Characterisation of alkyl-functionalised Si(1 1 1) using reflectometry and AC impedance spectroscopy

The past few years have seen a dramatic increase in the study of organic thin-film systems that are based on silicon-carbon covalent bonds for bio-passivation or bio-sensing applications. This approach to functionalizing Si wafers is in contrast to gold-thiol or siloxane chemistries and has been shown to lead to densely packed alkyl monolayers. In this study, a series of alkyl monolayers [CH₃(CH₂)_nCH=CH₂; n = 7, 9, 11, 13, 15] were directly covalent-linked to Si(1 1 1) wafers. The structures of these monolayers were studied using X-ray reflectometry (XRR) and AC impedance spectroscopy. Both techniques are sensitive to the variation in thickness with each addition of a CH₂ unit and thus provide a useful means for monitoring molecular-scale events. The combination of these techniques is able to probe not only the thickness, but also the interfacial roughness and capacitance of the layer at the immobilized surface with atomic resolution. Fundamental physical properties of these films such as chain canting angles were also determined.     

Adsorption of organic molecules by photochemical reaction on Cl:Si(1 1 1) and H:Si(1 1 1) evaluated by HREELS

The covalent attachment of alkyl groups to silicon surfaces, via carbon-silicon bond formation, has been attempted using gas-surface reactions starting from Cl-terminated Si(1 1 1) or H:Si(1 1 1) under ultraviolet light irradiation. The formation of Cl-terminated Si(1 1 1) and its resulting stability were examined prior to deposition of organic molecules. High-resolution electron energy loss spectroscopy (HREELS) was utilized for detecting surface-bound adsorbates. The detection of photo-deposited organic species on Cl:Si(1 1 1) from gas-phase CH₄ or CH₂CH₂ was not significant. On H:Si(1 1 1), it was evident that after the photoreaction with gas-phase C₂H₅Cl, C₂H₅ groups were chemically bonded to the surface Si atoms through single covalent bonds. The C₂H₅ groups were thermally stable at temperatures below 600 K. Alkyl monolayers prepared on silicon surfaces by dry process will lead to a new prospective technology of nanoscale fabrication and biochemical applications.     

Chemisorption of alkyl thiols and S-alkyl thiosulfates on Pt(1 1 1) and polycrystalline platinum surfaces

The self-assembled monolayers prepared from 1-dodecanethiol (C₁₂SH) or S-dodecylthiosulfate (Bunte salt, C₁₂SSO₃Na) have been characterised on polycrystalline gold and platinum surfaces and on Pt(1 1 1). Contact angle and impedance measurements show that the film quality decreases in the order Au/C₁₂SH > Pt/C₁₂SH ∼ Au/C₁₂SSO₃Na > Pt/C₁₂S SO₃Na. XPS measurements show that the S-SO₃ bond of organic thiosulfates is broken on platinum surfaces and the state of the surface-bound sulfur is indistinguishable from that of thiolate. On platinum three sulfur species are formed upon SAM formation and we suggest that the catalytic activity of platinum is responsible for their existence in pristine monolayers.     

PM-IRRAS studies of the adsorption and stability of organophosphonate monolayers on passivated NiTi surfaces

Alkylphosphonic acids of different alkyl chain lengths were adsorbed on electrochemically polished NiTi surfaces from ethanolic solutions. The electropolishing process led to passive films mainly composed of Ti-oxyhydroxide. The surface showed nanoscopic etching pits with a depths of about 2 nm and a diameter of about 20 nm. The interfacial binding mechanism of the phosphonic acid group to the oxyhydroxide surface and the ordering of the monolayer were spectroscopically analysed by means of infrared reflection absorption FTIR-spectroscopy with (PM-IRRAS) and without (IRRAS) photoelastic modulation. The comparison of IRRAS and PM-IRRAS data of the long chain octadecylphosphonic acid monolayer proved that the binding mechanism of the phosphonic acid group to the oxyhydroxide surface is based on a mono- or bidentate bond, which is not stable in the presence of high water activities. An alkyl chain length of 17 CH₂ groups is required for the formation of self-assembled monolayers, which are stable in aqueous environments. These long chain aliphatic organophosphonic acid monolayers were shown to inhibit anodic and cathodic surface reactions.     

Fabrication of nanostructures by selective growth of C60 and Si on Si(1 1 1) substrate

Using two types of selective growth, selective C₆₀ growth and selective Si growth, on a common Si(1 1 1) substrate, an array of C₆₀ nanoribbons with controlled values of width and thickness is fabricated. On a surface that has Si(1 1 1)√3 × √3R30°-Ag (referred to as Si(1 1 1)√3-Ag hereafter) and bare Si(1 1 1) regions at the same time, the preferential growth of C₆₀ multilayered film is recognized on the Si(1 1 1)√3-Ag region. The growth of Si selectively occurs on a bare Si(1 1 1) region if the substrate surface has C₆₀-adsorbed and bare Si(1 1 1) regions at the same time. As a demonstration of the use of these selective growths, we fabricate an array of well-isolated C₆₀ nanoribbons, which show a well-ordered molecular arrangement and have sizes of about 40 nm in widths and 3-4 nm in thicknesses.     

Self-assembling of cyano- and carboxyl-terminated monolayers using short-chain alkylsiloxane

A simple method was developed for the preparation of cyano- and carboxyl-terminated alkylsiloxane monolayers on the hydroxylated surface of the SiO₂/Si substrate through using adsorption and hydrolysis reaction of a short-chain 2-cyanoethyl triethoxysilane [(CH₃CH₂O)₃SiCH₂CH₂CN]. The contact angle and the X-ray photoelectron spectroscopy (XPS) measurements have proved that the cyano terminal group indeed formed on the substrate and was transformed into the carboxylic terminal group after hydrolysis. The ellipsometry shows the presence of an intact monolayer with thickness of around 0.7 nm before and during the hydrolysis reaction. The surface morphology was observed with atomic force microscopy (AFM) imaging. Those all indicate that uniform and ordered self-assembled monolayers (SAMs) were formed on the substrate.     

Scaling behavior of island density in submonolayer growth of CaF2 on vicinal Si(1 1 1)

We have studied the scaling behavior of two-dimensional island density during submonolayer growth of CaF₂ on vicinal Si(1 1 1) surfaces using scanning tunneling microscopy. We have analyzed the morphology of the Si(1 1 1) surfaces where CaF₂ partial monolayers with coverages of about 0.1 monolayer are deposited at ∼600 °C. The number density of terrace nucleated islands increases with substrate terrace width l as ∼l⁴ in a low island density regime. This scaling behavior is consistent with predictions for the case of the irreversible growth of islands.     

Integrity of functional self-assembled monolayers on hydrogen-terminated silicon-on-insulator wafers

Silicon-on-insulator (SOI) wafers are commonly used to design microelectronics, energy conversion, and sensing devices. Thin solid films on the surfaces of SOI wafers have been a subject of numerous studies. However, SOI wafers modified by self-assembled monolayers (SAMs) that can also be used as functional device platforms have been investigated to a much lesser extent. In the present work, tert-butoxycarbonyl (t-boc, (CH₃)₃-C-O-C(O)-)-protected 1-amino-10-undecene monolayers were covalently attached to a H-terminated SOI (1 0 0) surface. The modified wafers were characterized by X-ray photoelectron spectroscopy to confirm the stability of the SAM/Si interface and the integrity of the secondary amine in the SAM. The transmission electron microscopy investigation suggested that this t-boc-protected 1-amino-10-undecene SAM produces atomically flat interface with the 2 μm single crystalline silicon of the SOI wafer, that the SiO_x and both available Si/SiO_x interfaces are preserved, and that the organic monolayers are stable, with apparent thickness of 1.7 nm, which is consistent with the result of the density functional theory modeling of the molecular features within a SAM.     

Surfactant effect of Sb on the growth of MnSi1.7 layers on Si(0 0 1)

Deposition of one monolayer of Sb prior to the deposition of Mn at 600 °C is observed to increase the MnSi_1.7 island density by about two orders of magnitude as well as to change the crystalline orientation of the silicide grains. The preferential epitaxial orientation of MnSi_1.7 grains grown by this process is determined to be MnSi_1.7(1 0 0)[0 1 0]||Si(0 0 1)[1 0 0]. This growth procedure results in the silicide growth into the Si matrix. For comparison, the same deposition process carried out without Sb leads to silicide formation on top of the substrate surface. The observed morphological changes of the MnSi_1.7 layers can be explained by a reduced surface diffusion of the Mn atoms on Si(0 0 1) in presence of the Sb monolayer. Additionally, lateral Si diffusion is considered to be nearly suppressed, which is responsible for the observed silicide growth into the substrate.     

Oxidation of ultrathin indium layers on W(1 1 0)--a core-level photoemission study

We have studied the reaction of ultrathin In overlayers on W(1 1 0) with molecular oxygen at 300 K. At a coverage of 0.25 monolayers (ML) oxygen first chemisorbs dissociatively at free tungsten sites and oxidation of In occurs with some delay. At an In coverage of 1.2 ML complete oxidation of the closed overlayer is observed. Layers of 3 ML thickness first show rapid transformation from In to an In₂O₃-like species until an oxide monolayer is formed. Further oxidation occurs at much reduced rate. No oxygen-induced restructuring is observed for In at 300 K, in contrast to the response of Ag monolayers deposited on W(1 1 0).     

Preparation and tribological tests of thin fluoroorganic films

Adhesion, friction and consequent wear of sliding surfaces are the basic problems that limit the performance and reliability of microelectromechanical devices. Lubrication of these nano- and microscale contacts is different from traditional lubricants. Self-assembled monolayers (SAMs) chemically bonded to the substrate are considered to be the best solution of lubrication. The majority of these monolayers are hydrophobic providing low friction, adhesion and wear.Chemical vapor deposition was used to grow a fluorosilane film on silicon Si(1 0 0) and a condensed monolayer of 3-mercaptopropyltrimethoxysilane (MPTMS) on Au(1 1 1). The films were characterized by means of a contact angle analyzer for hydrophobicity, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) for identification of thin fluoroorganic monolayers deposited on silica surfaces and condensed monolayer MPTMS. Adhesion and friction measurements were performed using atomic force microscopy (AFM) and compared with measurements performed using a microtribometer operating in millinewton (mN) normal load range. Nanotribological measurements indicated that silica and MPTMS modified by fluorosilanes have the lowest friction coefficient and indicated a decrease friction coefficient with increasing fluoric alkyl chain length.     

Formation of strontium template on Si(1 0 0) by atomic layer deposition

The formation of ordered Sr overlayers on Si(1 0 0) by Atomic Layer Deposition (ALD) from bis(triisopropylcyclopentadienyl) Strontium (Sr(C₅ⁱPr₃H₂)₂) and H₂O has been investigated. SrO overlayers were deposited on a 1-2 nm SiO₂/Si(1 0 0) substrate, followed by a deoxidation process to remove the SiO₂ layer at high temperatures. Auger electron spectroscopy, Rutherford backscattering spectrometry, spectroscopic ellipsometry, and low-energy electron diffraction were used to investigate the progress of both ALD and deoxidation processes. Results show that an ordered Sr/Si(1 0 0) surface with 2 × 1 pattern can be obtained after depositing several monolayers of SrO on Si using ALD followed by an anneal at 800-850 °C. The (2 × 1) ordered Sr/Si(1 0 0) surface is known to be an excellent template for the epitaxial growth of SrTiO₃ (STO) oxide. The present results demonstrate that ALD is a potential alternative to molecular beam epitaxy methods for the fabrication of epitaxial oxides on semiconductor substrates.     

Initial stages of iron silicide formation on the Si(1 0 0)2 × 1 surface

The initial stages of iron silicide growth on the Si(1 0 0)2 × 1 surface during solid-phase synthesis were investigated by photoelectron spectroscopy using synchrotron radiation. The experiments were made on iron films of 1-50 monolayer (ML) thickness in the temperature range from room temperature to 750 °С. Our results support the existence of three stages in the Fe deposition on Si(1 0 0) at room temperature, which include formation of the Fe-Si solid solution, Fe₃Si silicide and an iron film. The critical Fe dose necessary for the solid solution to be transformed to the silicide is found to be 5 ML. The solid-phase reaction was found to depend on the deposited metal dose. At 5 ML, the reaction begins at 60 °С, and the solid-phase synthesis leads to the formation of only metastable silicides (FeSi with the CsCl-type structure, γ-FeSi₂ and α-FeSi₂). A specific feature of this process is Si segregation on the silicide films. At a thickness of 15 ML and more, we observed only stable phases, namely, Fe₃Si, ε-FeSi and β-FeSi₂.     

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

The general equation T_ove = L cos  θ ln(R_exp/R₀ + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO₂/SiO₂/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO₂ layer to the thickness of the HfO₂ overlayer was counterbalanced by multiplying the ratio between the intensity of Si⁴⁺ from a thick SiO₂ film and that of Si⁰ from a Si(1 0 0) substrate to the intensity of Si⁴⁺ from the HfO₂/SiO₂/Si(1 0 0) film. With this approximation, the thickness levels of the HfO₂ overlayers showed a small standard deviation of 0.03 nm in a series of HfO₂ (2 nm)/SiO₂ (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO₂ overlayers in a series of HfO₂ (1-4 nm)/SiO₂ (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO₂ overlayer could be determined.     

Strain relaxation and surface morphology of nickel oxide nanolayers

The surface morphology and the lattice constants of NiO overlayers in the thickness range of 1-20 monolayers (NiO nanolayers) on Pd(1 0 0) have been investigated by high-resolution spot profile low-energy electron diffraction (SPA-LEED) and scanning tunneling microscopy (STM). NiO islands grow epitaxially on Pd(1 0 0) on top of a c(4 × 2) Ni₃O₄ monolayer with a compressed strained lattice, which relaxes gradually attaining the bulk lattice constant at 10-12 monolayers. The strain relaxation is accompanied by the formation of small angle mosaic defect regions at the surface, which have been characterised quantitatively by following the behaviour of the satellites to the main Bragg diffraction rods. The analysis of the diffuse scattering intensity around the (0 0) diffraction spot reveals anisotropic NiO island shapes, whose orientation depends on the growth conditions. An incommensurate superlattice in LEED and STM at intermediate NiO coverages (∼2-6 monolayers) is observed and its origin is discussed.     

Adsorption and thermal decomposition of C60 on Co/Si(111)-7 × 7

We present a study on the adsorption and thermal decomposition of C₆₀ on Co covered Si(111)-7 × 7 using scanning tunneling microscopy and X-ray photoelectron spectroscopy. Co-induced magic clusters grown on Si(111)-7 × 7 are identified as a possible adsorption site where 51 ± 3% of C₆₀ molecules adsorb at room temperature. On Co/Si(111)-7 × 7, C₆₀ molecules start to decompose at 450 °C, and are completely dissociated to form SiC by 720 °C. This temperature is significantly lower than 910 °C at which C₆₀ completely dissociates on clean Si(111)-7 × 7. This is a possible low temperature method for growing crystalline SiC films using C₆₀ as a precursor molecule.     

Structural transition of pentacene monolayer on Ga bilayer: From brick-wall structure to herringbone pattern of molecular dimers

Utilizing the substrate of Ga bilayer grown on Si(1 1 1)-√3 × √3-Ga, we have investigated the structural transition of pentacene monolayer induced by moderate annealing. Short-range ordering has been observed in the monolayer pentacene deposited at room temperature. Annealing the sample at ∼350 K produced ordered pentacene monolayer with the “brick-wall” adsorption pattern. The STM images with sub-molecular resolution revealed that the orbital symmetry of the HOMO is reduced from D_2h to C_2v, due to the substrate-molecule interaction, while the deeper HOMO-1 orbital remains intact. Further annealing at ∼400 K led to the formation of molecular dimers as well as the structural transition from “brick-wall” packing to “herringbone” pattern.     

Measurement of optical and electrical properties of silicon microstructuring induced by ArF excimer laser at SF6 atmosphere

The irradiation of ArF excimer laser (193 nm) on Si wafer (〈1 1 1〉, n-type, arsenic-doped, 0.01 Ω cm) in SF₆ atmosphere, from vacuum to 1000 mbar, creates a regular self-assembled microstructure owning to a great number of microconical spikes covered with SiF₂ (fluorosilyl) layer containing sulfur impurities. The geometry of microstructure as well as the layer thickness varies with the gas pressure and the laser parameters, particularly duration, pulse energy and the dose. In this work, the electrical properties of the layer on the microstructured silicon have been investigated based on electrical impedance spectroscopy (EIS). The measured impedance significantly changes regarding to the unirradiated samples. It was shown that the corresponding electrical conductance and the dielectric constants of the layer are strongly dependent on the gas pressure and UV dose. The layer thickness was also determined in terms of SF₆ pressures.     

Scanning tunneling microscopy of surface-adsorbed fullerenes: C60, C70, and C84

Scanning tunneling microscopy (STM) is used to characterize partial monolayers of C₆₀, C₇₀, and C₈₄ adsorbed on the Au(1 1 1) surface at room temperature and under ambient conditions. A high degree of structural polymorphism is observed for monolayers of each of these fullerenes. For C₆₀, three lattice packings are observed, including a previously unreported 7 × 7 R21.8° structure that is stabilized by adjacent surface step defects. For C₇₀, two lattice packings are observed, and analysis of molecular features in STM images allows molecular binding geometry to be determined. In one of the two observed lattice structures, C₇₀ molecules align their long axis along the surface normal, while in the other, molecules align parallel to the surface and along a gold lattice direction. The parallel geometry is also preferred for isolated and loosely packed molecules on the surface. C₈₄ exhibits a large number of lattice orientations and no long-range order, and likely binds incommensurately on Au(1 1 1). Time series of images of partial C₇₀ monolayers show progressive surface modification as a result of perturbation by the STM tip; this is in contrast to the behavior of C₆₀, where alterations in surface structure at room temperature are thermally driven.     

Formation of 10-30 nm SiO2/Si structure with a uniform thickness at ∼120 °C by nitric acid oxidation method

Silicon dioxide (SiO₂) layers with a thickness more than 10 nm can be formed at ∼120 °C by direct Si oxidation with nitric acid (HNO₃). Si is initially immersed in 40 wt.% HNO₃ at the boiling temperature of 108 °C, which forms a ∼1 nm SiO₂ layer, and the immersion is continued after reaching the azeotropic point (i.e., 68 wt.% HNO₃ at 121 °C), resulting in an increase in the SiO₂ thickness. The nitric acid oxidation rates are the same for (1 1 1) and (1 0 0) orientations, and n-type and p-type Si wafers. The oxidation rate is constant at least up to 15 nm SiO₂ thickness (i.e., 1.5 nm/h for single crystalline Si and 3.4 nm/h for polycrystalline Si (poly-Si)), indicating that the interfacial reaction is the rate-determining step. SiO₂ layers with a uniform thickness are formed even on a rough surface of poly-Si thin film.