Fabrication and characterization chitosan/functionalized zinc oxide bionanocomposites and study of their antibacterial activity

This study deals with preparation and evaluation of properties of chitosan/zinc oxide bionanocomposites (CT/ZnO BNCs) with different amounts of modified zinc oxide nanoparticles (ZnO NPs) through ultrasonic irradiation technique. Due to the high surface energy and tendency for agglomeration, the surface ZnO NPs was modified by a coupling agent as 3-aminopropyltriethoxysilane (APS) to form APS–ZnO nanoparticles. Fourier transform infrared (FTIR) spectroscopy confirmed that APS was successfully grafted onto the ZnO nanoparticles surface. Thermogravimetric analysis (TGA) revealed a surface coverage of the coupling molecule of 2.6 wt%. The resulting bionanocomposites were characterized by FTIR spectra, X-ray diffraction patterns, and TGA. The antibacterial activity of bionanocomposite films was tested against gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis) and gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). The results of CT/ZnO BNCs revealed that the thermal and antibacterial properties obviously improved the presence of ZnO NPs in comparison with the pure CT and that this increase is higher when the NP content increases. Further, it was observed that antibacterial activity of the resulting hybrid biofilms showed somewhat higher for gram-positive bacteria compared to gram-negative bacteria.     

The effect of annealing on structural,optical and electrical properties of ZnS/porous silicon composites

ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I–V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diflraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature,the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550 nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I-V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.     

Effect of annealing on structural, optical and electrical properties of ZnS/porous silicon composites

ZnS films were prepared by pulsed laser deposition (PLD) on porous silicon (PS) substrates. This paper investigates the effect of annealing temperature on the structural, morphological, optical and electrical properties of ZnS/PS composites by x-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) and I--V characteristics. It is found that the ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction, and the intensity of diffraction peak increases with increasing annealing temperature, which is attributed to the grain growth and the enhancement of crystallinity of ZnS films. The smooth and uniform surface of the as-prepared ZnS/PS composite becomes rougher through annealing treatment, which is related to grain growth at the higher annealing temperature. With the increase of annealing temperature, the intensity of self-activated luminescence of ZnS increases, while the luminescence intensity of PS decreases, and a new green emission located around 550~nm appeared in the PL spectra of ZnS/PS composites which is ascribed to the defect-center luminescence of ZnS. The I--V characteristics of ZnS/PS heterojunctions exhibited rectifying behavior, and the forward current increases with increasing annealing temperature.     

Structure and photoluminescence properties of ZnS films grown on porous Si substrates

ZnS films were deposited on porous silicon (PS) substrates with different porosities. With the increase of PS substrate porosity, the XRD diffraction peak intensity decreases and the surface morphology of the ZnS films becomes rougher. Voids appear in the films, due to the increased roughness of PS structure. The photoluminescence (PL) spectra of the samples before and after deposition of ZnS were measured to study the effect of substrate porosity on the luminescence properties of ZnS/PS composites. As-prepared PS substrates emit strong red light. The red PL peak of PS after deposition of ZnS shows an obvious blueshift. As PS substrate porosity increases, the trend of blueshift increases. A green emission at about 550 nm was also observed when the porosity of PS increased, which is ascribed to the defect-center luminescence of ZnS. The effect of annealing time on the structural and luminescence properties of ZnS/PS composites were also studied. With the increase of annealing time, the XRD diffraction peak intensity and the self-activated luminescence intensity of ZnS increase, and, the surface morphology of the ZnS films becomes smooth and compact. However, the red emission intensity of PS decreases, which was associated with a redshift. White light emission was obtained by combining the luminescence of ZnS with the luminescence of PS.     

Surface properties of platinum thin films as a function of plasma treatment conditions

We examined the surface properties of platinum (Pt) thin films exposed to oxygen and argon plasma treatments and compared them to as-deposited Pt films. The surface wetting properties, refractive index and extinction coefficient of the Pt films were monitored as a function of time after different plasma treatments. Surfaces treated with an oxygen plasma were dramatically different from as-deposited Pt, whereas argon plasma treated surfaces were similar to as-deposited films. X-ray photoelectron spectroscopy confirmed the formation of platinum oxide on films treated with an oxygen plasma, while such oxide diminished after argon plasma treatment. Surface morphology studied with atomic force microscopy indicated a strong dependence of the surface roughness of the Pt films on the power and duration of the argon plasma used for the treatment. Based on these studies, an oxygen plasma treatment followed by a brief low-power argon plasma etch was developed for the purpose of regenerating clean and metallic Pt surfaces, and at the same time providing the smoothest possible surface morphology.     

Characterization of fluoroalkylsilane monolayer on polystyrene sphere arrays after plasma treatment

Polystyrene (PS) colloidal crystal films with well-ordered arrays of PS spheres treated with argon plasma and coated with fluoroalkylsilane (FAS) were characterized by means of spectroscopy ellipsometry, X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF-SIMS). The XPS analysis indicated that the FAS film on the plasma treated PS surface was a monolayer with an orderly packed CF₃ group pointing outwards from the surface. The chemical composition of the PS surface changed immediately after a very short period of argon plasma treatment, while the subsequent coating of FAS on the plasma treated PS surface further modified the surface chemistry. The untreated PS surface exhibited poor interaction with FAS molecules. XPS and ToF-SIMS analyses showed the plasma treatment involved the oxidation of PS surface, where oxygen functional groups -O and O were generated, promoting FAS deposition on the plasma treated surface with strong secondary ion fragments originating from the FAS. The overall results indicated that plasma treatment was beneficial to the deposition of the FAS monolayer.     

Efficient visible electroluminescence from porous silicon diodes with low driven voltage

By using n-butylamine as carbon resource, diamond-like carbon film (DLCF) was deposited on the p-n porous silicon (PS) surface by means of a radio-frequency glow discharge plasma system. Electroluminescent (EL) spectra show that EL intensity of the passivated PS diodes increases by 4.5 times and 30-nm blue-shift of EL peak occurs compared with the diodes without treatment and both of them are stable while the passivated diodes are exposed to the air indoor. The current-voltage (Ⅰ-Ⅴ) characteristics exhibit that the passivated diodes have a smaller series resistance and a lower onset voltage. The EL intensityvoltage (ⅠEL-Ⅴ) relations of the PS devices with different DLCF thicknesses show that only medium DLCF thickness is optimum. These experimental phenomena have been explained based on Raman spectra and IR spectra of the diamond-like carbon films and IR spectra of the passivated PS samples.     

Micro-layers of polystyrene film preventing metal oxidation: implications in cultural heritage conservation

Protection of surfaces directly exposed to the detrimental action of degradative agents (i.e. oxygen, air pollutants and bacteria) is one of the most important challenges in the field of conservation of works of art. Metallic objects are subjected to specific surface corrosion phenomena that, over the years, make mandatory the research of innovative materials that should avoid the direct contact between the metal surface and the weathering agents. In this paper, the set-up, characterisation and application of a new reversible material for preserving metal artefacts are reported. Micro-layers constituted of low-adhesive polystyrene (PS) films obtained from recycling waste packaging materials made of expanded PS were studied. The morphology and thickness of PS films were characterised by optical, atomic force and scanning electron microscopy (SEM). A further check on thickness was carried out by means of visible spectrophotometry doping the films with a hydrophobic dye. Thermal properties of the PS micro-layers were studied by means of differential scanning calorimetry coupled with optical microscopy. Permeability of the PS films to water vapour was also determined. The potential of the low-adhesive PS films, that enabled an easy removal in case of film deterioration, for preventing metal oxidation was investigated on brass specimens by simulating standard artificial corrosion programmes. Morphological and chemical (coupling the energy-dispersive X-rays spectrometry to SEM measurements) analyses carried out on these metal samples showed promising results in terms of surface protection against corrosion.     

Wettability and antibacterial activity of modified diamond-like carbon films

Diamond-like carbon (DLC) films can be used in a numerous industrial applications, including biomedical coatings with bactericidal properties. It has been demonstrated that DLC surface can be modified with oxygen plasma treatment. The purpose of this paper is to study the wettability and bactericidal activity of oxygen plasma-treated DLC films produced by plasma enhanced chemical vapor deposition technique. The sp³/sp² ratio increased after the treatment due to the increase in the generation of the unstable carbon bonds caused by the energetic ions, especially O-H group. The treated DLC surface becomes superhydrophilic and rougher, although the roughness values are still lower. DLC antibacterial activity did not increased with plasma treatment. Therefore, oxygen plasma treatment can be used to make superhydrophilic DLC but not to increase its bactericidal properties.     

End group effect on surface and interfacial segregation in PS-PMMA blend thin films

Thin films of polystyrene (PS)/poly (methyl methacrylate) (PMMA) blends with different end groups were investigated using ToF-SIMS and AFM. PS with -OH and -NH₂ end groups were blended in toluene solvent with pure PMMA homopolymer, and PMMA having anhydride end group. The ToF-SIMS spectra of PS-OH/PMMA resembled that of pure PS-PMMA blends showing an increase of PMMA intensity after annealing. On the contrary, the PS-NH₂ blended with PMMA showed an increase in PS intensity on the surface after annealing. The ToF-SIMS spectra were similar to that of a pure PS-PMMA di-block copolymer. These results indicate copolymer formation at the surface. The PS-NH₂ with PMMA-anhydride blend spectra showed very slight changes in spectra before and after annealing and the AFM images revealed spinodal bi-continuous structures on the surface before and after annealing. The copolymer formation is found to occur in the as-cast film itself and not after thermal treatment.     

An XPS study on the attachment of triethoxsilylbutyraldehyde to two titanium surfaces as a way to bond chitosan

A bioactive coating has the ability to create a strong interface between bone tissue and implant. Chitosan, a biopolymer derived from the exoskeletons of shellfish, exhibits many bioactive properties that make it an ideal material for use as a coating such as antibacterial, biodegradable, non-toxic, and the ability to attract and promote bone cell growth and organized bone formation. A previous study reported on the bonding of chitosan to a titanium surface using a three-step process. In the current study, 86.4% de-acetylated chitosan coatings were bound to implant quality titanium in a two-step process that involved the deposition of triethoxsilylbutyraldehyde (TESBA) in toluene, followed by a reaction between the aldehyde of TESBA with chitosan. The chitosan coatings were examined on two different metal treatments to determine if any major differences in the ability of titanium to bind chitosan could be detected. The surface of the titanium metal and the individual reaction steps were examined using X-ray photoelectron spectroscopy (XPS). Following the deposition of TESBA, significant changes were seen in the amounts of oxygen, silicon, carbon, and titanium present on the titanium surface, which were consistent with the anticipated reaction steps. It was demonstrated that more TESBA was bound to the piranha-treated titanium surface as compared to the passivated titanium surface. The two different silane molecules, aminopropyltriethoxysilane (APTES) and TESBA, did not affect the chemistry of the resultant chitosan films. XPS showed that both the formation of unwanted polysiloxanes and the removal of the reactive terminal groups were prevented by using toluene as the carrier solvent to bond TESBA to the titanium surfaces, instead of an aqueous solvent. Qualitatively, the chitosan films demonstrated improved adhesion after using toluene, as the films remained attached to the titanium surface even when placed under the ultra-high vacuum necessary for XPS, unlike the chitosan films deposited using an aqueous solvent, which were removed when exposed to the ultra-high vacuum environment of XPS.     

Deposition of carbon films using close space sublimation

Carbon films are fabricated for the first time using an inexpensive and ecologically safe modified method of close space sublimation at atmospheric pressure. They are deposited onto quartz, glass, glass ceramic (Pyroceram), and silicon substrates. The main properties of the films (such as the growth rate, morphology and structure, optical properties, the dependences of these properties on the deposition temperature and the substrate material) are studied by X-ray diffraction, atomic force microscopy, multiangular ellipsometry, and the measurement of transmission and reflectance spectra in the visible and near ultraviolet regions. The growth rate is 5 nm/min at a film nucleation temperature of 800°C. The film thickness varies from 0.2 to 2.2 μm, and the minimum surface roughness is 0.5 nm. The refractive indices of the films range from 1.3 to 1.8 depending on the growth and subsequent heat treatment conditions. The optical energy gap is 5.4 eV.     

Modification of surface properties of polypropylene (PP) film using DC glow discharge air plasma

The industrial use of polypropylene (PP) films is limited because of undesirable properties such as poor adhesion and printability. In the present study, a DC glow discharge plasma has been used to improve the surface properties of PP films and make it useful for technical applications. The change in hydrophilicity of modified PP film surface was investigated by contact angle (CA) and surface energy measurements as a function of exposure time. In addition, plasma-treated PP films have been subjected to an ageing process to determine the durability of the plasma treatment. Changes in morphological and chemical composition of PP films were analyzed by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The improvement in adhesion was studied by measuring T-peel and lap shear strength. The results show that the surface hydrophilicity has been improved due to the increase in the roughness and the introduction of oxygen-containing polar groups. The AFM observation on PP film shows that the roughness of the surface increased due to plasma treatment. Analysis of chemical binding states and surface chemical composition by XPS showed an increase in the formation of polar functional groups and the concentration of oxygen content on the plasma-processed PP film surfaces. T-peel and lap shear test for adhesion strength measurement showed that the adhesion strength of the plasma-modified PP films increased compared with untreated films surface.     

Enhanced near-band-edge emission and field emission properties from plasma treated ZnO nanowires

Near-band-edge emission in photoluminescence of ZnO nanowires was found to be significantly improved after plasma treatment. The ratio of ultraviolet emission peak intensity before and after plasma treatment is as high as 3.5. Field emission properties were considerably enhanced after plasma treatment as well. Current emission density has been increased two orders of magnitude under the same electric field. Passivation of surface states and surface morphology change were found to be responsible for such an effective improvement. Our results suggest that the plasma treatment method is effective in enhancing both the near-band-edge emission in photoluminescence and field electron emission performance from ZnO nanowires.     

Ion bombardment of amorphous silicon films during plasma-enhanced chemical vapor deposition in an rf discharge

The characteristics of ion and electron fluxes to the surface of a growing silicon film are investigated in various rf discharge regimes in silane at frequencies of 13.56 MHz and 58 MHz in plasma-enhanced chemical vapor-deposition (PECVD) apparatus. The energy spectra of the ions and electrons bombarding the growing film are measured. The electronic properties of films grown under various degrees of ion bombardment are studied. The correlation of these properties with the ion parameters in the rf discharge plasma during film growth is discussed. Zh. Tekh. Fiz. 68, 52–59 (February 1998)     

高速沉积本征微晶硅的优化及其在太阳电池中的应用

采用高压高功率的甚高频等离子体增强化学气相沉积（VHF-PECVD）技术高速（沉积速率约为1.2 nm/s）沉积了一系列不同厚度的本征微晶硅薄膜,并通过Raman谱和XRD谱的测试,研究了高速沉积时本征微晶硅薄膜的微结构演变特性及其对电池性能的影响.针对其微结构特性及高速沉积本身存在的离子轰击作用强的特点,提出了在沉积微晶硅薄膜过程中采用功率梯度的方法,达到有效地控制薄膜微结构变化的目的,并在一定功率梯度范围内降低了电子温度,提高了薄膜质量,从而使电池效率明显提高.最后在沉积速率为1.2 nm/s时,制备 关键词： 高速沉积 微晶硅薄膜 微结构演变 功率梯度     

White light luminescence from annealed thin ZnO deposited porous silicon

In this study, photoluminescence (PL) properties of annealed ZnO thin films deposited onto a porous silicon (PS) surface by rf-sputtering were investigated. A huge blue shift of luminescence from the ZnO deposited onto the PS surface and a broadband luminescence (white luminescence) across most of the visible spectrum were obtained after the heat treatment at 950 °C in air. The results of Fourier Transform Infrared Spectroscopy (FTIR) analysis suggested that the porous silicon surface was oxidized after ZnO deposition and the broadband luminescence was due to the conversion of Si-H bonds to Si-O-Si bonds on the PS surface. The underlying mechanisms of the broadband PL were discussed by using oxygen-bonding model for the PS and native defects model for ZnO. The experimental results suggested that the heat treatment provides a relatively easy way to achieve white luminescence from thin ZnO deposited porous silicon.     

Some physical properties of In doped copper oxide films produced by ultrasonic spray pyrolysis

In this work, we have reported the effect of In doping on structural, optical and surface properties of copper oxide films obtained by a low-cost ultrasonic spray pyrolysis technique. Thicknesses, refractive indices and extinction coefficients of the films have been determined by Spectroscopic ellipsometry technique using Cauchy-Urbach model for fitting. A very good agreement was found between experimental and theoretical parameters with low MSE values. Transmission and reflectance spectra have been taken by UV Spectrophotometer, and band gap values have been determined by optical method. Structural properties of the films were investigated with X-ray diffraction patterns. In doping caused the films to growth through some certain directions. Atomic force microscope images have been taken to see the effect of In doping on surface topography and roughness of copper oxide films. Surface properties of undoped films have been improved by In doping. Lowest roughness values have been obtained for In doping at 1%. As a result, we have concluded that properties of copper oxide films which are commonly used in solar cells may have improved by In doping (especially In doped at 1%).     

MOCVD法生长SAWF用ZnO/Diamond/Si多层结构

使用等离子体辅助MOCVD系统在金刚石,硅衬底上成功地制备了氧化锌多层薄膜材料,通过两步生长法对薄膜质量进行了优化。XRD测试显示优化后的样品具有c轴的择优取向生长,PL谱测试表明样品经优化后不仅深能级发射峰消失,同时紫外发射峰增强。对优化后的样品的表面测试显示出较低的表面粗糙度。比较氧化锌多层薄膜结构的声表面波频散曲线,ZnO薄膜声表面滤波器受膜厚和衬底材料的影响较大。当ZnO薄膜较薄时,在它上面的传播速度将与衬底上的传播速度接近,与其他衬底上生长的薄膜相比,以金刚石这种快声速材料为衬底的ZnO多层薄膜结构,声表面波滤波器的中心频率将提高1倍左右。     

Enhanced antibacterial performance of hybrid semiconductor nanomaterials: ZnO/SnO2 nanocomposite thin films

The nano-sized coupled oxides ZnO/SnO₂ thin films in a molar ratio of 2:1 (Z2S), 1:1 (ZS) and 1:2 (ZS2) were prepared using sol-gel dip coating method and characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-vis spectroscopy. Escherichia coli (E. coli, ATCC 25922) was selected as a model for the Gram-negative bacteria to evaluate antibacterial property of composite samples compared with single ZnO (Z) and single SnO₂ (S) films. The antibacterial activity has been studied applying the so-called antibacterial drop test under UV illumination. The bactericidal activity was estimated by relative number of bacteria survived calculated from the number of viable cells which form colonies on the nutrient agar plates. The influence of the SnO₂-ZnO nanocomposite composition on the structural features and on the antibacterial properties of the thin films are reported and discussed. It is found that all coatings exhibited a high antibacterial activity. The coupled oxide photocatalyst Z2S has better photocatalytic activity to bacteria inactivation than ZS, ZS2, Z and S films. Furthermore, nanostructured films were active even in the absence of irradiation.