Chemical interactions in noncontact AFM on semiconductor surfaces: Si(111), Si(100) and GaAs(110)

Total-energy pseudopotential calculations are used to study the imaging process in noncontact atomic force microscopy (AFM) on Si(111), Si(100) and GaAs(110) surfaces. The chemical bonding interaction between a localised dangling bond on the atom at the apex of the tip and the dangling bonds on the adatoms in the surface is shown to dominate the forces and the force gradients and, hence, to provide atomic resolution. The lateral resolution capabilities are tested in both the Si(100) and the GaAs(110) surfaces. In the first case, the two atoms in a dimer can be resolved due to the dimer flip induced by the interaction with the tip during the scan, while in the GaAs(110), we identify the anion sublattice as the one observed in the experimental images.     

Development of a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA), and its application to Auger photoelectron coincidence spectroscopy (APECS)

We have developed a miniature double-pass cylindrical mirror electron energy analyzer (DPCMA) with an outer diameter of 26 mm. The DPCMA consists of a shield for the electric field, inner and outer cylinders, two pinholes with a diameter of 2.0 mm, and an electron multiplier. By assembling the DPCMA in a coaxially symmetric mirror electron energy analyzer (ASMA) coaxially and confocally we developed an analyzer for Auger photoelectron coincidence spectroscopy (APECS). The performance was estimated by measuring the Si-LVV-Auger Si-1s-photoelectron coincidence spectra of clean Si(1 1 1). The electron-energy resolution of the DPCMA was estimated to be E/ΔE = 20. This value is better than that of the miniature single-pass CMA (E/ΔE = 12) that was used in the previous APECS analyzer.     

Study of ion desorption induced by a resonant core-level excitation of condensed H2O using Auger electron photo-ion coincidence (AEPICO) spectroscopy combined with synchrotron radiation

Ion desorption induced by a resonant excitation of O 1s of condensed amorphous H₂O has been studied by total ion and total electron yield spectroscopy, nonderivative Auger electron spectroscopy (AES) and Auger electron photo-ion coincidence (AEPICO) spectroscopy. The spectrum of total ion yield divided by total electron yield exhibits a characteristic threshold peak at hν = 533.4 eV, which is assigned to the 4a₁ ← O 1s resonant transition. The AES at the 4a₁ ← O 1s resonance is interpreted as being composed of the spectator-AES of the surface H₂O, and the normal-AES of the bulk H₂O, where the 4a₁ electron is delocalized before Auger transitions. H⁺ is found to be the only ion species in AEPICO spectra measured at the 4a₁ ← O 1s resonance and at the O 1s ionization (hν = 560 eV). The electron kinetic energy dependence of the AEPICO yield (AEPICO yield spectrum) at the 4a₁ ← O 1s resonance is found to be greatly different from that at the O 1s ionization. The peak positions of the AEPICO yield spectrum at the 4a₁ ← O 1s resonance are found to correspond to those of the spectator-AES of the surface H₂O, which is extracted from the AES at the 4a₁ ← O 1s resonance. Furthermore, the AEPICO yield is greatly enhanced at the 4a₁ ← O 1s resonance as compared with that at the O 1s ionization. On the basis of these results, a spectator-Auger-stimulated ion desorption mechanism and/or ultra-fast ion desorption mechanism are concluded to be responsible for the H⁺ desorption at the 4a₁ ← O 1s resonance. The enhancement of the H⁺ yield is ascribed to the O---H anti-bonding character of the 4a₁ orbital.     

Desorption of H ions from water chemisorbed on Si(100) by O 1s excitation - an Auger electron-photoion coincidence spectroscopy study

Auger electron-photoion coincidence (AEPICO) spectroscopy, which has been recently developed and proved to be a very powerful technique for investigating the dynamics of desorption induced by the core-level excitation, is applied to the investigation of Auger-stimulated ion desorption from the chemisorbed-water-Si(100) surface induced by O 1s excitation. It is shown that the fast relaxation of the excited state with a core hole and an excited electron takes place before the core hole decay, and that the desorption yield is enhanced by the shake-up (and/or shake-off) excitation. The relative cross-section for Auger-stimulated ion desorption is estimated, and is shown to increase as holes are created at deeper levels of the valence bands as the final state of the Auger decay. A comparison is also made with condensed H₂O.     

Oxidation of heated diamond C(100):H surfaces

This paper extends a previous study (Pehrsson and Mercer, submitted to Surf. Sci.) on unheated, hydrogenated, natural diamond (100) surfaces oxidized with thermally activated oxygen (O^*₂). In this paper, the oxidation is performed at substrate temperatures from T_sub=24 to 670°C. The diamond surface composition and structure were then investigated with high resolution electron energy loss spectroscopy (HREELS), Auger electron spectroscopy (AES), electron loss spectroscopy (ELS) and low energy electron diffraction (LEED).

The oxygen coverage (θ) increased in two stages, as it did during oxidation at T<80°C. However, there are fundamental differences between the oxidation of nominally unheated and heated diamond surfaces. This difference is attributed to simultaneous adsorption and rapid desorption of oxygen species at higher temperatures; the desorption step is much slower without heating. The initial oxidation rates were similar regardless of the substrate temperatures, but the peak coverage (θ) was lower at higher temperatures. For example, θ plateaued at 0.4±0.1 ML at 600°C. The lower saturation coverage is again attributed to oxygen desorption during oxidation. Consistent results were obtained on fully oxidized surfaces, which when heated in vacuum to T_sub=600°C, lost 60% of their adsorbed oxygen. ELS revealed few C=C dimers on the oxidized surfaces, and more graphitization than on unheated surfaces. Oxidation at elevated temperatures also increased the carbonyl to ether ratio, reflecting etching-induced changes in the types of surface sites. The carbonyl and C–H stretch frequencies increased with oxygen dose due to formation of higher oxidation states and/or hydrogen bonding between adjacent groups. The oxygen types did not interconvert when the oxidized surfaces were heated in vacuum. Oxygen desorption generated a much more reactive surface than heating-induced dehydrogenation of the smooth, hydrogenated surface.     

X-ray photoelectron and X-ray Auger electron spectroscopy studies of heavy ion irradiated C60 films

The influence of 200 MeV Au ion irradiation on the surface properties of polycrystalline fullerene films has been investigated. The X-ray photoelectron and X-ray Auger electron spectroscopies are employed to study the ion-induced modification of the fullerene, near the surface region. The shift of C 1s core level and decrease in intensity of shake-up satellite were used to investigate the structural changes (like sp² to sp³ conversion) and reduction of π electrons, respectively, under heavy ion irradiation. Further, X-ray Auger electron spectroscopy was employed to investigate hybridization conversion qualitatively as a function of ion fluence.     

新型高分辨率电子能量损失谱仪与表面元激发研究

高分辨率电子能量损失谱仪利用单色平行电子束入射样品表面,与表面吸附基团的化学键振动、表面声子、电子及其集体激发模式等相互作用而被散射,通过分析散射电子的能量和动量,可以测量表面化学键、晶格动力学、电子态占据以及表面等离激元等的精确信息,是表面科学研究的有力工具.最近,能够对电子能量、动量做二维成像探测分析的半球形电子能量分析器被引入电子能量损失谱仪,实现了高能量、动量分辨率的高效率测量.在对FeSe/SrTiO_3界面超导增强物理机制的研究中,不同厚度的FeSe膜表面的电子能量损失谱表明衬底光学声子产生的偶极电场能够穿透到薄膜内部,诱导较强的电子-声子耦合作用,从而增强薄膜中电子的配对作用,进而使超导转变温度显著提高.三维拓扑绝缘体Bi_2Se_3表面大动量范围的电子能量损失谱还显示出一支奇异的电子集体激发模式,其色散特征不受晶格周期性的限制,而且其寿命和强度几乎不随动量的增加而衰减.这说明在拓扑绝缘体表面,不仅是狄拉克电子态本身,其集体激发也受到拓扑保护.充分发挥新型电子能量损失谱仪观测表面元激发分辨率高、动态范围大的优势,将有力地推动表面界面凝聚态物理问题研究的深入和发展.     

Frenkel exciton model of electron energy loss spectroscopy in -PTCDA

Recent experimental findings concerning electron energy loss spectroscopy in -Perylene-tetracarboxylic-dianhydride are analysed in terms of a Frenkel exciton model. Taking into account the energy dispersion of excitations with finite momentum transfer, the k-dependence of the dielectric tensor and the corresponding electron energy loss functions can be calculated. The exciton dispersion with a minimum at k≠0 yields a red shift of the lineshape of loss functions at large k, as observed experimentally.     

Mo(CO)6在清洁的和氧化的Si(111)表面上吸附的对比

采用高分辨电子能量损失谱对比研究Mo(CO)₆在清洁的、预吸附氧的和深度氧化的Si(111)表面上的吸附行为. 吸附Mo(CO)₆的C-O伸缩振动模式向低频方向移动,说明Mo(CO)₆与清洁Si(111)和SiO₂/Si(111)表面发生了不同的相互作用,前者较弱而后者较强. 与SiO₂/Si(111)表面的强相互作用可能引起Mo(CO)₆部分解离,形成部分分解的羰基钼物种.     

Surface segregation of aluminum atoms on Cu-9 at.% Al(1 1 1) studied by Auger electron spectroscopy and low energy electron diffraction

Auger electron spectroscopy (AES) and low energy electron diffraction (LEED) were applied to investigate the segregation of aluminum atoms on a Cu-9 at.% Al(1 1 1) surface. We observed that the Al concentration in the top layer ranged between about 9 and 36 at.% after the sample we used was annealed at different temperatures. The phenomenon of Al atoms segregating on the surfaces was explained well by considering the diffusion length of Al atoms in bulk Cu. LEED measurements showed that R30° structures grew as the concentration of Al atoms increased. The segregation phenomena on surfaces resulted in a stable two-dimensional Cu₆₇Al₃₃ alloy phase in the top layer.     

Structural phase transitions at clean and metal-covered Si(111) surfaces investigated by RHEED spot analysis

Structural phase transitions between various kinds of superlattice structures formed on a Si(111) surface have been investigated by spot analysis of reflection high-energy electron diffraction (RHEED). Reversible transitions induced by temperature changes and irreversible ones induced by metal depositions were observed. Detailed discussions on the dynamics of the phase transitions are made by quantitative analyses of integrated spot intensity and profile. For a phase transition of 7′7  1′1 structures on a clean Si(111) surface, a hysteresis with temperature difference of 5°C. between in heating and cooling processes was found in the spot intensity change, indicating a first-order transition. Hysteresis was hardly recognized, on the other hand, for transitions of Au-induced superstructures (5×2-Au or ×-Au)  1×1-Au. The spot profiles were found to be broadened during the transition of Si(111)-×-Au  1×1-Au, which was a signature of a continuous transition, while the profiles remained unchanged during the transitions of the 7×7  1×1 and 5×2-Au  1×1-Au phases. Structural conversions induced by In adsorption on the Si(111) surface kept at constant temperatures were also analyzed. The conversions at room temperature were totally dependent on the initial substrate surface structures; the 7×7 surface did not show any structural conversion with In adsorption, while the ×-In surface successively converted to a 2×2 and a × phase with coverage increase. The structural transitions at elevated temperatures were sensitively dependent on the temperatures. Sequences of transitions among the 7×7, 4×1, ×, 1×, and ×4 were quantitatively revealed as changes in RHEED spot intensity.     

Preparation and properties of GaN films on Si(111) substrates

High-quality gallium nitride (GaN) films were prepared on Si(111) substrates by sputtering post-annealing-reaction technique. XRD, XPS, and SEM measurement results indicate that polycrystalline GaN with hexagonal structure was successfully prepared. Intense room- temperature photoluminescence that peaked at 354 nm of the films is observed. The bandgap of these films has a blueshift with respect to bulk GaN.     

Limitation of Auger electron spectroscopy in the determination of the metal-on-oxide growth mode: Pd on MgO(100)

A discussion on the use of Auger electron spectroscopy as a quantitative tool to determine the growth mode of metals on single crystal oxide surfaces is presented. In the case of Pd grown epitaxially on MgO(100), the three-dimensional character of the growth is easily seen at coverage above one monolayer. However, in the submonolayer regime, and mainly at low substrate temperatures, the AES results are ambiguous. The combination of AES with the more sensitive helium-atom diffraction method allows us to demonstrate that the growth is three-dimensional from the early stages, the particles becoming flatter when the substrate temperature decreases. We compare our results with other growth studies on different metal/oxide systems. At low temperature, the ideal growth modes are not always observed, the final morphology of the films being determined mainly by kinetic effects. Thus a pseudo-Stranski-Krastanov growth mode is often obtained with formation of 2D islands followed by 3D clustering from a critical submonolayer coverage.     

The effect of adsorbed atomic hydrogen on the growth of ultrathin silicon films on Ge(100) studied by positron-annihilation-induced Auger electron spectroscopy (PAES)

The effects of adsorbed atomic hydrogen on the stability of silicon films grown on a Ge(100) substrate were studied by using positron-annihilation-induced Auger electron spectroscopy (PAES) and electron-induced Auger electron spectroscopy (EAES). PAES is almost exclusively sensitive to the topmost atomic layer due to the trapping of positrons in an image potential well just outside the surface before annihilation. This surface specificity was exploited in the study of film stability and interfacial mixing during the growth of silicon on Ge(100). The PAES results show that the prior adsorption of hydrogen prevented the segregation of germanium on top of the deposited silicon, and that the hydrogen adsorption was useful in growing a thermally stable structure.     

Structural phase transition on Si(001) and Ge(001) surfaces

Among a variety of solid surfaces, Si(001) and Ge(001) have been most extensively studied. Although they seem to be rather simple systems, there have been many conflicting arguments about the atomic structure on these surfaces. We first present experimental evidence indicating that the buckled dimer is the basic building block and that the structural phase transition between the low-temperature c(4x2) structure and the high-temperature (2x1) structure is of the order-disorder type. We then review recent theoretical work on this phase transition. The real system is mapped onto a model Ising-spin system and the interaction parameters are derived from total-energy calculations for different arrangements of buckled dimers. The calculated critical temperature agrees reasonably well with the experimental one. It is pointed out that the nature of the phase transition is crucially affected by a small amount of defects on the real surfaces.     

Silicon surface passivation by aluminium oxide studied with electron energy loss spectroscopy

The origin behind crystalline silicon surface passivation by Al₂O₃ films is studied in detail by means of spatially‐resolved electron energy loss spectroscopy. The bonding configurations of Al and O are studied in as‐deposited and annealed Al₂O₃ films grown on c‐Si substrates by plasma‐assisted and thermal atomic layer deposition. The results confirm the presence of an interfacial SiO₂‐like film and demonstrate changes in the ratio between tetrahedrally and octahedrally coordinated Al in the films after annealing. These observations reveal the underlying origin of c‐Si surface passivation by Al₂O₃. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Quantitative Auger electron spectroscopy analysis of binary alloys with separate matrix correction factors for bulk and surface

A new method which takes into account the separate matrix correction factors for bulk and surface has been tried out for quantitative Auger electron spectroscopy analysis of binary alloys. The calculations use an iteration scheme. It has been applied to the Fe-Cr alloys studied at this Centre and the Auger electron spectroscopy data for the other alloy systems available in literature. The results are now more compatible with the expectation that the surface composition is different from the bulk.     

Construction of an electron analyzer with a wide acceptance solid angle

We have developed a new electron energy analyzer with a large solid angle of 0.14π, which is comparable to that of cylindrical mirror analyzer. Typical energy resolution was ΔE/E₀ ∼ 0.016 for the aperture of 1 mm and central radius of 100 mm, and typical angular resolution was less than 0.5°.