Optical properties of Ag nanocrystals in Sc and O sequentially implanted silica

The implantation of Sc and O results in the modification of the silica with polarizable Sc³⁺ ions. During annealing the Sc ions are incorporated with the O in the network to form a Sc-O-silicate layer. Subsequent implantation of Ag into this layer results in the formation of Ag metal nanocrystals with significantly modified optical properties compared to samples without the Sc ions. The size distribution of the Ag nanocrystals narrowed with increasing Sc concentration, due to the gradual elimination of a band of large Ag clusters. The incorporation of the Sc results in a shift in the wavelength of the surface plasmon resonance of the Ag nanocrystals and a change in the magnitude of the surface plasmon resonance absorption. The results are interpreted using effective medium theory.     

Oxygen and silver diffusion into float glass

In the float glass process, molten glass is floated on a molten metallic tin bath, such that tin penetrates the glass surface. Consequently, the glass has distinctly two different faces; the tin-penetrated face (bottom face) and the opposite face (top face). In this paper, the effects of tin on oxygen and silver diffusion into the top and bottom faces of a soda–lime–silica float glass are reported. It was revealed that oxygen diffusion from the atmosphere into the bottom face at temperatures above glass transition temperature was extremely suppressed near the surface region of the glass. This was not observed for the top face. This effect was ascribed to chemical reactions between the diffused oxygen and Sn²⁺ near the surface of the glass. Silver diffusion was also influenced by the tin due to chemical reactions of Ag⁺ ions with Sn²⁺, leading to the precipitation of nanometer-sized Ag crystals. As a result, the coloration due to the surface plasmon resonance of the Ag crystals was significantly different between the top and bottom faces because of differences in the nucleation and growth processes associated with the Ag crystals.     

Amorphous carbon-based films with surface-plasmon-enhanced full-color photoluminescence

A series of amorphous carbon-based films were deposited on the nanostructured Ag layers to observe surface plasmon (SP) enhanced photoluminescence (PL). The dependence of PL peak wavelength and intensity on the film composition and the nanostructure of the Ag layers were systematically investigated. The PL wavelength was tuned from 442 nm to 635 nm by varying the carbon content of the as-deposited carbon-based films. The nanostructure of Ag layers varied from nanoparticles (NPs) to continuous films via process control. With the SPs generated at the carbon-based film/Ag layer interface, the PL intensity was found to be significantly enhanced with a peak enhancement factor of 6, and the light emission range of the composite films was extended to 434–653 nm. The dependence of PL intensity on the spectral overlap between the carbon-based films and plasmon resonant Ag layers, Ag surface morphology and the internal quantum efficiency (IQE) of the carbon-based films was discussed. The redshift of SP resonance with the increasing refractive index of the upper carbon-based films was observed.     

Complementary study of the internal porous silicon layers formed under high-dose implantation of helium ions

The surface layers of Si(001) substrates subjected to plasma-immersion implantation of helium ions with an energy of 2–5 keV and a dose of 5 × 10¹⁷ cm^–2 have been investigated using high-resolution X-ray reflectivity, Rutherford backscattering, and transmission electron microscopy. The electron density depth profile in the surface layer formed by helium ions is obtained, and its elemental and phase compositions are determined. This layer is found to have a complex structure and consist of an upper amorphous sublayer and a layer with a porosity of 30–35% beneath. It is shown that the porous layer has the sharpest boundaries at a lower energy of implantable ions.     

A pitch of helicoid of chiral liquid crystals and surface plasmon excitation: A theoretical study

ABSTRACT

Surface plasmon resonance (SPR) is widely used in different types of optical detection schemes and for light manipulation. There are a lot of experimental and theoretical investigations about the influence of different media, adjacent to the metal layer, on SPR. However, the influence of liquid crystal (LC) layer is not fully revealed. There are only few publications considering Kretshmann configuration with LC layer sandwiched between the prism and metal layer. Respectively, a lot of questions regarding the influence of LC properties on the surface plasmon resonance (SPR) are still open. The aim of this paper is to fill this gap.     

Evidence of nucleation and growth of metal Cu and Ag nanoparticles in lustre: AFM surface characterization

Lustre is one of the most interesting ancient ceramic decorations. Recent studies demonstrated that lustre correspond to a nanostructured thin layer formed by metallic copper and metallic silver nanocrystals embedded in a glass matrix. The aim of this paper is to improve the comprehension of lustre nature and the mechanisms of its formation focusing special attention on glaze surface nanotopography and the crystalline particles size and distribution. Lustre reproductions were studied during the lustre formation process and compared to medieval lustre layers. Lustre reproductions and ancient lustre surfaces were observed by means of White Light Interferometry, Atom Forces Microscopy, X-ray Diffraction and Electron Microprobe. These observations shown that lustre layer does not appear as a superimposed layer on the top of the glaze but as a surface roughness resulting by the nanocrystals growth inside the glassy matrix. Chemical Microprobe Analysis of lustre reproductions indicates that Cu and (later) Ag are introduced into the glaze by ion-exchange with alkalis (Na and K) from the glaze. White Light Interferometry and Atomic Forces Microscopy showed that surface roughness increase during the lustre formation process as a result of metal nanoparticles growth. Silver particles appear heterogeneously distributed and have a smaller size and higher roughness than copper particles on ancient lustre. This paper confirmed that lustre formation process involves two steps process: ion exchange and crystallization (nucleation and crystal growth) of Cu and Ag metal nanoparticles inside the glassy matrix.     

Photoinduced electron transfer and surface plasmon resonance in materials consisting of pyrene fluorophore and Au nanorods immobilized on MCM-48 surface

Mesoporous silica of the MCM-48 type as a support for fluorophore molecules was functionalized with 3-aminopropyl and 3-thiolopropyl groups. Then, molecules consisting of a fluorophore pyrene group and receptor fragments with donor N and O atoms were covalently attached by grafting of carboxyl groups to amino groups on a mesoporous silica surface. Additionally, Au nanorods were attached to thiol groups on the same surface. The vicinity of Au nanorods in a material with pyrene derivatives covalently grafted on the functionalized MCM-48 silica enhanced fluorescence of the composite material due to the surface plasmon resonance effect. The fluorescence emission of the prepared recognition material is quenched specifically owing to the photoinduced electron transfer effect after coordination reactions with Cu(II) ions. Moreover, the material exhibits selectivity for Cu(II) cations in aqueous solutions in presence of such metal ions as: alkali, alkaline earth, transition and heavy metals. During UV irradiation the studied material undergoes slowly photochemical degradation as a potential recognition element.     

Ag precipitation and optical behavior in Na2O---B2O3 glasses

Ag particles of different sizes in the nanometer range were produced in Na₂O---B₂O₃ glasses containing Ag₂O by the melt-quenching and heat-treatment method. The quenching rate was 10³ K s⁻¹ and the heat treatment was at 738 K for 2–300 h. The precipitation was dependent on diffusion limited growth. The optical absorption of Ag particles in the glasses was measured and correlated to the distribution of particle radii. The peak energy of the surface plasmon resonance was blue shifted and the width decreased with increasing average particle radius. These results are compared with previous data on similar systems.     

Nano-composite soda lime silicate glass prepared using silver ion exchange

Commercial soda lime silicate glasses have been subjected to ion exchange at different temperatures ranging from 320 to 500 °C in a molten mixture of AgNO₃ and NaNO₃ with molar ratio of 10:90, 02:98 and 50:50 for different time periods ranging from 40 to 180 min. Optical and structural properties of the ion exchanged glass are measured using UV–Vis–NIR absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, fluorescence spectroscopy and transmission electron microscopy (TEM). Signature of silver nanoparticle formation is obtained from the UV–Vis–NIR spectra, which shows a peak at 425 nm due to surface plasmon resonance (SPR). Replacement of Na⁺ ions by Ag⁺ ions is inferred from FTIR spectra. Fluorescence spectra reveal the formation of Ag⁰ atoms from Ag⁺ ions at higher temperatures. TEM image shows the silver nanoparticles of average size 3.75 nm. At exchange temperature of 500 °C Ag nanoparticles are formed without post-exchange annealing treatment.     

Enhancement of optical birefringence in tellurite glasses containing silver nanoparticles induced via thermal poling

Wavelength-selective enhancement of optical birefringence has been observed in a tellurite glass containing silver nanoparticles (Ag NPs) induced via thermal poling. The birefringence appears as an optical rotation of linearly polarized light; a large optical rotation is observed at around the wavelength of localized surface plasmon resonance (LSPR) of Ag NPs. The optic axis is oriented along the electric field applied during the thermal poling, suggesting that birefringence induced in the glass matrix through the thermal poling is drastically enhanced by the NPs at around the LSPR. Because of the birefringence of the matrix, the wavelength of LSPR shifts depending on the polarization state of the incident light, which in turn induces the polarization dependence of the real part of the refractive index via the Kramers–Kronig relation.     

Formation of nanoparticles in soda-lime glasses by single and double ion implantation

Structural characteristics and optical properties of monometallic and bimetallic Ag and Au nanoparticles in the surface region of soda-lime glass fabricated by ion implantation have been studied by transmission electron microscopy and optical spectroscopy. As a result it has been found that both, implantation dose and process temperature, strongly influence the metal nanoparticle formation governed by ion diffusion and metal precipitation as well as the involved stress generation around the particles. Thus, the mean size of metal nanoparticles and the width of the particle containing region beneath the glass surface increase with increasing temperature as well as implanted dose. Upon sequential high-dose double implantation to form bimetallic Ag–Au nanoparticles a rather complex configuration has been obtained. Particles of sizes above a threshold of 5–10 nm exhibit distinct image contrast features indicating the development of central voids whose sizes are proportional to the outer particle diameter.     

Corrosion behavior and in vitro biocompatibility of Zr–Al–Co–Ag bulk metallic glasses: An experimental case study

Ni- and Cu–free Zr–Al–Co–Ag bulk metallic glasses (BMGs) were synthesized by copper mold casting. The effects of Ag addition for partially replacing Co of Zr₅₃Al₁₆Co₃₁ BMG on the corrosion behavior, surface chemistry and in vitro biocompatibility of BMGs were investigated. The Zr–Al–Co–Ag BMGs are spontaneously passivated with low passive current densities in phosphate buffered saline (PBS) solution. Partial substitution of Co by Ag is effective in improving the corrosion resistance of the Zr–Al–Co BMG. X-ray photoelectron spectroscopy (XPS) measurements reveal that the Ag addition increases the concentration of Zr and decreases the concentration of Al in the surface passive film of BMGs, which is responsible for the enhanced corrosion resistance of Zr–Al–Co–Ag BMGs. Mouse MC3T3-E1 pre-osteoblast cell proliferation results and morphology observations show that the Zr–Al–Co–Ag BMGs exhibit comparable cell viability and proliferation activity with those of Ti–6Al–4V alloy, demonstrating their good biocompatibility. The high corrosion resistance in PBS and low in vitro cytotoxicity of Zr–Al–Co–Ag BMGs suggest an initial biocompatibility for biomedical applications.     

Relations between the optical properties of Cu–Ag:Si3N4 nanocermets and the microstructure of the metallic nanoclusters

Ion beam sputtering has been used to prepare Ag/Cu, Ag and Cu nanoclusters embedded in a Si₃N₄ dielectric matrix with the goal to correlate structural information and optical properties. The optical transmittance spectra of the bimetallic nanoclusters are compared with those obtained in the case of the single metallic nanocermets in the as-deposited state. The influence of a post annealing treatment, at different temperatures, on the optical properties of the bimetallic nanocermets is also discussed. The nanocluster structure has been investigated by X-ray absorption spectroscopy and X-ray diffraction. The chemical composition has been analysed by Rutherford backscattering spectroscopy. The surface plasmon resonance occurring after annealing in a definite temperature range is interpreted as due to the specific atomic arrangement resulting from this treatment.     

Influence of heat treatment on the colour of Au and Ag glasses produced by the sol-gel pathway

In this work, coloured glasses were produced based on the synthesis of gold and silver nanoparticles by the sol-gel process having in mind their application in art works. Gold and silver were used separately or as a mixture by varying the mole fractions in order to get a range of colours from yellow to red. The gold and silver nanoparticles were prepared by the reduction of tetrachloroauric acid and silver nitrate with sodium citrate in aqueous solutions which were further introduced in the sol-gel system. Attention was focused on the thermal treatment of the sol-gel samples. Different temperatures were used in order to determine their influence on the obtained colour. The glasses were characterized by UV-Vis absorption spectroscopy and the size of the nanoparticles was examined by transmission electron microscopy (TEM).The range of colours mentioned above is obtained either by preparing nanoparticles of each metal and mixing them or by preparing nanoparticles from solutions containing initially ions of both metals. In the former case, two surface plasmon resonance (SPR) bands were observed for temperatures below 200 °C while higher temperatures promote the formation of alloys between the Ag and Au nanoparticles. In the latter case, only one SPR band is observed and the nanoparticle size distribution is narrower. The results were explained by nanoparticle aggregation promoted by temperature. Glasses containing only Ag did not present the typical yellow colour above 300 °C but it was shown that the colour could be stabilized if Au was added in small amounts (Au/Ag molar ratio 0.1).     

Ag-AgCl/Al2O3复合光催化材料的制备与光催化性能研究

以介孔γ-Al2O3为载体,采用化学沉积-光还原法制备了具有表面金属等离子体效应的Ag-AgCl/Al2O3复合光催化材料.用SEM、TEM、XRD及UV-Vis能谱等对复合材料进行了结构和性能表征,并以10 mg/L的亚甲基蓝(MB)溶液为目标降解物,对复合材料的光催化性能进行了评价.实验结果表明,复合光催化材料在可见光下光照60 min后对亚甲基蓝的降解率达95;以上,总有机碳TOC去除率约为65;,实验制备的Ag-AgCl/Al2O3具有很高的可见光催化活性,循环使用5次后依然具有90;以上的MB降解率.     

Ag2O/TiO2异质结的光催化活性及耐光腐蚀性研究

以钛酸丁酯、硝酸铋和硝酸银为原料,FTO为基底,采用水热法结合超声沉积法合成了Ag2 O/TiO2异质结光催化剂.采用场发射扫描电子显微镜(FESEM)、X射线衍射仪(XRD)、紫外-可见吸收光谱(UV-Vis)分析测试手段对样品的形貌和结构进行了表征.结果表明,Ag2O/TiO2异质结是由直径约200 ～ 300 nm的TiO2纳米棒镶嵌着Ag2O纳米颗粒组成,与TiO2纳米棒阵列相比,Ag2O/TiO2异质结在可见光区有明显的光吸收.Ag2O/TiO2异质结的光催化效率明显提高.尤为重要的是,经光处理后,最终得到稳定的Ag-Ag2O/TiO2三元体系,并对Ag-Ag2 O/TiO2三元体系提高光催化稳定性和活性的机理进行了分析.     

Changes in surface morphology of silicate glass induced by fast electron irradiation

Binary potassium-silicate glass was irradiated with a defocused electron beam. During the irradiation the alkali ions migrate from the surface into the depth and alkali ions depleted layer is created near the surface. Such changes in the chemical composition are also accompanied with changes of the glass structure and finally result in the volume changes of the irradiated glass. This was directly studied using atomic force microscope (AFM). A series of exposures with energy of electrons of 7–50 keV and with different doses were performed. For low doses the irradiated glass is continuously depressed with the increasing dose, indicating this way the structural changes leading to the volume compaction. It is suggested the compaction is caused by the relaxation processes of the silica subnetwork. A further increase of the electron dose causes a formation of the small bump inside the center of the depression. The bump arises with the dose and finally exceeds the surrounding surface. It is suggested that the expansion is connected with the migration of alkali ions and the formation of Si–O–O–Si bonds which result in the formation of new rings with new space requirements.     

Production and Study of Silver Nanoparticles by 532 nm Laser Pulse Ablation in NaCl Solution

In this experimental research, silver nanoparticles are produced in NaCl solution by the laser ablation method. Our aim was to investigate the effect of the amount of NaCl in the ablation medium on the characteristics of nanoparticles. A 7 ns pulsed Neodymium YAG laser (Nd:YAG) at 5 J/cm2 fluence and 532 nm wavelength was employed to produce Ag nanoparticles in distilled water with four different concentrations of NaCl. The optical properties, size distribution, and agglomeration of nanoparticles were investigated by several diagnostics. The UV–Visible absorption spectra of the Ag nanoparticles exhibit absorptions in the UV region because of surface plasmon resonance. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to study the size distribution and morphology of nanoparticles. Dynamic light scattering (DLS) was employed to measure the hydrodynamic size of nanoparticles in suspensions. With X-ray diffraction (XRD) pattern, the lattice structure of nanoparticles was studied. Fourier transform infrared (FTIR), photoluminescence (PL) spectra were obtained to observe the molecular structure and atomic energy levels of particles.     

Up-conversion enhancement in Er3 +-Ag co-doped zinc tellurite glass: Effect of heat treatment

The melt quenching method was used to synthesize the Ag⁰ nanoparticles and Er^3 + ions co-doped zinc tellurite glass. The glasses were characterized by differential thermal analyzer, UV–VIS-IR absorption, photoluminescence spectroscopy and TEM imaging. Heat treatment at different annealing time intervals above the glass transition temperature was applied to reduce the Ag⁺ ions to Ag⁰ NPs. The influence of heat treatment on structural and optical properties is examined. Intense and broad up-conversion emissions of silver are recorded in the visible region. Up-conversion luminescence spectra revealed three major emission peaks at 520, 550 and 650 nm originating from ²H_11/2, ⁴S_3/2 and ⁴F_9/2 levels, respectively. An efficient enhancement in visible region is observed for samples containing silver NPs. The absorption plasmon peaks are evidenced around 560 and 594 nm. The effect of localized surface plasmon resonance and the energy transfer from the surface of silver NP to trivalent erbium ions are described as the sources of enhancement.     

Influence of the chemical nature of implanted ions on the structure of a silicon layer damaged by implantation

The influence of the implantation of silicon single crystals by fluorine, nitrogen, oxygen, and neon ions on the distribution of strain and the static Debye-Waller factor in the crystal lattice over the implanted-layer depth has been investigated by high-resolution X-ray diffraction. The density depth distribution in the surface layer of native oxide has been measured by X-ray reflectometry. Room-temperature implantation conditions have ensured the equality of the suggested ranges of ions of different masses and the energies transferred by them to the target. It is convincingly shown that the change in the structural parameters of the radiation-damaged silicon layer and the native oxide layer depend on the chemical activity of the implanted ions.