Surface-enhanced Raman scattering substrate of silver nanoparticles depositing on AAO template fabricated by magnetron sputtering

In this report, we describe a fabrication process of low-cost and highly sensitive SERS substrates by using a simple anodizing setup and a low-energy magnetron sputtering method. The structure of the SERS substrates consists of silver nanoparticles deposited on a layer of anodic aluminum oxide (AAO) template. The fabricated SERS substrates are investigated by a scanning electron microscope (SEM), a transmission electron microscope (TEM), and a confocal Raman spectroscope. We have verified from the surface morphology that the fabricated SERS substrates consist of high-density round-shape silver nanoparticles where their size distribution ranges from 10 to 30 nm on the top and the bottom of nanopores. The surface-enhanced Raman scattering activities of these nanostructures are demonstrated using methylene blue (MB) as probing molecules. The detection limit of 10⁻⁸ M can be achieved from this SERS substrate.     

Silver nanoparticles deposited on anodic aluminum oxide template using magnetron sputtering for surface-enhanced Raman scattering substrate

Low-cost and highly sensitive surface-enhanced Raman scattering (SERS) substrates have been fabricated by a simple anodizing process and a magnetron sputtering deposition. The substrates, which consist of silver nanoparticles embedded on anodic aluminum oxide (AAO) templates, are investigated by a scanning electron microscope and a confocal Raman spectroscopy. The SERS activities are demonstrated by Raman scattering from adsorbed solutions of methylene blue and pyridine on the SERS substrate surface. The most optimized SERS substrate contains the silver nanoparticles, with a size distribution of 10-30 nm, deposited on the AAO template. From a calculation, the SERS enhancement factor is as high as 8.5 × 10⁷, which suggests strong potentials for direct applications in the chemical detection and analyses.     

Single-crystal silver nanowires: Preparation and Surface-enhanced Raman Scattering (SERS) property

Ordered Ag nanowire arrays with high aspect ratio and high density self-supporting Ag nanowire patterns were successfully prepared using potentiostatic electrodeposition within the confined nanochannels of a commercial porous anodic aluminium oxide (AAO) template. X-ray diffraction and selected area electron diffraction analysis show that the as-synthesized samples have preferred (220) orientation. Transmission electron microscopy and scanning electron microscopy investigation reveal that large-area and ordered Ag nanowire arrays with smooth surface and uniform diameter were synthesized. Surface-enhanced Raman Scattering (SERS) spectra show that the Ag nanowire arrays as substrates have high SERS activity.     

Preparation of silver nanoparticles by photo-reduction for surface-enhanced Raman scattering

A substrate for surface-enhanced Raman scattering (SERS) has been developed. Based on the surface-catalyzed reduction of Ag⁺ by citrate on the silver nanoparticles surface under light irradiation, small silver seeds on a quartz slide can be enlarged. The optical properties and characteristics of the silver films have been investigated by ultraviolet-visible spectroscopy, scan electron microscope and atomic force microscopy (AFM). The results indicate that the particle size and shape are different at different reduction time. At the first 3 h, some triangular and hexagonal nanoparticles formed; with the reduction proceeding, the shape of the silver particles became irregular and the size became larger. The silver films obtained are very suitable as SERS active substrate. The relationship between SERS intensity and the reduction time has been investigated for 1,4-bis[2-(4-pyridyl)ethenyl]-benzene molecule adsorbed on the silver film. The SERS intensity reached a maximum at 8 h reduction. The AFM measurements indicate that roughness features with an average size of 100 nm are present on the surface, which yielded the strongest SERS signal. Pyridine was used as a probe molecule to investigate the enhancement factor (EF) of the silver films. According to the formalism of Tian and co-workers, the EF of the silver films is estimated to be 3.4 × 10⁵. The silver film that can remain active for more than 50 days would seem to be suitable for various analytical applications.     

Au/Si-NPA复合纳米体系的SERS增强能力研究

利用具有准周期结构的硅纳米孔柱阵列(silicon nanoprous pillar array,Si-NPA)为衬底使用浸渍法制备优化Au/Si-NPA活性基底。并利用最优化制备的Au/Si-NPA活性基底对罗丹明6G(Rhoda-mine 6G,R6G)进行探测,研究其表面增强拉曼散射(surface enhanced Raman scattering,SERS)光谱并对其增强原理进行解释。     

Influence of substrate direct current bias voltage on microcrystalline silicon growth during radio-frequency magnetron sputtering

Hydrogenated microcrystalline silicon (μc-Si:H) thin films were prepared on glass, aluminum-covered glass and Si wafer substrates at various substrate bias voltages (V_sb) between -400 and +50 V, and the influence of V_sb on their structural properties was investigated. The crystallinity (crystalline volume fraction and crystallite size) of the μc-Si:H films deposited on glass remained unchanged with respect to V_sb. For μc-Si:H films deposited on aluminum within the V_sb range of -20 to +50 V, the crystallinity also remained unchanged and showed the same crystallinity as that of the films deposited on glass substrate. However, the crystallinity of the μc-Si:H films deposited on aluminum-covered substrate was reduced as V_sb decreased from -20 to -100 V, and the film at V_sb=-400 V was completely amorphous.     

Surface-enhanced Raman scattering inside Au@Ag core/shell nanorods

The design and synthesis of plasmonic nanoparticles with Raman-active molecules embedded inside them are of significant interest for sensing and imaging applications.However,direct synthesis of such nanostructures with controllable shape,size,and plasmonic properties remains extremely challenging.Here we report on the preparation of uniform Au@Ag core/shell nanorods with controllable Ag shells of 1 to 25 nm in thickness.1,4-Aminothiophenol (4-ATP) molecules,used as the Raman reporters,were located between the Au core and the Ag shell.Successful embedding of reporter molecules inside the core/shell nanoparticles was confirmed by the absence of selective oxidation of the amino groups,as measured by Raman spectroscopy.The dependence of Raman intensity on the location of the reporter molecules in the inside and outside of the nanorods was studied.The molecules in the interior showed strong and uniform Raman intensity,at least an order of magnitude higher than that of the molecules on the nanoparticle surface.In contrast to the usual surface-functionalized Raman tags,aggregation and clustering of nanoparticles with embedded molecules decreased the surface-enhanced Raman scattering (SERS) signal.The findings from this study provide the basis for a novel detection technique of low analyte concentration utilizing the high SERS response of molecules inside the core/shell metal nanostructures.As an example,we show robust SERS detection of thiram fungicide as low as 10-9 M in solutions.     

Ultrafast pump-probe spectroscopy studies of CeO2 thin film deposited on Ni-W substrate by RF magnetron sputtering

This study presents the first investigation of rapid dynamical processes that occur in pure CeO₂ thin film, using ultra fast pump-probe spectroscopy at room temperature. For this purpose we have used a single (200) oriented CeO₂ film deposited on biaxially textured Ni-W substrate by RF magnetron sputtering technique. The ultrafast transient spectra show initial sharp rise transition followed by an exponential photon decay. This rise time is about 10 ps irrespective of the probe wavelengths range 500–800 nm. The initial decay constant (τ) at 500 nm probe wavelength is found to be 171 ps, while at 800 nm probe wavelength it is 107.5 ps. The ultrafast absorption spectra show two absorption peaks at 745 and 800 nm, and are attributed to the electronic transitions from ²F_7/2–²F_5/2 and ¹S₀–¹F₃ respectively. The relatively high intensity absorption peak at 745 nm indicates dominant f–f electronic transition. Further, the absorption peak at 745 nm splits into two distinct peaks with respect to delay time, and is attributed to the charge transfer in between Ce⁴⁺ and Ce³⁺ ions. These results indicate that CeO₂ itself is a potential candidate and can be used for optical applications.     

Functional properties of ceramic-Ag nanocomposite coatings produced by magnetron sputtering

In recent years, the use of nanocomposite materials to functionalize surfaces has been investigated, taking advantage of the complementary properties of the nanocomposite constituents. Among this family of materials, ceramic-Ag coatings have been widely studied due to the large variety of functionalities that silver possesses and the possibility of tuning the coating’s practical features by selecting the proper matrix to support this noble metal. Therefore, this review focuses on the effects of silver nanoparticles on the functional properties of ceramic-Ag nanocomposites. The chemistry, structure, morphology and topography of the coatings are analyzed with respect to the changes produced by the silver nanoparticles’ distribution, amount and sizes and by altering production process variables. To offer a clear understanding of the functionalities of these materials, the optical, electrical, mechanical, tribological, electrochemical and biological properties reported in the last decade are reviewed, focusing on the ability to tune such properties by modifying the silver distribution, morphology and composition. In particular, the surface plasmon resonance, self-lubricating ability and antibacterial effect of silver are covered in detail, establishing their correlation with factors such as silver diffusion, segregation and ionization.     

Properties of Ce-doped ITO films deposited on polymer substrate by DC magnetron sputtering

Ce-doped indium tin oxide (ITO:Ce) films were deposited on flexible polyimide substrates by DC magnetron sputtering using ITO targets containing various CeO₂ contents (CeO₂ : 0, 0.5, 3.0, 4.0, 6.0 wt.%) at room temperature and post-annealed at 200 °C. The crystallinity of the ITO films decreased with increasing Ce content, and it led to a decrease in surface roughness. In addition, a relatively small change in resistance in dynamic stress mode was obtained for ITO:Ce films even after the annealing at high temperature (200 °C). The minimum resistivity of the amorphous ITO:Ce films was 3.96 × 10^− 4 Ωcm, which was deposited using a 3.0 wt.% CeO₂ doped ITO target. The amorphous ITO:Ce films not only have comparable electrical properties to the polycrystalline films but also have a crystallization temperature > 200 °C. In addition, the amorphous ITO:Ce film showed stable mechanical properties in the bended state.     

Microwave assisted template synthesis of silver nanoparticles

Easier, less time consuming, green processes, which yield silver nanoparticles of uniform size, shape and morphology are of interest. Various methods for synthesis, such as conventional temperature assisted process, controlled reaction at elevated temperatures, and microwave assisted process have been evaluated for the kind of silver nanoparticles synthesized. Starch has been employed as a template and reducing agent. Electron microscopy, photon correlation spectroscopy and surface plasmon resonance have been employed to characterize the silver nanoparticles synthesized. Compared to conventional methods, microwave assisted synthesis was faster and provided particles with an average particle size of 12 nm. Further, the starch functions as template, preventing the aggregation of silver nanoparticles.     

Structural analysis of amorphous Si films prepared by magnetron sputtering

A study is presented on the structural changes occurring in thin amorphous silicon (a-Si) during thermal treatments. The a-Si films were deposited on single-crystalline Si substrates held at room temperature by magnetron sputtering of a Si target in pure Ar atmosphere, and therefore the films were hydrogen-free. All samples were annealed in vacuum and subsequently studied by electron paramagnetic resonance (EPR) and grazing incidence X-ray diffraction (GIXRD). A slight increase in the dangling bonds content at lower annealing temperatures, and then a strong increase of it at around 650 °C, suggested significant structural changes. The samples were also studied by grazing incidence small-angle X-ray scattering (GISAXS) which confirmed changes at the nanometric scale attributed to voids in the material. A nice correlation of the results of the three techniques shows advantages of this approach in the analysis of structural changes in a-Si material.     

Optical investigation of GaSb thin films grown on GaAs by metalorganic magnetron sputtering

Metalorganic magnetron sputtering (MOMS) technology has been applied to the growth of epitaxial GaSb layers on GaAs (001). Optical studies are performed on a series of GaSb/GaAs samples grown under different growth conditions. Raman scattering measurements indicated the improvement of the crystalline quality of the GaSb thin film from the interface toward the surface with decreasing substrate growth temperature from 480 °C to 400 °C. Fourier transform infrared (FTIR) reflectance revealed the possible existence of an intermixed GaSb-GaAs layer near the interface. In UV reflectance spectra, the shapes of the high energy transition bands were found to be associated with the GaSb film quality.     

Diagnosis of breast cancer by analysis of sialic acid concentrations in human saliva by surface-enhanced Raman spectroscopy of silver nanoparticles

Breast cancer is the most common type of malignant tumor among women and their second leading cause of cancer-related deaths.The most common method for screening and diagnosis is mammography.Nonetheless,two main problems have been identified.First,the dose of radiation received during the test prevents the method from the use on women who are ＜ 40 years old.Second,there can be mammogram failure owing to the lack of tumor contrast with the fibrous tissue.Therefore,there is a need for screening methods that will help to identify high-risk cases.We developed a biological marker test that can help to identify them.Increased levels of sialic acid (SA) in saliva are known to correlated with breast cancer.In this study,we evaluated the feasibility of Raman spectroscopy as a method for quantification of SA in saliva,using citrate-reduced silver nanoparticles (cit-Ag-NPs) as a surface-enhanced Raman spectroscopy (SERS) substrate.Quantification of SA was accomplished by measuring its intensity in saliva and comparing it with a calibration curve of SA standards.The mean SA concentration in saliva was found to be significantly higher among 100 breast cancer patients (18.3 ± 9.4 mg·dL-1;mean ± SD) than among 106 healthy controls (3.5 ± 1.0 mg·dL-1).The SERS test showed sensitivity of 94％ and specificity 98％ for detection of patients with breast cancer,assuming that SA concentration ＞ 7 mg·dL-1 is a cutoff for positive test results.Our findings prove the usefulness of this SERS technique as a simple,convenient,and highly sensitive method of quantitative analysis of SA in saliva.The simplicity of this nanotechnological test may help to substantially reduce the mortality among patients with breast cancer by providing women with a simple,noninvasive screening test that can be applied regardless of age or density of breast tissue.     

Atomic scale microstructures of high-k HfSiO thin films fabricated by magnetron sputtering

High-k hafnium-silicate films were deposited by RF magnetron sputtering approach on silicon wafer. The microstructure has been investigated using the combination of transmission electron microscopy and atom probe tomography. It was evidenced that the elaborated HfSiO thin films subsequently annealed at 950 °C during 15 min leads to a complex phase separated nanostructure where silica, hafnia and silicon nanoclusters coexist. The formation of silicon nanoclusters in hafnia-based host was never reported before. The results demonstrate the capability of RF magnetron sputtering to pave the way for realization of nanomemory devices based on silicon clusters embedded in high-k matrix.     

衬底温度对磁控溅射制备外延ZnO薄膜结构特性的影响

在不同的衬底温度下,采用磁控溅射方法在蓝宝石(0001)衬底上制备了外延生长的ZnO薄膜.采用原子力显微镜(AFM)、X射线衍射仪(XRD)、可见-紫外分光光度计系统研究了衬底温度对ZnO薄膜微观结构和光学特性的影响.AFM结果表明在不同村底温度制备的ZnO薄膜具有较为均匀的ZnO晶粒,且晶粒的尺寸随衬底温度的增加逐渐增大.XRD结果显示不同温度生长的ZnO薄膜均为外延生长,400℃生长的薄膜具有最好的结晶质量;光学透射谱显示在370nm附近均出现一个较陡的吸收边,表明制备的ZnO薄膜具有较高的质量,其光学能带隙随着衬底温度的增加而减小.     

Quantitative enhanced Raman scattering of labeled DNA from gold and silver nanoparticles

Surface-enhanced resonance Raman scattering (SERRS) from silver nanoparticles using 514.5-nm excitation has been shown to offer huge potential for applications in highly sensitive multiplexed DNA assays. If the technique is to be applied to real biological samples and integrated with other methods, then the use of gold nanoparticles and longer wavelengths of excitation are desirable. The data presented here demonstrate that dye-labeled oligonucleotide sequences can be directly detected by SERRS using gold nanoparticles in a quantitative manner for the first time. The performance of gold and silver nanoparticles as SERRS substrates was assessed using 514.5-, 632.8-, and 785-nm excitation and a range of 13 commercially available dye-labeled oligonucleotides. The quantitative response allowed the limit of detection to be determined for each case and demonstrates that the technique is highly effective, sensitive, and versatile. The possibility of excitation at multiple wavelengths further enhances the multiplexing potential of the technique. The importance of effectively combining the optical properties of the nanoparticle and the dye label is demonstrated. For example, at 632.8-nm excitation, the dye BODIPY TR-X and gold nanoparticles make a strong SERRS combination with very little background fluorescence. This study allows the choice of nanoparticle and dye label for particular experimental setups, and significantly expands the applicability of enhanced Raman scattering for use in many disciplines.     

Surface-enhanced Raman scattering dendritic substrates fabricated by deposition of gold and silver on silicon

This paper reports a study on the preparation of gold nanoparticles and silver dendrites on silicon substrates by immersion plating. Firstly, gold was deposited onto silicon wafer from HF aqueous solution containing HAuCl4. Then, the silicon wafer deposited gold was dipped into HF aqueous solution of AgNO3 to form silver coating gold film. Scanning electron microscopy reveals a uniform gold film consisted of gold nanoparticles and rough silver coating gold film containing uniform dendritic structures on silicon surface. By SERS (surface-enhanced Raman scattering) measurements, the fabricated gold and silver coating gold substrates activity toward SERS is assessed. The SERS spectra of crystal violet on the fabricated substrates reflect the different SERS activities on gold nanoparticles film and silver coating gold dendrites film. Compared with pure gold film on silicon, the film of silver coating gold dendrites film significantly increased the SERS intensity. As the fabrication process is very simple, cost-effective and reproducible, and the fabricated silver coating gold substrate is of excellent enhancement ability, spatial uniformity and good stability.     

Low-temperature deposited Titanium-doped zinc oxide thin films on the flexible PET substrate by DC magnetron sputtering

Transparent conducting Titanium-doped zinc oxide thin films (TZO) with high transparency and relatively low resistivity were firstly deposited on water-cooled polyethylene terephthalate (PET) substrates at room temperature by DC magnetron sputtering. The microstructure, optical and electrical properties of the deposited films were investigated and discussed. The XRD patterns show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity decreases when the sputtering power increases from 45 W to 60 W. However, as the puttering power continue increases from 60 W to 90 W, the electrical resistivity increases rapidly. When the puttering power is 60 W, the films deposited on PET substrate have the lowest resistivity of 4.72 × 10⁻⁴ Ω cm and a relatively high transmittance of above 92% in the visible range.     

交流磁控溅射制备ZAO薄膜工艺参数的研究

对于交流磁控溅射氧化锌铝陶瓷靶材制备ZAO薄膜,研究了氧流量、基体温度、靶电流密度、铝的掺杂量、本底真空压力和工作气体压力对ZAO薄膜电学性能的影响规律,优化了工艺参数,为工业化生产提供了实验依据.