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The detection of specific pesticides on food products is essential as these substances pose health risks due to their toxicity. The use of surface-enhanced Raman spectroscopy (SERS) takes advantage of the straightforward technique to obtain fingerprint spectra of target analytes. In this study, SERS-active substrates are made using Au nanoparticles (NPs) coated with a layer of polymer and followed by imprinting with a pesticide&ndash, Cypermethrin, as a molecularly imprinted polymer (MIP). Cypermethrin was eventually removed and formed as template cavities, then denoted as Au NP/MIP, to capture the analogous molecules. The captured molecules situated in-between the areas of high electromagnetic field formed by plasmonic Au NPs result in an effect of SERS. The formation of Au NP/MIP was, respectively, studied through morphological analysis using transmission electron microscopy (TEM) and compositional analysis using X-ray photoelectron spectroscopy (XPS). Two relatively similar pesticides, Cypermethrin and Permethrin, were used as analytes. The results showed that Au NP/MIP was competent to detect both similar molecules despite the imprint being made only by Cypermethrin. Nevertheless, Au NP/MIP has a limited number of imprinted cavities that result in sensing only low concentrations of a pesticide solution. Au NP/MIP is thus a specific design for detecting analogous molecules similar to its template structure.

Surface-enhanced Raman scattering (SERS) technique is competent to trace detection of target species, down to the single molecule level. The detection sensitivity is presumably degraded by the presence of non-specific binding molecules that occupy a SERS-active site (or hot spot) on the substrate surface. In this study, a silver hollow nano-sphere (Ag HNS) with cavity has been particularly designed, followed by depositing dielectric nanoparticles (Di NPs) upon Ag HNS. In the integrated nanostructures, Di NPs/Ag HNS were furthermore confirmed by cutting through the cross sections using the Focused Ion Beam (FIB) technique, which provides the Scanning Electron Microscope (SEM) with Energy-dispersive Spectroscope (EDS) mode for identifying the distribution of Di NPs upon Ag HNS. The results have indicated that Di NPs/Ag HNS exhibits small diameter of cavity, and among Di NPs in this study, Al2O3 with lower dielectric constant provides a much higher SERS enhancement factor (e.g., ~6.2 &times, 107). In this study, to detect trace amounts (e.g., 0.01 ppm) of Ampicillin in water or milk solution, Al2O3 NPs/Ag HNS was found to be more efficient and less influenced by non-specific binding molecules in milk. A substrate with integrated plasmonic and dielectric components was designed to increase the adsorption of target species and to repulse non-specific binding molecules from SERS-active sites.

This study identifies a procedure for the calibration of the Z-magnification of an atomic force microscope below 10 nm by single-atom steps and gives an uncertainty evaluation. A Si(111) surface with periodically arranged single-atom steps was used as a standard reference. The lattice constant of the Si(111) is 0.312 nm, which is traced to SI units through X-ray diffraction. The 33 layers of continuous stacked single-atom steps were scanned and step heights ranging from 0.3 nm to 10 nm were measured and analyzed. The influential factors of calibration for the Z-magnification of an atomic force microscope were identified to estimate the uncertainty according to ISO/IEC Guide 98-3:2008. The relative expanded uncertainties ranged from 4.7% to 5.9%.

As the devices scale down, HfO2 is an excellent gate dielectric material and can replace SiO2 in complementary metal-oxide semiconductor technology. However, the mechanical property-based reliability such as wear resistance and deformation mechanism are rarely understood. This paper describes the effect of annealing treatment on 20-nm-thick HfO2 films under varying applied normal forces (31.3–104.2 μN). According to grazing incident X-ray diffraction analysis, the HfO2 thin films changed from amorphous to polycrystalline structure after annealing treatment. The scratch depth relative to initial surface was proportional to normal force. In addition, plowing behavior dominated the deformation mechanism in the form of lumps along the edge of groove by atomic force microscopy images. The annealing-induced crystallization resulted in reduced penetration depth, coefficient of friction, and wear rate at all applied normal forces, indicating that the surface hardness and wear resistance of HfO2 thin films can be enhanced through appropriate annealing treatment. Furthermore, substrate effect caused negative correlation between wear resistance and normal force was not obvious to annealed samples. It could be attributed to the broadening of HfSixOy interfacial layer which enhanced the structure strength.

Accurate determination of Young's modulus and Poisson's ratio is critical when characterizing the mechanical properties of ultra-thin films. In this work, a method to simultaneously measure the Young's modulus and Poisson's ratio of thin films by X-ray techniques combined with a four-point bending fixture is presented. The four-point bending fixture was carried out to purposely induce stresses on the thin film and cause a curvature of the film/wafer system. The induced stresses were measured by the modified conventional X-ray diffraction for film measurements. At the same time, the curvature of the film/wafer system was measured by the X-ray rocking curve. With the film stress derived from the curvature according to the Stoney formula, both the Poisson's ratio and the Young's modulus were evaluated from the plot of lattice d -spacing changes (strain) versus cos 2 α sin 2 ψ . The method was applied to determine thin copper films (~ 180 nm). The estimated Poisson's ratios ranged from 0.18 to 0.24. Compared to the 0.34 for bulk Cu, the deviation between the bulk and the film properties was above ~ 30%. The Young's modulus of the films is 116.7 ± 2.9 GPa, which was comparable to those reported in the literature for ~ 128 GPa.

Nanoscale scratches are applied using an atomic force microscope (AFM) to investigate the mechanical aspect of the material removal process in chemical–mechanical polishing. The scratching experiments are carried out with the AFM, whose probe has an SiO2 particle (radius ~ 400 nm) bonded to it, at low normal forces in deionized (DI) water and a slurry. The experimental results show that the scratch depth increases with increasing normal force. Under a constant force, the scratch depth of the surface in the slurry is significantly larger than that in DI water. This is due to a soft passivation layer generated during chemical interactions on the copper surface. The passivation layer significantly affects the coefficient of friction (COF) and wear rate. At a low scratch depth (below 20 nm), the COF obtained in DI water is ~ 1.74 times larger than that obtained in the slurry. The wear rate obtained in the slurry is larger than that obtained in the DI water.

10-nm-thick atomic layer deposited HfO 2 films were characterized in terms of wear resistance and indentation hardness to investigate the thermal annealing induced impacts on mechanical properties. The wear resistance of ultra-thin films at low loads was characterized using nano-scratch tests with an atomic force microscope. The depth of the nano-scratches decreases with increasing annealing temperature, indicating that the hardness of the annealed films increases with the annealing temperatures. Surface nanoindentation was also performed to confirm the nanoscratch test results. The hardness variation of the annealed films is due to the generation of HfSi x O y induced by the thermal annealing. X-ray photoelectron spectroscopy measurements proved that the hardness of formed HfSi x O y with increasing annealing temperatures. The existence of HfSi x O y broadens the interface, and causes the increase of the interfacial layer thickness. As a result, the surface hardness increases with the increasing HfSi x O y induced by the thermal annealing.

Ultra-thin hafnium dioxide (HfO2) is used to replace silicon dioxide to meet the required transistor feature size in advanced semiconductor industry. The process integration compatibility and long-term reliability for the transistors depend on the mechanical performance of ultra-thin HfO2 films. The criteria of reliability including wear resistance, thermal fatigue, and stress-driven failure rely on film adhesion significantly. The adhesion and variations in mechanical properties induced by thermal annealing of the ultra-thin HfO2 films deposited on silicon wafers (HfO2/SiO2/Si) are not fully understood. In this work, the mechanical properties of an atomic layer deposited HfO2 (nominal thickness ≈10 nm) on a silicon wafer were characterized by the diamond-coated tip of an atomic force microscope and compared with those of annealed samples. The results indicate that the annealing process leads to the formation of crystallized HfO2 phases for the atomic layer deposited HfO2. The HfSixOy complex formed at the interface between HfO2 and SiO2/Si, where the thermal diffusion of Hf, Si, and O atoms occurred. The annealing process increases the surface hardness of crystallized HfO2 film and therefore the resistance to nano-scratches. In addition, the annealing process significantly decreases the harmonic contact stiffness (or thereafter eliminate the stress at the interface) and increases the nano-hardness, as measured by vertically sensitive nano-indentation. Quality assessments on as-deposited and annealed HfO2 films can be thereafter used to estimate the mechanical properties and adhesion of ultra-thin HfO2 films on SiO2/Si substrates.

The material removal mechanism of chemical mechanical polishing is simplified as a single nanoparticle scratching the surface of a Cu film based on contact mechanics that relates the size of scratches to the applied force. Scratch experiments were carried out using an atomic force microscope with a SiO2 spherical tip with a radius of 400 nm at low normal forces under three environmental conditions, namely air, deionized (DI) water, and slurry. The experimental results show that for a given force, the scratch depth in a slurry environment is significantly larger than that in a DI water environment, which is due to the slurry chemically interacting with the Cu film surface to generate a soft passivation layer. Consequently, the wear rate in the slurry environment was significantly larger than wear rates in the air environment and in the DI water environment, due to the soft passivation layer generation in the slurry environment. The coefficient of friction (COF) in an air environment is ∼205% and ∼356% larger than those in DI water and slurry environments, respectively, at a given scratch depth. The difference in the COF is due to the effect of buoyancy force in the liquids.

To meet challenges for a smaller transistor feature size, ultra-thin HfO2 high-k dielectric has been used to replace SiO2 for the gate dielectric. In order to accurately analyze the ultra-thin HfO2 films by grazing incidence X-ray reflectivity (GIXRR), an appropriate material model with a proper layer structure is required. However, the accurate model is difficult to obtain, since the interfaces between layers of the ultra-thin HfO2 films are not easily identified, especially when post-deposition annealing process is applied. In this paper, 3.0 nm HfO2 films were prepared by atomic layer deposition on p-type silicon wafer, and annealed in Ar environment with temperatures up to 1000 °C. The layer structures and the role of the interfacial layer of the films in the post-deposition annealing processes were evaluated by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The experimental results and analysis showed that layer thicknesses, crystal phases and chemical structures of the ultra-thin HfO2 films were significantly dependent on annealing temperatures. The binding energy shifts of Hf 4f, O 1s, and Si 2p elements revealed the formation of Hf silicate (Hf–O–Si bonding) with increasing annealing temperatures. Due to the silicate formation and increasing silicon oxide formation, the interface broadening is highly expected. The structure analysis of the GIXRR spectra using the modified material structure model from the XPS analysis confirmed the interfacial broadening induced by the post-deposition annealing.

To achieve efficient Cu-Chemical–Mechanical Polishing planarization at miniaturized device dimensions, there is a need for a better understanding of the surface integrity induced by the process. Surface quality and stresses are the two selected indices in this article to evaluate the Cu-CMP process induced surface integrity. The thickness of the passivation layer and the penetration depth of abrasives are considered as the main effects for the generations of surface qualities and residual stress. Experimental validation on copper films on silicon wafer was performed by CMP with different pads and slurries to generate varied residual stresses and surface qualities. Depth of scratches and surface roughness were measured by the atomic force microscope. The stress measurements of the thin films were performed by a Grazing Incident X-ray diffraction instrument with its principles based upon modified sin2Ψ method. Accordingly, the surface roughness and stress were related to the thickness of the passivation layer and the CMP process conditions. When the penetration depth is larger than the passivation layer thickness, the roughness values are mainly decided by the selection of pads and the resultant penetration depth. In addition, the residual stress profiles are dependent on the CMP process conditions which include the slurries and pad parameters. The stress profile obtained for the slurry SDK with soft pad Politex composed smallest maximum tensile stress below the surface and a steady transition of stress profile compared to the stress profile obtained at the initial condition. At the condition for the same slurry SDK, but with a hard pad of IC1000, the CMP process induced larger maximum stress and sharper profile transition.

Small angle X-ray scattering (SAXS) was used to characterize the cross section of nanoline gratings fabricated with electron beam lithography (EBL) patterning followed by anisotropic wet etching into a single crystal silicon substrate. SAXS results at normal incidence clearly bear the signature of positional dependent linewidth within the gratings; such non-uniformity is subsequently confirmed with scanning electron microscopy. The proximity effect of EBL is believed to be the cause of the spatial variations of linewidth. To quantitatively fit the SAXS results the linewidth near the periphery of the patterned field needs to be 80% greater than that in the central region, whereas the cross section of nanolines can be modeled as a simple rectangular shape, as expected from the anisotropic wet etching process.

Demands for substrate and film surface planarizations significantly increase as the feature sizes of Integrated Circuit (IC) components continue to shrink. Chemical Mechanical Polishing (CMP), incorporating chemical and mechanical interactions to planarize chemically modified surface layers, has been one of the major manufacturing processes to provide global and local surface planarizations in IC fabrications. Not only is the material removal rate a concern, the qualities of the CMP produced surface are critical as well, such as surface finish, defects and surface stresses. This paper is to examine the CMP produced surface roughness on tungsten or W thin films based on the CMP process conditions. The W thin films with thickness below 1000 nm on silicon wafer were chemical-mechanical polished at different down pressures and platen speeds to produce different surface roughness. The surface roughness measurements were performed by an atomic force microscope (DI D3100). Results show that the quality of surface finish (R a value) is determined by the combined effects of down pressures and platen speeds. An optimal polishing condition is, then, possible for selecting the down pressures and platen speeds.