Surfaces

Antiseptics and disinfectants are extensively used for a variety of topical and hard-surface applications. A wide variety of biocides as active chemical agents is found in these products, including alcohols, phenols, iodine, and chlorine. Many of these active agents demonstrate broad-spectrum antimicrobial activity; however, the mode of action of these agents is not well-documented. This review is focused on several examples of ionic systems based on ionic surfactants and ionic liquids as well as nanomaterials and nanoparticles acting as antiseptics and disinfectants for surfaces. It is important to note that many of these biocides may be used singly or in combination in a variety of products, which vary considerably in activity against microorganisms. Antimicrobial activity can be influenced by several factors such as formulation effects, presence of an organic load, synergy, temperature, dilution, and test method. The most promissory compounds based on ionic systems and nanomaterials published in mainly the last decade is chronologically reported in this review. Full article

Conductive polymers are nowadays attracting great attention for their peculiar mechanical, electrical and optical proprieties. In particular, PEDOT can be used in a wide range of innovative applications, from electroluminescent devices to photovoltaics. In this work, the electrochemical deposition of 3,4 ethylenedioxythiophene (EDOT) was performed on various substrates (ITO, thin films of gold and palladium on silicon wafers) by means of both potentiostatic and potentiodynamic techniques. This was intended to further expand the applications of electrochemically deposited PEDOT, particularly regarding the preparation of thin films in tight contact with electrode surfaces. This allows one to obtain systems prone to be used as electrodes in stacked devices. Chronoamperometric experiments were performed to study the nucleation and growth process of PEDOT. SEM, ESEM and AFM analysis allowed the characterization of the morphology of the polymeric films obtained. Raman and visible spectroscopy confirmed the high-quality of the coatings on the different substrates. Then, the PEDOT films were used as the base material for the further electrodeposition of a copper layer. In this way, a hybrid electronic device was obtained, by using electrochemical methods only. The high conductivity and ohmic behavior of the device were confirmed over a wide range of frequencies with electrical impedance spectroscopy analysis. Full article

In this contribution, the variational problem for the Kirchhoff plate based on the modified strain gradient theory (MSGT) is derived, and the Euler-Lagrange equations governing the equation of motion are obtained. The Galerkin-type weak form, upon which the finite element method is constructed, is derived from the variational problem. The shape functions which satisfy the governing homogeneous partial differential equation are derived as extensions of Adini-Clough-Melosh (ACM) and Bogner-Fox-Schmit (BFS) plate element formulations by introducing additional curvature degrees of freedom (DOF) on each node. Based on the proposed set of shape functions, 20-, 24-, 28- and 32- DOF modified strain gradient theory-based higher-order Kirchhoff microplate element are proposed. The performance of the elements are demonstrated in terms of various tests and representative boundary value problems. Length scale parameters for gold are also proposed based on experiments reported in literature. Full article

Thin films of ZnWO₄, a promising photocatalytic and scintillator material, were deposited for the first time using a reactive dual magnetron sputtering procedure. A ZnO target was operated using an RF signal, and a W target was operated using a DC signal. The power on the ZnO target was changed so that it would match the sputtering rate of the W target operated at 25 W. The effects of the process parameters were characterized using optical spectroscopy, X-ray diffraction, and scanning electron microscopy, including energy dispersive X-ray spectroscopy as well as X-ray photoelectron spectroscopy. It was found that stoichiometric microcrystalline ZnWO₄ thin films could be obtained, by operating the ZnO target during the sputtering procedure at a power of 55 W and by post-annealing the resulting thin films for at least 10 h at 600 °C. As FTO coated glass substrates were used, annealing led as well to the incorporation of Na, resulting in n+ doped ZnWO₄ thin films. Full article

Adding uniaxial in-plane anisotropy to the otherwise four-fold Si(001) surface has for a long time been known to be possible via epitaxial deposition of a single atomic layer of calcium fluoride (CaF₂), which forms an array of micron-long (110) oriented parallel stripes when the substrate temperature during the growth is kept in the range of 700–800 °C. As shown in the present paper, a fine control over dimensions and periodicity of the stripe array is possible through the introduction of a two-stage growth process at which the (110) orientation of the fluorite layer is settled at the high-temperature nucleation stage, while the stripes of controllable dimensions are formed at the second stage. By varying the substrate temperature at the second growth stage in the range of 800–400 °C, the stripe arrays with a periodicity from above 30 nm to below 10 nm can be fabricated with the height variation changing accordingly. Such variability can be of use in the applications in which the striped fluorite surface is used to influence the anisotropy of other functional (e.g., magnetically ordered or organic) materials grown on top. While large CaF₂ stripes can be easily characterized by direct space techniques such as atomic force microscopy, the study of the shape and in-plane correlation between the stripes of a much smaller size is most effectively achieved through the use of grazing incidence reciprocal space techniques applied in the present paper. The discussed universal approach to 3D reciprocal space mapping utilizing scattering of X-rays and high-energy electrons offers a complementary way to study samples with arrays of long and narrow one-dimensional stripes at their surface. Full article

Residual stress and thermal stress of a film/substrate system are determined based on the curvature measurement with a 3D digital image correlation method (DIC) and calculation of the thin-film stresses by the extension of Stoney’s formula. A Ni film electroplated on a H62Cu plate is used to verify the proposed method. The full fields of nonuniform thin-film stresses are obtained in a room temperature to high-temperature environment of 200 °C, which can be potentially extended to higher temperatures. These results provide a fundamental approach to understanding thin-film stresses and a feasible measurement method for high temperature. Full article

The surface functionalization of oxide-free hydrogen-terminated silicon (Si−H) enables predictably tuning its electronic properties, by incorporating tailored functionality for applications such as photovoltaics, biosensing and molecular electronics devices. Most of the available chemical functionalization approaches require an external radical initiator, such as UV light, heat or chemical reagents. Here, we report forming organic monolayers on Si–H surfaces using molecules comprising terminal alcohol (–OH) groups. Self-assembled monolayer (SAM) formation is spontaneous, requires no external stimuli–and yields Si–O–C covalently bound monolayers. The SAMs were characterized by X-ray photoelectron spectroscopy (XPS) to determine the chemical bonding, by X-ray reflectometry (XRR) to determine the monolayers thicknesses on the surface and by atomic force microscopy (AFM) to probe surface topography and surface roughness. The redox activity and the electrochemical properties of the SAMs were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The availability and the ease of incorporating OH groups in organic molecules, makes this spontaneous grafting as a reliable method to attach molecules to Si surfaces in applications ranging from sensing to molecular electronics where incorporating radical initiator setups is not accessible. Full article

Polytetrafluoroethylene (PTFE), polyhexafluoropropylene (PHFP) and polychlorotrifluoroethylene (PCTFE) were heated to their decomposition temperature in a high vacuum. The emitted fragments passed an electron cloud, condensed on a substrate and formed fluoropolymer film. Growth rate of PTFE and PHFP films increased up to a factor five in the presence of the electron cloud. Mass spectrometry revealed changes in the mass spectra of fragments generated by thermal decomposition only and formed under electron activation. The observed changes were different for each fluoropolymer. Infrared spectroscopy (IRS) showed that the structure of the films was close to the structure of the bulk polymers. Atomic force microscopy (AFM) has revealed different morphologies of PTFE, PHFP and PCTFE films, suggesting a Volmer–Weber growth mechanism for PTFE and PHFP but a Frank-van der Merwe one for PCTFE. All films were smooth at nanoscale and transparent from ultraviolet to near-infrared region. Additional radio frequency (RF) plasma ignited in the emitted fragments at a low pressure increased mechanical characteristics of the films without losing their optical transparency and smoothness. Full article

Boron- and cerium-doped titania (Anatase) were prepared via sol-gel method. Phase composition and morphology were assessed by X-ray diffraction (XRD), scanning electronic microscopy (SEM), BET, diffuse reflectance spectra (DRS), and XPS. Photo-electrochemistry of these materials, deposited onto fluorine-doped SnO₂ (FTO), was investigated in acid and acid-containing methanol. The boron-doped sample showed the best opto-electronic properties among the investigated samples. On the other hand, the cerium-doped titania samples annihilate to a certain extent the titania surface states, however, photogenerated charge separation was limited, and certainly associated to surface Ce³⁺/Ce⁴⁺ species. The substitutional effect of boron ions for O sites and interstitial sites was confirmed by XRD and XPS analyses. Full article

Decontamination of water from radionuclides contaminants is a key priority in environmental cleanup and requires intensive effort to be cleared. In this paper, a microporous iron-doped zeolite-like sodium zirconosilicate ([email protected]) was designed through hydrothermal synthesis with various Si/Zr ratios of 5, 10, and 20, respectively. The synthesized materials of [email protected] materials were well characterized by various techniques such as XRD, SEM, TEM, and N₂ adsorption–desorption measurements. Furthermore, the [email protected] and [email protected] samples had a crystalline structure related to the Zr–O–Si bond, unlike the [email protected] which had an overall amorphous structure. The fabricated [email protected] nanocomposite showed a superb capability to remove cesium ions from ultra-dilute concentrations, and the maximum adsorption capacity was 21.5 mg g^–1 at natural pH values through an ion exchange mechanism. The results of cesium ions adsorption were found to follow the pseudo-first-order kinetics and the Langmuir isotherm model. The microporous iron-doped sodium zirconosilicate is described as an adsorbent candidate for the removal of ultra-traces concentrations of Cs(I) ions. Full article

Single-molecular devices show remarkable potential for applications in downscale electronic devices. The adsorption behavior of a molecule on a metal surface is of great importance from both fundamental and technological points of view. Herein, based on first-principles calculations, the adsorption of a 4,4″-diamino-p-terphenyl (DAT) molecule on a Cu(001) surface has been systematically explored. The most stable configuration is the DAT molecule lying flat with a rotation angle of 13° relative to the [100] surface direction. It was found that the adsorption sites of benzene rings and nitrogen atoms in the DAT molecule have important influences on the stability of the adsorption configuration. Electron density differences analysis shows that the electrons accumulate at the DAT-Cu(001) interface. The density of states projected on a DAT molecule of DAT/Cu(001) exhibits a metallic character, while the freestanding ones are semiconducting, indicating a strong interaction between the DAT molecule and the Cu(001) surface in the most stable adsorption configuration. These results provide useful information for tuning the properties and functions of DAT molecules, and may offer useful insights for other organic molecule/surface systems. Full article

We present here a method for the quantitative prediction of the spectroscopic specular reflectivity line-shape in anisotropic layered media. The method is based on a 4 × 4 matrix formalism and on the simulation from the first principles (through density functional theory—DFT) of the anisotropic absorption cross-section. The approach was used to simulate the reflectivity at the oxygen K-edge of a 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) thin film on Au(111). The effect of film thickness, orientation of the molecules, and grazing incidence angle were considered. The simulation results were compared to the experiment, permitting us to derive information on the film geometry, thickness, and morphology, as well as the electronic structure. Full article

Hexagonal molybdenum trioxide (h-MoO₃) was synthesized by microwave-assisted hydrothermal method, allowing an ultrafast growth of unidimensional microrods with well-faceted morphology. The crystalline structure of this metastable phase was confirmed by X-ray diffraction (XRD) and Raman spectroscopy. Scanning electron microscopy (SEM) showed that hexagonal microrods can be obtained in one minute with well-defined exposed facets and the fine control of morphology. Sensing tests of the acetone biomarker revealed that the h-MoO₃ microrods exhibit, at low ppm level, good sensor signal, fast response/recovery times, selectivity to different interferent gases, and a lower detection limit of 400 ppb. Full article

Here, we present a proof-of-concept experiment where phase engineering at the nanoscale of 2D transition metal dichalcogenides (TMDC) flakes (from semiconducting 2H phase to metallic 1T phase) can be achieved by thermal annealing of a TMDC/Au/mica system. The local dewetting of Au particles and resulting tensile strain produced on the TMDC flakes, strongly bound to the Au surface through effective S-Au bonds, can induce a local structural phase transition. An important role is also played by the defects induced by the thermal annealing: when vacancies are present, the threshold strain needed to trigger the phase transition is significantly reduced. Scanning photoelectron microscopy (SPEM) was revealed to be the perfect tool to monitor the described phenomena. Full article

The lack of scalable synthesis of transition metal dichalcogenides, such as molybdenum disulfide (MoS₂), has proved to be a significant bottleneck in realization of fundamental devices and has hindered the commercialization of these materials in technologically relevant applications. In this study, a cost-efficient and versatile thin-film fabrication technique based on ionized jet deposition (IJD), i.e., a technique potentially providing high processing efficiency and scalability, is used to grow MoS₂ thin films on silicon substrates. The operating conditions of IJD were found to influence mainly the ablation efficiency of the target and only slightly the quality of the deposited MoS₂ thin film. All as-deposited films show chemical properties typical of MoS₂ with an excess of free, elemental sulfur that can be removed by post-deposition annealing at 300–400 °C, which also promotes MoS₂ crystallization. The formation of an interface comprised of several silicon oxide species was observed between MoS₂ and the silicon substrate, which is suggested to originate from etching and oxidizing processes of dissociated water molecules in the vacuum chamber during growth. The present study paves the way to further design and improve the IJD approach for TMDC-based devices and other relevant technological applications. Full article

The surface functionalization of inorganic nanoparticles is an important tool for the production of homogeneous nanocomposites. The chemical adaptation of the nano-filler surface can lead to effective weak to strong interactions between the fillers and the organic matrix. Here we present a detailed systematic study of different surface-functionalized particles in combination with a SAXS method for the systematic investigation of the interface interaction in the development of epoxy nanocomposites. We investigated the effect of surface modification of spherical SiO₂ nanoparticles with 9 nm and 72 nm diameter and crystalline ZrO₂ nanoparticles with 22 nm diameter on the homogeneous distribution of the fillers in diethylenetriamine (DETA) cured bisphenol-F-diglycidylether epoxy resin nanocomposites. Unmodified nanoparticles were compared with surface-modified oxides having diethylene glycol monomethyl ethers (DEG), 1,2-diols, or epoxy groups attached to the surface. The influence of surface modification on dispersion quality was investigated by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) for inorganic filler contents of 3, 5 and 10 wt%. It was shown that the dispersion quality can be optimized by varying the coupling agent end group to obtain homogeneous and transparent nanomaterials. UV/VIS measurements confirmed the transparency/translucency of the obtained materials. The relationship between particle–matrix interaction and particle–particle interaction plays a decisive role in homogeneity and is controlled by the surface groups as well as by the type, size, and morphology of the nanoparticles themselves. Full article

This research investigates deformation behavior of polystyrene (PS) as a thermoplastic resist material for the thermal nanoimprint lithography (T-NIL) process. Molecular dynamics modeling was conducted on a PS substrate with dimensions 58 × 65 × 61 Å that was imprinted with a rigid, spherical indenter. The effect of indenter size, force, and imprinting duration were evaluated in terms of indentation depth, penetration depth, recovery depth, and recovery percentage of the polymer. The results show that the largest indenter, regardless of force, has the most significant impact on deformation behavior. The 40 Å indenter with a 1 µN of force caused the surface molecules to descend to the lowest point compared to the other indenters. An increase in indenter size resulted in higher penetration depth, recovery depth, and recovery percentage. Higher durations of imprint cycle (400 fs) resulted in plastic deformation of the PS material with minimal recovery (4 Å). The results of this research lay the foundation for explaining the effect of several T-NIL process parameters on virgin PS thermoplastic resist material. Full article