extra peak arising at a wavelength of 650 nm.     

Research on Electron Emission from Dielectric Materials by a Monte Carlo Method

The charge accumulation in an insulating material under an electron beam bombardment exerts a significant influence to scanning electron microscopic imaging. This work investigates the charging formation process by a self-consistent Monte Carlo simulation of charge production and transportation based on a charge dynamics model. The charging effect in a semi-infinite SiO₂ bulk and SiO₂ trapezoidal lines on a SiO₂ or Si substrate has been studied. We used two methods to calculate the spatial distributions of electric potential and electric field for two different systems respectively: the image charge method was used to deal with a semi-infinite bulk, and, random walk method to solve the Poisson equation for a complex geometric structure. The dynamic charging behavior depending on irradiation time has been investigated for SiO₂. The simulated CD-SEM images of SiO₂ trapezoidal lines with charging effect included were compared well with experimental results, showing the contrast change of SEM image along with scanning frames due to charging.     

Electron-beam charging of dielectrics preirradiated with moderate-energy ions and electrons

The effects of charging of dielectric targets irradiated with moderate-energy electrons in a scanning electron microscope are examined. Considerable differences in the kinetics of charging of the reference samples and the samples preirradiated with ions and electrons are reported. These differences are attributed to the processes of radiation-induced defect formation in Al₂O₃ (sapphire) and SiO₂ that are, however, dissimilar in nature. The contributions of surface structure modification and changes in the electrophysical parameters of the surface (specifically, the charge spreading effect) are revealed. Critical doses of irradiation with Ar⁺ ions and electrons inducing active defect formation in dielectric targets and critical values of internal charge fields producing a significant contribution to the temporal parameters of Al₂O₃ and SiO₂ charging are determined.     

Auger-induced rearrangement of an ion-bombarded/SiO2 surface: Influence of electron energy

Ion bombardment of SiO₂ produces an understoichiometric surface layer containing a distribution of bonding states: SiO₂, SiO _x and free Si. Under the electron beam probe, a redistribution occurs, favoring the SiO₂ and free Si states at the expense of SiO _x , without loss of oxygen. The free Si yield exhibits the same energy dependence as the Auger yield of the Si LVV transition, thus pointing to Auger-induced bond rupture as the primary damaging event.     

Interfacial structures of LaAlO<Subscript>3</Subscript> films on Si(100) substrates

This paper investigates the interfacial characteristics of LaAlO₃ (LAO) and LaAlO_xN_y (LAON) films deposited directly on silicon substrates by the pulsed-laser deposition technique. High-resolution transmission electron microscopy (HRTEM) pictures indicate that an interfacial reaction between LAO and Si often exists. The interfacial layer thickness of LAO films deposited in a nitrogen ambient atmosphere is smaller than that of LAO films deposited in an oxygen ambient atmosphere. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were used to study the composition of the interfacial layer. The shift of the La 3d photoelectron peak to a higher binding energy compared to LaAlO₃, the shift of the Al 2p peak to a higher binding energy compared to LaAlO₃, the shift of the Si 2p peak to a lower binding energy compared to SiO₂ and the intermediate location of the O 1s peak compared to LaAlO₃ and SiO₂ indicate the existence of a La–Al–Si–O bonding structure, which was also proved by the AES depth profile of LAO films. It can be concluded that the interfacial layer is not simply SiO₂ but a compound of La–Al–Si–O. PACS 77.84.Bw; 77.84.-s; 77.55.+f     

High resolution Auger electron spectroscopy of metallic copper

Part of the LMM Auger spectrum from metallic copper has been studied in a high resolution X-ray photoelectron spectrometer. Fine structure not earlier reported has been observed. The main L₃M_4,5M_4,5 peak is very narrow, 1.0 eV, although the valence band is involved in the transition. The agreement between experimental and calculated Auger electron energies is very good. Since fine structure is found to be an intrinsic property in Auger spectra the interpretation of “satellite” peaks as due to electron—plasmon interactions should be used with care. The L₃M_4,5M_4,5 peak is very sensitive to the copper surface conditions. Surface oxygen affects the peak in a characteristic way.     

Electron and ion beam effects in auger electron spectrometry

In Auger Electron Spectrometry relatively high primary electron current density is usually used in order to obtain a good signal-to-noise ratio. As a consequence, a number of phenomena occurs, which can substantially modify—or even destroy—the sample, and impair the results of the analysis.

In this communication we report some observations on the electron and ion beam interaction on some of the insulating and conducting films used in the silicon device technology. Among the materials considered, silicon nitride and P-doped silicon dioxide are of primary interest, and will be treated in some detail; results on other films, both insulating (Al₂O₃, B-doped SiO₂, etc.) and conducting (Al-Si alloys) will also be reported.

The electron beam causes the oxides (B, Al, Si, P) to be reduced, as shown by the decrease of the height of the low energy, chemically shifted peaks (B_KVV, Al_LVV, Si_Lvv, P_Lvv) and by the contemporary increase of the height of the elemental peaks. In phosphorus doped glasses the electron beam also induces a strong surface P enrichment, followed by a P desorption. Silicon nitride was found to be quite stable against the e-b irradiation in “good” vacuum, but very sensitive to the e-b induced oxidation even at (total) pressure as low as 5 × 10¹⁰ torr. This is a very important fact to be taken into account when evaluating thin Si₃N₄ films, because it can change the apparent film stoichiometry.

Some metallic films are also preferentially oxidized by the electron beam; in Al/Si diluted alloy (0.1÷2% silicon) a strong surface silicon enrichment was found to take phase on small-grained thin films, but not on bulk material.

Our results show that much care has to be taken when performing or interpreting the AES data, and how to use, in some cases, the e-b irradiation effects to increase the sensitivity of the method.     

Desorption of atomic particles and surface modification of fluorides under electron irradiation

Low-energy electron stimulated desorption (ESD) and surface modifications of CaF₂ and BaF₂ single crystals were experimentally studied at different surface temperatures. A technique based on the dependence of the surface composition on the electron irradiation dose was applied to determining the ESD cross section. The surface composition was measured by Auger electron spectroscopy (AES). Surface topography was examined by atomic force microscopy (AFM). The ESD mechanisms for fluorides were discussed.     

Binding energy shift in photoemission spectroscopy study of Ni clusters deposited on rutile TiO2 surfaces

Cluster-size-dependent binding energy (BE) shifts of Ni 2p_3/2 spectra in Ni clusters with respect to bulk Ni metal have been studied as a function of Ni coverage on clean rutile TiO₂(0 0 1) surfaces at room temperature. Auger parameter (AP) analysis of photoelectron spectra has been employed and revealed an obvious initial state contribution at the coverage of 0.5 monolayers (ML). The initial state effect was demonstrated to be strongly affected by the substrate and was assigned to a combination of eigenvalue shift in surface core-level shift (SCLS) and charge transfer between the metal clusters and substrates. The TiO₂(0 0 1) surface stoichiometry was found to introduce different charge transfer behaviors. Our results experimentally present that the Ni clusters are charged positively on stoichiomtric TiO₂ surface and less positively or even negatively on various reduced surfaces.