Surface properties of thin gold layers sputtered on polymers

Thin gold layers were sputtered on the foils of polypropylene-PP, polyethyleneterephthalate-PET, polystyrene-PS, polyethylene-PE and polytetrafluoroethylene-PTFE modified by Ar+ plasma. Surface properties of pristine, plasma treated and gold coated polymers were characterized by two-points method (sheet electrical resistance), electrokinetical analysis (zeta-potential, surface chemistry), goniometry (contact angle), electron paramagnetic resonance (concentration of radicals), atomic force microscopy (AFM, surface morphology and roughness) and scratch test (mechanical properties). Zeta potential and contact angle, as assumed, differ dramatically for plasma treated polymers and for the polymers deposited by Au layers. AFM images indicate that after gold deposition on polymers the surface roughness and the surface morphology change depending on pristine polymer surfaces (roughness and morphology) and sputtering time. Electrical measurements resulted in fact that with increasing layer thickness, the sheet resistance of the gold layer decreases for all polymers with increasing sputtering time. Lower adhesive destruction is observed on the gold layer deposited on plasma treated PE in comparison with pristine.     

Surface relief of crystalline quartz etched in a planar plasma reactor

The surface morphology of dry etched crystalline quartz was studied by transmission electron microscopy (replica technique). The experiments were carried out by reactive ion etching (RIE), plasma etching and argon sputter etching. Argon sputter etching does not alter the sample surface. RIE and plasma etching lead to surface roughness when an aluminum electrode is used. The cone-like asperities produced, typical of the beginning of etching, develop into island-like relief during a longer experiment. It is concluded that the surface roughness is caused by the combined action of backscattering of aluminum particles and their protecting effect in a CF₄ plasma.     

Grafting of gold nanoparticles on polyethyleneterephthalate using dithiol interlayer

Two different procedures of grafting of polyethyleneterephthalate (PET), modified by plasma treatment, with gold nanoparticles (nanospheres) are studied. In the first procedure the PET foil was grafted with biphenyl-4,4′-dithiol and subsequently with gold nanoparticles. In the second one the PET foil was grafted with gold nanoparticles previously coated by the same dithiol. X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and electrokinetic analysis were used for characterization of the polymer surface at different modification steps. Gold nanoparticles were characterized by ultraviolet–visible spectroscopy. The first procedure was found to be more effective. It was proved that the dithiol was chemically bonded to the surface of the plasma activated PET and it mediates subsequent grafting of the gold nanoparticles.     

Preparation of thermosensitive gold nanoparticles by plasma pretreatment and UV grafted polymerization

This work is to develop an easy method of plasma treatment and graft polymerization to prepare thermosensitive gold nanoparticles. Gold nanoparticles (Nano-Au) were reduced by trisodium citrate combined with hydrogen tetrachloroaurate(III) tetrahydrate (chloroauric acid) and modified with 11-mercaptoundecanoic acid (MUA) by the self-assembly monolayers (SAM). The surface graft polymerization of N-isopropylacrylamide (NIPAAm) was carried out by two steps, using O₂ plasma pretreatment of the surface on MUA SAM modified Nano-Au to form the peroxide groups on Nano-Au(MUA), and then subsequently using UV light to induce grafting with thermosensitive polymer. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to direct investigation of the particle size and morphology in situ. The diameters of the gold nanoparticles measured from the TEM images are in good agreement with data measured at room temperature which is about 15 nm. The thermosensitive gold nanoparticles were characterized by chemical structure of surface (ESCA) and Fourier-transform infrared spectroscopy (FTIR). ESCA result suggests that plasma treatments can be employed to generate peroxides on the Nano-Au(MUA) for the subsequent UV graft polymerization of PNIPAAm.     

Application of level set method in simulation of surface roughness in nanotechnologies

One of the limiting factors in applications of plasma etching in nanotechnologies in general will be the control of plasma induced roughness or perhaps control of surface roughness by plasma etching. In this paper we consider roughening of nanocomposite materials during plasma etching for two etching modes (isotropic and anisotropic) by using a level set method. It was found that the presence of two phases with different etch rates (the ratio of the two etch rates is s and the abundance of one phase is p) affects the evolution of the surface roughness and that the etch rate is higher during the isotropic process as compared to the anisotropic process for all values of s and p. At the same time, in case of isotropic process, the higher s leads to a higher overall etch rate. The obtained results apart from their theoretical relevance, have practical implications for surface treatment of nanocomposite materials.     

Irregular shaping of polystyrene nanosphere array by plasma etching

The morphology of nanospheres is crucial for designing the nanofabrication in the nanosphere lithography. Here, by plasma etching, the controllable tailoring of the nanosphere is realized and its morphology dependence on the initial shape, microscopic roughness, and the etching conditions is investigated quantitatively. The results show that the shape evolution strongly depends on the etching gas, power, and process duration. Particularly, the aspect ratio (diameter/height) significantly increases with violent etching, turning the spherical shape into tiny ellipsoidal nanoparticles. The findings are practical to the protocol of non-uniform etching of nanoobjects and provide the useful design tool for the device fabrication at nanoscale.     

Formation and metrology of dual scale nano-morphology on SF(6) plasma etched silicon surfaces

Surface roughness and nano-morphology in SF(6) plasma etched silicon substrates are investigated in a helicon type plasma reactor as a function of etching time and process parameters. The plasma etched surfaces are analyzed by atomic force microscopy. It is found that dual scale nano-roughness is formatted on the silicon surface comprising an underlying nano-roughness and superimposed nano-mounds. Detailed metrological quantification is proposed for the characterization of dual scale surface morphology. As etching proceeds, the mounds become higher, fewer and wider, and the underlying nano-roughness also increases. Increase in wafer temperature leads to smoother surfaces with lower, fewer and wider nano-mounds. A mechanism based on the deposition of etch inhibiting particles during the etching process is proposed for the explanation of the experimental behavior. In addition, appropriately designed experiments are conducted, and they confirm the presence of this?mechanism.     

A facile synthesis of lipid stabilized gold nanoparticles: a step towards biodegradable biosensors

A new class of polylactone was successfully synthesized and utilized for the encapsulation and stabilization of gold nanoparticles. Core/shell nanoparticle architecture, in which a layer of this polymer surrounds the nanoparticle core have been investigated both as a means to improve the stability and surface chemistry and as a way of accessing unique physical properties that are not possible from one nano-material alone. Given the fact that only few systems has so far been developed for the encapsulation of nanoparticles, our success in using a new biodegradable biopolymer with inbuilt functionality reveals the robustness of this work. The biodegradability of this polylactone was evaluated using scanning electron microscopy (SEM). The morphology and stability of these gold-polymer hybrids were evaluated by using the transmission electron microscopy (TEM) and UV-VIS spectroscopy.     

Plasma-modified and polyethylene glycol-grafted polymers for potential tissue engineering applications

Modified and grafted polymers may serve as building blocks for creating artificial bioinspired nanostructured surfaces for tissue engineering. Polyethylene (PE) and polystyrene (PS) were modified by Ar plasma and the surface of the plasma activated polymers was grafted with polyethylene glycol (PEG). The changes in the surface wettability (contact angle) of the modified polymers were examined by goniometry. Atomic Force Microscopy (AFM) was used to determine the surface roughness and morphology and electrokinetical analysis (Zeta potential) characterized surface chemistry of the modified polymers. Plasma treatment and subsequent PEG grafting lead to dramatic changes in the polymer surface morphology, roughness and wettability. The plasma treated and PEG grafted polymers were seeded with rat vascular smooth muscle cells (VSMCs) and their adhesion and proliferation were studied. Biological tests, performed in vitro, show increased adhesion and proliferation of cells on modified polymers. Grafting with PEG increases cell proliferation, especially on PS. The cell proliferation was shown to be an increasing function of PEG molecular weight.     

Statistical demonstration of the relative effect of surface chemistry and roughness on human osteoblast short-term adhesion

The effects of material composition, surface chemistry or surface topography on cell attachment (short-term adhesion) have been largely studied on bone-derived cells. However, no statistical demonstration of these effects has been performed until now. With this objective, we quantified the attachment after 24 hours of human osteoblasts on pure titanium, titanium alloy and stainless steel substrates presenting 6 different surface morphologies and 2 different roughness amplitude obtained by sand-blasting, electro-erosion, acid etching, polishing and machine-tooling. The coating by a gold-palladium layer of these surfaces allowed determining the relative effect of the surface roughness and of the surface chemistry. By multiple analysis of variance, we demonstrated that neither material composition nor surface roughness amplitude influenced cell attachment except on sandblasted pure titanium substrates. On the contrary, a high significant influence of the process used to produce the surface was observed meaning that the main influent factor on cell attachment could be either the surface morphology or the surface chemistry induced by the process. As the coating of surfaces by a gold-palladium layer decreased significantly the attachment of cells on the majority of substrates, we concluded that attachment is rather influenced by surface chemistry than by surface topography.     

Argon plasma treatment of glass surfaces

The effect of argon plasma treatment of glass surfaces is studied by FTIR and SEM. The argon plasma on cleaned glass surfaces resulted in increased surface area due to microetching and surface rearrangement of the silicate network as indicated by the observed changes in the Si-O stretching infrared absorption. The result was a relative increase in surface hydrophilicity which could be optimized by the plasma reaction conditions. The etching action of the argon plasma on the substrate surfaces facilitated the removal of the micrometre thick sizing from the commercial fibres accompanied by little loss in tensile strength. Plasma was also used to graft selected monomers to the surface of glass fibres for enhancement of bond compatibility in a composite system. This grafting treatment was followed by an argon etching step. The argon plasma action on the coated surfaces improved the wettability further and increased the sur face area. Changes in surface chemistry that accompanied the argon etching treatment were very subtle in the case of the plasma polymer of allylamine, but proved significant in the case of the plasma polymer of hexamethyldisiloxane. On the latter surfaces, rearrangement of the siloxane (Si-O-Si) bonds to silylmethylene (Si-(CH₂) _n -Si) groups is suggested.     

Plasma processing for surface optical modifications of PET films

The plasma interaction with the surface produces modifications of its chemical structure or morphology. Surface modifications through cold plasma occur, thanks to the high plasma reactivity and ability to affect the surface of materials.The present work shows the surface modification of polyethylene terephthalate (PET) films after the exposure both to low-pressure plasma (film deposition by plasma enhanced chemical vapour deposition) and to an atmospheric pressure dielectric barrier discharge (surface etching). After plasma treatment we have analysed the effect on the PET surface.For the atmospheric pressure plasma-treated samples, contact angle and atomic force microscope analysis enable us to determine roughness changes. For the low-pressure plasma samples, contact angles and Fourier transform infrared absorption spectroscopy analysis are used to estimate the chemical composition of the deposition and focused ion beam analysis to collect the image and calculate the thickness of plasma deposition.Both plasma treatments (film deposition and etching) cause changes in optical properties as indicated by reflectivity measurements.     

Controlled nucleation and growth of surface-confined gold nanoparticles on a (3-aminopropyl)trimethoxysilane-modified glass slide: a strategy for SPR substrates

The thickness of the gold film and its morphology, including the surface roughness, are very important for getting a good, reproducible response in the SPR technique. Here, we report a novel alternative approach for preparing SPR-active substrates that is completely solution-based. Our strategy is based on self-assembly of the gold colloid monolayer on a (3-aminopropyl)trimethoxysilane-modified glass slide, followed by electroless gold plating. Using this method, the thickness of films can be easily controlled at the nanometer scale by setting the plating time in the same conditions. Surface roughness and morphology of gold films can be modified by both tuning the size of gold nanoparticles and agitation during the plating. Surface evolution of the Au film was followed in real time by UV-vis spectroscopy and in situ SPRS. To assess the surface roughness and electrochemical stability of the Au films, atomic force microscopy and cyclic voltammetry were used. In addition, the stability of the gold adhesion is demonstrated by three methods. The as-prepared Au films on substrates are reproducible and stable, which allows them to be used as electrodes for electrochemical experiments and as platforms for studying SAMs.     

Grafting of gold nanoparticles and nanorods on plasma-treated polymers by thiols

Grafting of gold nanoparticles and nanorods on the surface of polymers, modified by plasma discharge, is studied with the aim to create structures with potential applications in electronics or tissue engineering. Surfaces of polyethyleneterephthalate and polytetrafluoroethylene were modified by plasma discharge and subsequently, grafted with 2-mercaptoethanol, 4,4′-biphenyldithiol, and cysteamine. The thiols are expected to be fixed via one of –OH, –SH or –NH₂ groups to reactive places on the polymer surface created by the plasma treatment. “Free” –SH groups are allowed to interact (graft) with gold nanoparticles and nanorods. Gold nano-objects were characterized before grafting by transmission electron microscopy and UV–Vis spectroscopy. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and electrokinetic analysis (zeta potential determination) were used for the characterization of polymer surface at different modification phases. It was proved by FTIR and XPS measurements that the thiols were chemically bonded on the surface of the plasma-treated polymers, and they mediate subsequent grafting of the gold nano-objects. On the surfaces, modified polymers were indicated some objects by AFM, size of which was dramatically larger in comparison with that of original nanoparticles and nanorods. This result and the other results of UV–Vis spectroscopy indicate an aggregation of deposited gold nano-objects.     

原位聚合制备PLLA/Fe3O4磁性复合微球及其表征

介绍了一种新的PLLA/Fe3O4磁性复合微球的制备方法——表面引发开环聚合法,先利用硅烷偶联剂Z-6040对Fe3O4进行改性,在其表面引入羟基,再通过羟基引发丙交酯在磁粒子表面开环聚合制备PLLA/Fe3O4磁性复合微球。探讨了复合微球的形成机理,对磁粒子改性效果和微球形貌、粒径、结构、磁含量及磁性能等进行了表征,并详细研究了磁性复合微球性能的影响因素。     

Impact of oxygen and argon plasma exposure on the roughness of gold film surfaces

The impact of oxygen and argon plasma exposure on the roughness of gold film Quartz Crystal Microbalance (QCM) electrodes is reported here, employing low levels of gas uptake and scanning tunneling microscope measurements to probe the post-exposure surface morphology. For equal exposure times, argon plasma bombardment is observed to produce both greater material removal and greater change in surface roughness. A possible explanation for this is that the oxygen plasma produces a protective gold oxide layer, which may remove the contaminants from the surface without creating defects in the gold surface. The result is also consistent with prior reports of chemical cleaning of the surface by reactive oxygen ions. Pentane gas adsorption on the argon bombarded QCM surfaces was, moreover, observed to occur at pressures that are several orders of magnitude lower than that for an unbombarded surface.     

Surface Modification of Ti6Al4V Open Porous Structures Produced by Additive Manufacturing

Additive manufacturing techniques can be used to produce micro‐porous structures with global morphological properties that are highly controlled through robust computer design. Despite these advantages, most of these techniques still hold several functional constraints, resulting from present technical device limits and consequently the inability to control surface morphology at a microscale level. In this study, a novel protocol for surface modification of 3D titanium alloy‐based open porous structures is developed, which applies a combination of chemical etching (CHE) and electrochemical polishing (ECP) using HF‐based solutions. This protocol achieves significant and controllable roughness reduction of additive manufactured 3D Ti6Al4V open porous structures. Chemical etching mainly removes the attached powder grains, while ECP further decreases the roughness. In this way the heterogeneity of the strut surface roughness throughout the full 3D structure is effectively removed.     

Ar + H2 plasma etching for improved adhesion of PVD coatings on steel substrates

Ar + H₂ plasma cleaning has been described for the surface modification of the steel substrates, which removes oxides and other contaminants from substrate surface effectively leading to a better adhesion of the physical vapor deposited (PVD) coatings. Approximately 1.1-1.3 μm thick TiAlN coatings were deposited on plasma treated (Ar and Ar + H₂) and untreated mild steel (MS) substrates. A mechanism has been put forward to explain the effect of plasma treatment on the substrate surface based upon the data obtained from X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The XPS measurements on untreated and Ar + H₂ plasma etched MS substrates indicated that the untreated substrate surface mainly consisted of Fe₃O₄, whereas, after etching the concentration of oxides decreased considerably. The FESEM and the AFM results showed changes in the surface morphology and an increase in the substrate roughness as a result of Ar + H₂ plasma etching. Removal of oxide/contaminants, formation of coarser surface and increased substrate surface roughness as a result of Ar + H₂ plasma etching facilitate good mechanical interlocking at the substrate surface, leading to a better adhesion of the deposited PVD coatings. The adhesion of TiAlN coating could be increased further by incorporating a very thin Ti interlayer.     

Chemical stabilization of gold coated by silver core-shell nanoparticles via electron transfer

Silver nanoparticles are notoriously susceptible to oxidation, yet gold nanoparticles coated in silver exhibit a unique electronic interaction that occurs at the interface of the two metals, leading to enhanced stability properties for the silver shell. In order to probe the phenomenon, the stability of gold nanoparticles coated by silver was studied in the presence of various chloride-containing electrolytes. It was found that a critical silver shell thickness of approximately 1 nm exists that cannot be oxidatively etched from the particle surface: this is in contrast to the observation of complete oxidative etching for monometallic silver nanoparticles. The results are discussed in terms of particle composition, structure and morphology before and after exposing the particles to the electrolytes. Raman analysis of the reporter molecule 3-amino-1,2,4-triazole-5-thiol adsorbed on the particle surface illustrates the feasibility of using gold coated by silver nanoparticle probes in sensing applications that require the presence of high levels of salt. The results provide insight into the manipulation of the electronic and stability properties for gold- and silver-based nanoparticles.     

GaN etch rate and surface roughness evolution in Cl2/Ar based inductively coupled plasma etching

Cl₂/Ar based inductively coupled plasma (ICP) etching of GaN is investigated using photoresist mask in a consequential restricted domain of pressure < 1.2 Pa and radio frequency (RF) sample power < 100 W, for selective mesa etching. The etch characteristics and root-mean-square (rms) surface roughness are studied as a function of process parameters viz. process pressure, Cl₂ percentage in total flow rate ratio, and RF sample power at a constant ICP power, to achieve moderate GaN etch rate with anisotropic profiles and smooth surface morphology. The etch rate and resultant surface roughness of etched surface increased with pressure mainly due to dominant reactant limited etch regime. The etch rate and surface roughness show strong dependence on RF sample power with the former increasing and the later decreasing with the applied RF sample power up to 80 W. The process etch yield variation with applied RF sample power is also reported. The studied etch parameters result in highly anisotropic mesa structures with Ga rich etched surface.