Force Curve Measurements with the AFM: Application to the In Situ Determination of Grafted Silicon-Wafer Surface Energies

The atomic force microscope (AFM) can be used to perform surface force measurements in the quasi-static mode (cantilever is not oscillating) to investigate nanoscale surface properties. Nevertheless, there is still a lack of literature proposing a complete systematic and rigorous experimental procedure that enables one to obtain reproducible and significant quantitative data. This article focuses on the fundamental experimental difficulties arising when making force curve measurements with the AFM in air. On the basis of this AFM calibration procedure, quantitative assessment values were used to determine, in situ, SAM (or Self Assembled Monolayer)-tip thermodynamic work of adhesion at a local scale, which have been found to be in good agreement with quoted values. Finally, determination of surface energies of functionalised silicon wafers (as received, CH₃, OH functionalised silicon wafers) with the AFM (at a local scale) is also proposed and compared with the values obtained by wettability (at a macroscopic scale). In particular, the effect of the capillary forces is discussed.     

The preparation and characterisation of nanometre platinum colloids on silicon wafers as model catalysts

Platinum particles of 2 nm diameter have been immobilised on oxidised silicon wafers by spin coating with colloidal solutions and characterised by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The coverage and dispersion of the Pt colloids on the Si wafer are controlled by varying the concentration and the spin speed. Under optimal conditions mono-dispersed Pt colloids on silicon wafers are prepared. For the Pt colloids immobilised on the Si wafer, the majority of the stabilising ligands are removed through a reduction (with H₂ at 200°C) or an oxidation (in air at 300°C) procedure. AFM showed that particle sizes are retained after the reduction procedure, while significant sintering occurs after oxidation. The mechanism of ligand removal was studied using an in situ XPS reaction cell. This revised version was published online in July 2006 with corrections to the Cover Date.     

Self-Assembled Monolayers of Vinyltriethoxysilane and Vinyltrichlorosilane Deposited on Silicon Dioxide Surfaces

Abstract

This study was aimed at deposition of self-assembled monolayers (SAMs) using vinyltriethoxysilane (VTES) and vinyltrichlorosilane (VTCS) molecules chemisorbed on silicon dioxide surfaces. The kinetics of SAM formation on planar glass substrates and silicon wafers was characterized by contact angle measurements. The surface free energy and its dispersion and polar components enabled to estimate the time of immersion required to deposit compact SAMs. Adsorption of organosilane molecules as a function of immersion time was characterized by X-ray photoelectron spectroscopy. The SAM thickness was evaluated by spectroscopic ellipsometry. Surface topography of deposited layers was investigated by atomic force microscopy (AFM). The VTCS/glass combination exhibited the fastest kinetics but the deposit was not uniform and included local agglomerates. The hydrophobic vinyl groups at deposit surface resulted in a surface free energy of 32 mJ/m².     

Usefulness of surfactants in reducing particle adhesion and their effectiveness in cleaning silicon wafers

The effectiveness of surfactants (sodium dodecyl sulfate and dodecyl amine hydrochloride) in the cleaning of silicon wafers has been investigated using atomic force microscopy and image analysis. Recognizing that the surface of SC-1-cleaned silicon wafers is essentially SiO₂ atomic force microscopy was used to determine the interaction forces for the silica/silica and silica/alumina systems with and without surfactant present in solution. Experimental force vs. separation distance curves were found to be in good agreement with theoretical predictions based on electrostatic and van der Waals interactions. Interestingly, the pull-off forces obtained from atomic force microscopy measurements were very close to the adhesion forces calculated on the basis of van der Waals interactions at very close separations. The results from image analysis further confirmed the usefulness of surfactants in reducing particle adhesion and their effectiveness in cleaning silicon wafers. Finally, the results from this study suggest that a more complete understanding of particle interaction forces should be of considerable importance to the electronics industry.     

Microscopic study of electrical properties of CrSi<Subscript>2</Subscript> nanocrystals in silicon

Semiconducting CrSi₂ nanocrystallites (NCs) were grown by reactive deposition epitaxy of Cr onto n -type silicon and covered with a 50-nm epitaxial silicon cap. Two types of samples were investigated: in one of them, the NCs were localized near the deposition depth, and in the other they migrated near the surface. The electrical characteristics were investigated in Schottky junctions by current-voltage and capacitance-voltage measurements. Atomic force microscopy (AFM), conductive AFM and scanning probe capacitance microscopy (SCM) were applied to reveal morphology and local electrical properties. The scanning probe methods yielded specific information, and tapping-mode AFM has shown up to 13-nm-high large-area protrusions not seen in the contact-mode AFM. The electrical interaction of the vibrating scanning tip results in virtual deformation of the surface. SCM has revealed NCs deep below the surface not seen by AFM. The electrically active probe yielded significantly better spatial resolution than AFM. The conductive AFM measurements have shown that the Cr-related point defects near the surface are responsible for the leakage of the macroscopic Schottky junctions, and also that NCs near the surface are sensitive to the mechanical and electrical stress induced by the scanning probe.     

Multifractal characterization of unworn hydrogel contact lens surfaces

Purpose: The aim of this work was to estimate the multifractal spectra of 3D surface roughness for unworn hydrogel contact lenses (CL), obtained with atomic force microscopy (AFM) analysis. Materials and methods: Contact lenses made from vifilcon A (Focus® Monthly Toric Visitint® model, CIBA Vision Corp.) were investigated. CL surface roughness was studied by AFM in tapping‐mode™, in an aqueous environment, on square areas ranging from 1 to 4 μm². A detailed methodology for CL surface multifractal characterization, which may be applied for AFM data, was presented. Results: The CL surface roughness revealed multifractal geometry at various magnifications. The generalized dimension D_q and the singularity spectrum f(α) provided quantitative values that characterize the local scale properties of CL surface geometry at nanometer scale. Conclusions: Multifractal analysis provides different yet complementary information to that offered by traditional surface statistical parameters. POLYM. ENG. SCI., 54:1066–1080, 2014. © 2013 Society of Plastics Engineers     

Frictional behaviour of vertically aligned carbon nanotube films

Vertically aligned CNT films were grown on polycrystalline β-SiC wafers by the surface decomposition method. Their frictional behaviours were investigated by AFM at the nanometer scales. Compared with DLC film and silicon wafers, they demonstrate an extremely low friction coefficient at the nanometer scale about 0.03-0.04. The effect of the surface topography on the friction coefficient is obvious for the aligned CNT film sliding at the nanometer scale. This implies that the excellent tribological properties of the vertically aligned CNT films, combined with their small dimensions and structural perfection, might lead to significant improvement of the performance of nano-devices.     

AFM and Multiple Transmission-Reflection Infrared Spectroscopy (MTR-IR) Studies on Formation of Air-Stable Supported Lipid Bilayers

Supported lipid bilayers (SLBs) were prepared by deposition of unilamellar vesicles on a silicon substrate. Atomic force microscopy (AFM) and a new Multiple Transmission-Reflection Infrared Spectroscopy (MTR-IR) developed by us were used to trace the dynamic formation of lipid bilayers on the silicon surfaces. The evolution from deformation of vesicles to formation of bilayers can be distinguished clearly by AFM imaging. MTR-IR provided high quality infrared spectra of ultrathin lipid bilayers with high sensitivity and high signal to noise ratio (SNR). The structural and orientational changes during vesicle’s fusion were monitored with MTR-IR. MTR-IR shows superiority over other infrared approaches for ultrathin films on standard silicon wafers in view of its economy and high sensitivity. Both MTR-IR and AFM results were consistent with each other and they provided more information for understanding the self-assembling procedure of SLBs.     

Photocatalytic activity of Cr-doped TiO2 nanoparticles deposited on porous multicrystalline silicon films

This work deals with the deposition of Cr-doped TiO₂ thin films on porous silicon (PS) prepared from electrochemical anodization of multicrystalline (mc-Si) Si wafers. The effect of Cr doping on the properties of the TiO₂-Cr/PS/Si samples has been investigated by means of X-ray diffraction (XRD), atomic force microcopy (AFM), photoluminescence, lifetime, and laser beam-induced current (LBIC) measurements. The photocatalytic activity is carried out on TiO₂-Cr/PS/Si samples. It was found that the TiO₂-Cr/PS/mc-Si type structure degrades an organic pollutant (amido black) under ultraviolet (UV) light. A noticeable degradation of the pollutant is obtained for a Cr doping of 2 at. %. This result is discussed in light of LBIC and photoluminescence measurements.     

Surface interaction of Cu (NO3)2(H2O)2.5 with oxidised Si(100)

Model catalysts were prepared by spin-coating untreated and hydrated silicon wafers using Cu(NO₃)₂(H₂O)_2.5 solved in cyclohexanone as precursor. The prepared surfaces were examined by atomic force microscopy and Rutherford backscattering spectrometry. Spin-coating untreated silicon wafers resulted in clusters composed of small particles. The use of hydrated silicon wafers as substrate resulted in highly disperse small particles. We attribute the difference in surface morphology to the presence of more silanol groups on the surface of the hydrated wafers.     

Plasma-activated direct bonding of diamond-on-insulator wafers to thermal oxide grown silicon wafers

Diamond-on-insulator (DOI) wafers featuring ultrananocrystalline diamond are studied via atomic force microscopy, profilometer and wafer bow measurements. Plasma-activated direct bonding of DOI wafers to thermal oxide grown silicon wafers is investigated under vacuum. DOI wafer with chemical mechanical polishing (CMP) on the diamond surface makes a poor bonding to silicon wafers with thermal oxide. Our results show that plasma enhanced chemical vapor deposition of silicon dioxide on top of the DOI wafer, CMP of the oxide layer and annealing are essential to achieve very high quality direct bonding to thermal oxide grown on silicon wafers. Plasma activation results in the formation of high quality bonds without exceeding 550 °C in the direct wafer bonding process.     

Determining Surface Potential of the Bitumen‐Water Interface at Nanoscale Resolution using Atomic Force Microscopy

Atomic force microscopy (AFM) was used to measure the surface forces between a silicon nitride AFM tip and a deposited layer of Athabasca bitumen; the measurements were carried out in pure water (pH 6.0–6.5) and 1 mM KCl solution (pH 9). An AFM pyramidal‐shaped tip was moved stepwise using an operator‐controlled offset (10 nm per step) and the tip‐bitumen colloidal forces were measured at each location. Surface charge densities at the bitumen‐water interface were calculated from the measured colloidal forces using a theoretical model that combined both electrostatic and van der Waals forces for a conical tip‐flat substrate system. Fitted values of the bitumen surface charge density ranged from –0.002 to –0.004 C/m² in water (pH 6.0–6.5), and –0.005 to –0.022 C/m² in KCl solution (pH 9); the variation of local charge density along the bitumen surface appeared random. Bitumen surface potentials were also calculated from the surface charge densities using the Graham equation; the values ranged from –90 to –130 mV in water, and –45 to –110 mV in KCl solution. This study suggests the presence of bitumen surface domains of different surface charge densities/surface potentials. The domains are estimated to have characteristic sizes of 20 to 40 nm or less.     

Silicon Nitride Colloidal Probe Measurements: Interparticle Forces and the Role of Surface-Segment Interactions in Poly(acrylic acid) Adsorption from Aqueous Solution

Direct measurements of forces between silicon nitride surfaces in the presence of poly(acrylic acid) (PAA) are presented. The force-distance curves were obtained at pH > pH_iep with an atomic force microscopy (AFM) colloidal-probe technique using a novel spherical silicon nitride probe attached to the AFM cantilever. We found that PAA adsorbs onto the negatively charged silicon nitride surface, which results in an increased repulsive surface potential. The steric contribution to the interparticle repulsion is small and the layer conformation remains flat even at high surface potentials or high ionic strength. The general features of the stabilization of ceramic powders with PAA are discussed; we suggest that PAA adsorbs onto silicon nitride by sequential adsorption of neighboring segments ("zipping"), which results in a flat conformation. In contrast, the long-range steric force found in the ZrO₂/PAA system at pH > pH_iep arises because the stretched equilibrium bulk conformation of the highly charged polymer is preserved via the formation of strong, irreversible surface-segment bonds on adsorption.     

AFM adhesion force measurements on conversion-coated EN AW-6082-T6 aluminium

Atomic force microscopy (AFM) has been used to measure the adhesion force between functionalised AFM tips and smooth surfaces of an EN AW-6082-T6 aluminium alloy, both before and after application of different conversion coatings. In addition, the surface of a sapphire sample was studied as a model aluminium surface. The results obtained for the sapphire surface were highly reproducible, and were used as a mean to establish proper routines for the more complex industrial surfaces. The adhesion force between a chromate conversion-coated (CCC) EN AW-6082-T6 aluminium alloy and a COOH functionalised tip was significantly increased compared to the uncoated surface, probably as a result of strong hydrogen bonding. However, the adhesion force decreased with time during the first 24 h after treatment due to aging of the CCC. Chromate-free Ti–Zr-based treatment also increased the adhesion, but the adhesion force varied significantly due to non-uniform deposition and composition of the conversion coating. The measured AFM adhesion forces correlated qualitatively with macroscopic adhesion test results obtained previously for these specific conversion coatings. The AFM technique may thus provide useful information on the adhesion behaviour of heterogeneous conversion-coated aluminium surfaces.     

Evaluation of citric acid added cleaning solution for removal of metallic contaminants on Si wafer surface

We have investigated cleaning solutions based on citric acid (CA) to remove metallic contaminants from the silicon wafer surface. Silicon wafers were intentionally contaminated with Fe, Ca, Zn, Na, Al and Cu standard solution by spin coating method and cleaned in various CA-added cleaning solutions. The concentration of metallic contaminants on the silicon wafer surface before and after cleaning was analyzed by vapor phase decomposition/inductively coupled plasma-mass spectrometry (VPD/ICP-MS). And the surface micro-roughness was also measured by atomic force microscopy (AFM) to evaluate the effect of cleaning solutions. It was found that acidic CA/H₂O solution has the ability to remove metallic contaminants from silicon surfaces. Fe, Ca, Zn and Na on silicon surface were decreased from the order of 10¹² atoms/cm² to the order of 10⁹ atoms/cm² even at low CA concentration, low temperature of CA solution and with short immersion time. CA was also effective in alkali cleaning solution. Fe, Ca, Zn, Na and Cu were reduced down to the order of 10⁹ atoms/cm² in CA added with NH₄OH/H₂O₂/H₂O solution without degradation of surface micro-roughness.     

Nanoscale electro-structural characterisation of ohmic contacts formed on p-type implanted 4H-SiC

This work reports a nanoscale electro-structural characterisation of Ti/Al ohmic contacts formed on p-type Al-implanted silicon carbide (4H-SiC). The morphological and the electrical properties of the Al-implanted layer, annealed at 1700°C with or without a protective capping layer, and of the ohmic contacts were studied using atomic force microscopy [AFM], transmission line model measurements and local current measurements performed with conductive AFM.     

Crystallographic anisotropy of growth and etch rates of CVD diamond

The investigation of orientation dependent crystal growth and etch processes can provide deep insights into the underlying mechanisms and thus helps to validate theoretical models. Here, we report on homoepitaxial diamond growth and oxygen etch experiments on polished, polycrystalline CVD diamond wafers by use of electron backscatter diffraction (EBSD) and white-light interferometry (WLI). Atomic force microscopy (AFM) was applied to provide additional atomic scale surface morphology information. The main advantage of using polycrystalline diamond substrates with almost random grain orientation is that it allows determining the orientation dependent growth (etch) rate for different orientations within one experiment. Specifically, we studied the effect of methane concentration on the diamond growth rate, using a microwave plasma CVD process. At 1% methane concentration a maximum of the growth rate near <100> and a minimum near <111> is detected. Increasing the methane concentration up to 5% shifts the maximum towards <110> while the minimum stays at <111>. Etch rate measurements in a microwave powered oxygen plasma reveal a pronounced maximum at <111>. We also made a first attempt to interpret our experimental data in terms of local micro-faceting of high-indexed planes.     

A study of adhesion forces by atomic force microscopy

An atomic force microscope (AFM) was used to investigate Si₃N₄ tip interactions with various materials in four different liquid media (water, ethanol, ethylene glycol, and formamide). The adhesion forces calculated using surface energies and the values measured experimentally were compared. For all materials, the calculated adhesion force closely correlated with AFM measurements, except in water. In the case of water, the AFM experiments showed strong adhesion, whereas theoretically (van Oss-Chaudhury-Good model) repulsion is predicted. The difference observed is discussed in terms of the chemical interactions between Si₃N₄ and water.     

Near-surface processing on AlGaN/GaN heterostructures: a nanoscale electrical and structural characterization

The effects of near-surface processing on the properties of AlGaN/GaN heterostructures were studied, combining conventional electrical characterization on high-electron mobility transistors (HEMTs), with advanced characterization techniques with nanometer scale resolution, i.e., transmission electron microscopy, atomic force microscopy (AFM) and conductive atomic force microscopy (C-AFM). In particular, a CHF₃-based plasma process in the gate region resulted in a shift of the threshold voltage in HEMT devices towards less negative values. Two-dimensional current maps acquired by C-AFM on the sample surface allowed us to monitor the local electrical modifications induced by the plasma fluorine incorporated in the material.     

Boron carbide films deposited by a magnetron sputter–ion plating process: film composition and tribological properties

Amorphous boron carbide films were deposited onto silicon substrates by a magnetron sputter–ion plating process in an argon plasma atmosphere (0.25 Pa) using a B₄C target. The substrates were polarized with a d.c. bias voltage in the range from 0 to −100 V. The film composition and the presence of contaminants were determined by ion beam analysis (IBA). The nanoscale tribological properties were investigated by atomic force microscopy (AFM). IBA revealed that the boron/carbon atomic ratio is around 4 and that oxygen contamination does not exceed 10 at.%. The hydrogen content is below 2 at.%. The film density is nearly the bulk value for all biases applied to the substrate. AFM measurements show that the surface roughness decreases with increase of bias from 0.85 to 0.15 nm. The friction coefficient obtained by lateral force measurements follows the same trend, decreasing with increasing bias from 0.25 to 0.1. Wear measurements were performed and the wear depth decreased for films with lower friction coefficients. A mechanism based on the removal of a modified B₄C surface layer is proposed to explain the wear results.