Preparation, structure, and properties of metal nanocomposites in lithium niobate

Crystals of lithium niobate LiNbO₃ are implanted with 60-keV Cu^? ions at different ion fluxes to a fluence of 2 × 10¹⁷ ions/cm². The structure and the linear and nonlinear optical properties of the implanted layers are investigated. The optical transmission and ion-induced photon spectra of the LiNbO₃ crystals are measured in the course of implantation. It is revealed that the implantation brings about the formation of complex nanocomposites consisting of metallic copper nanoparticles and nanodomains of the matrix. The distributions of nanoparticles and nanodomains in the implanted layers do not correlate with each other. It is shown that the variations in the linear and nonlinear optical absorption of the nanocomposites are predominantly determined by the changes in the chemical composition and the structure of the matrix.     

Optical properties of ZnO and Al2O3 implanted with silver ions

ZnO and Al₂O₃ samples implanted with 30-keV silver ions with fluences in the interval (0.25–1.00) × 10¹⁷ ions/cm² are studied by the method of optical photometry in the visible part of the spectrum. The optical transmission spectra of the implanted samples exhibit a selective band associated with surface plasmon resonance absorption of silver nanoparticles. The intensity of this band nonmonotonically depends on the implantation fluence. The silver ion depth distribution in the samples is calculated. It is shown that the non-monotonicity observed in experiments is due to an increase in the substrate sputtering ratio with increasing implantation fluence. It is found that vacuum thermal annealing of the implanted Al₂O₃ layers up to 700°C causes a considerable narrowing of the plasmon absorption bandwidth without a tangible change in its intensity. At higher annealing temperatures, the plasmon absorption band broadens and its intensity drops. Annealing of the ZnO films under such conditions causes their complete vaporization.     

Synthesis of silver nanocomposites by SCF impregnation of matrices of synthetic opal and Vycor glass by the Ag(hfac)COD precursor

Silver-containing nanocomposites were prepared by impregnating Vycor glass (a pore diameter of 4 nm) and synthesized opal matrices (an interstitial void size of 40 nm) with cyclooctadiene complex of silver hexafluoroacetylacetonate (Ag(hfac)COD), a silver precursor, dissolved in supercritical carbon dioxide and were examined by optical absorption spectroscopy, atomic force microscopy, and electron spin-resonance spectroscopy. It was demonstrated that the absorption spectra of Vycor glass and opal matrices impregnated with Ag(hfac)COD molecules and subjected to thermal treatment in air at temperatures above 50°C exhibit plasmon resonances characteristic of Ag nanoparticles at 420–430 nm. The peculiarities of the plasmon resonance band for both types of samples were attributed to the morphology of the pore space in which silver particles are formed. Paramagnetic Cu(hfac)₂ molecules (copper hexafluoroacetylacetonate) were used as a spectroscopic probe for estimating the distribution of the precursor in the pores of Vycor glass and opal matrices during supercritical fluid impregnation.     

In situ-monitored enhancement and quenching effect of Cu nanoclusters on Sm3+ photoluminescence in glass

An assessment of the influence of heat treatment temperature and retention time on the optical properties of a Cu⁺ and Sm³⁺ co-doped phosphate glass of interest to photonic applications is reported. Particularly, the enhancement of the orange-red photoluminescence (PL) from Sm³⁺ ions has been realized in the glass through the development of non-plasmonic Cu clusters. It was exposed during an in situ isothermal treatment wherein optical absorption and PL were monitored together in real time. Following the PL increase, a drop in the Sm³⁺ emission intensity was produced concurring with the appearance of Cu nanoparticles (NPs) exhibiting the surface plasmon resonance. Hence, the connection between energy donor (sensitizing) effects of small Cu clusters and the energy acceptor (quenching) character of Cu NPs is supported. It is the first time to the author's knowledge that the enhancement of Sm³⁺ luminescence via Cu clusters embedded in glass is indicated.     

Effect of thermal treatment on linear optical properties of Cu nanoclusters

Silica glass was implanted with 50 keV Cu⁺ ions at various fluences from 6×10¹⁵ to 8×10¹⁶ ions/cm² and thermally-annealed in air between room temperature to 1200 °C. UV/visible spectroscopy measurements reveal absorption bands at characteristics surface plasmon resonance (SPR) frequencies, signifying the formation of copper colloids in silica, even without thermal treatments. Such copper nanoclusters can be attributed to the relatively high mobility of copper atoms, even at ambient conditions. Using the equation derived from the framework of free-electron theory, the average radii of the Cu particles were found to be in the range 2-4 nm from the experimental surface plasmon absorption peaks. Radioluminescence (RL) spectra exhibited broad bands at 410 and 530 nm, associated with the presence of Cu⁺ ions in the as-implanted samples. The effect of thermal annealing in air on absorption and emission spectra of these Cu-implanted samples, as well as the formation of copper nanoclusters from original Cu⁺ ions, is discussed.     

Te/TeO2-SiO2复合薄膜的吸收和非线性光学特性研究

应用分光光度计测量Te/TeO₂-SiO₂复合薄膜的透射光谱和吸收光谱, 在480nm附近观察到Te颗粒引起的等离子体共振吸收峰; 采用Z扫描技术研究了共振(激发波长为532 nm)和非共振情况下(激发波长1064 nm) 不同电位制备薄膜的Te颗粒状态与复合薄膜的三阶非线性极化率的关系. 基于有效介质理论对复合薄膜的三阶非线性效应进行分析, 研究Te颗粒大小对Te/TeO₂-SiO₂复合薄膜的非线性光学性质的影响及其产生机理. 结果表明薄膜制备过电位增大, Te的粒径减小, 颗粒数量多, 颗粒分布趋于均匀, 使得金属颗粒的表面等离子体共振峰红移, 吸收强度增强, 导致三阶非线性光学效应增强, χ⁽³⁾由1064 nm的5.12×10^-7 esu增大为532 nm的8.11×10^-7 esu. 关键词： 碲 二氧化碲 复合薄膜 三阶非线性     

Metal-polymer composite films based on polyacrylonitrile and silver nanoparticles. Preparation and properties

The structures consisting of silver nanoparticles and polyacrylonitrile (PAN) are synthesized by the photopolymerization method yielding a homogeneous dispersion and a small size spread of nanoinclusions in PAN matrices, which is observed in images of transmission electron microscopy. The optical properties of the nanocomposites are studied to depend upon conditions of their obtaining. The minimum in the transmission spectra in a wavelength region of 430 nm, which is attributed to the surface plasmon resonance of silver nanoparticles, is found. The absorption peaks in the infrared range are observed at ∼820 and ∼1110 cm⁻¹ for the silver nitrate (AgNO₃) and the photoinitiator, respectively.     

Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering

Microcrystalline cellulose is a porous natural material which can be used both as a support for nanoparticles and as a reducer of metal ions. Cellulose supported nanoparticles can act as catalysts in many reactions. Cu, CuO, and Cu₂O particles were prepared in microcrystalline cellulose by adding a solution of copper salt to the insoluble cellulose matrix and by reducing the copper ions with several reducers. The porous nanocomposites were studied using anomalous small angle X-ray scattering (ASAXS), X-ray absorption spectroscopy, and X-ray diffraction. Reduction of Cu²⁺ with cellulose in ammonium hydrate medium yielded crystalline CuO nanoparticles and the crystallite size was about 6–20 nm irrespective of the copper concentration. The size distribution of the CuO particles was determined with ASAXS measurements and coincided with the crystallite sizes. Using sodium borohydrate or hydrazine sulfate as a reducer both metallic Cu and Cu₂O nanoparticles were obtained and the crystallite size and the oxidation state depended on the amount of reducer.     

Enhanced nonlinear optical responses in metal-glass nanocomposites

The “engineered” nonlinear nanocomposite materials with extremely large values of optical Kerr susceptibility and fast temporal responses that can be precisely tuned to satisfy the requirements of switching applications is of current interest in photonics. Metal quantum-dot composite glasses can exhibit enhanced optical susceptibility, χ⁽³⁾, whose real and imaginary parts are related to the intensity-dependent refractive index and two-photon absorption coefficient, respectively. Classical (dielectric) and quantum confinement effects come into play in the nonlinear optical responses of these nanocomposites. Metal nanocluster-glass composites have been synthesized by 200 keV Cu⁺ and 1.5 MeV Au⁺ ion implantations in fused silica glasses at a dose of 3 × 10¹⁶ ions/cm², followed by thermal annealing in reducing atmosphere to promote cluster growth. UV-Visible spectroscopy has revealed prominent linear absorption bands at characteristic surface plasmon resonance (SPR) frequencies signifying appreciable formation of copper and gold colloids in glass matrices. Third-order optical properties of the composite materials have been studied by Z-Scan and Anti-Resonant Interferometric Nonlinear Spectroscopy (ARINS) measurements. The sign of nonlinear refraction is readily obtained from the Z-Scan signatures. The ARINS technique utilizes the dressing of two unequal-intensity counter-propagating pulsed light beams with differential nonlinear phases, which occur upon traversing the sample if it exhibits nonlinear optical response. This difference in phase manifests itself in the intensity-dependent transmission. The nonlinear refractive index, nonlinear absorption coefficient, the real and imaginary parts of the third-order optical susceptibility have been extracted.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

Tuning the plasmon resonance of metallic tin nanocrystals in Si-based materials

The optical properties of metallic tin nanoparticles embedded in silicon-based host materials were studied. Thin films containing the nanoparticles were produced using RF magnetron sputtering followed by ex situ heat treatment. Transmission electron microscopy was used to determine the nanoparticle shape and size distribution; spherical, metallic tin nanoparticles were always found. The presence of a localized surface plasmon resonance in the nanoparticles was observed when SiO₂ and amorphous silicon were the host materials. Optical spectroscopy revealed that the localized surface plasmon resonance is at approximately 5.5 eV for tin nanoparticles in SiO₂, and at approximately 2.5 eV in amorphous silicon. The size of the tin nanoparticles in SiO₂ can be varied by changing the tin content of the films; this was used to tune the localized surface plasmon resonance.     

Fabrication of composite based on GeSi with Ag nanoparticles using ion implantation

Comparative analysis of the structural and optical properties of composite layers fabricated with the aid of implantation of single-crystalline silicon (c-Si) using Ge⁺ (40 keV/1 × 10¹⁷ ions/cm²) and Ag⁺ (30 keV/1.5 × 10¹⁷ ions/cm²) ions and sequential irradiation using Ge⁺ and Ag⁺ ions is presented. The implantation of the Ge⁺ ions leads to the formation of Ge: Si fine-grain amorphous surface layer with a thickness of 60 nm and a grain size of 20–40 nm. The implantation of c-Si using Ag⁺ ions results in the formation of submicron porous amorphous a-Si structure with a thickness of about 50 nm containing ion-synthesized Ag nanoparticles. The penetration of the Ag⁺ ions in the Ge: Si layer stimulates the formation of pores with Ag nanoparticles with more uniform size distribution. The reflection spectra of the implanted Ag: Si and Ag: GeSi layers exhibit a sharp decrease in the intensity in the UV (220–420 nm) spectral interval relative to the intensity of c-Si by more than 50% owing to the amorphization and structuring of surface. The formation of Ag nanoparticles in the implanted layers gives rise to a selective band of the plasmon resonance at a wavelength of about 820 nm in the optical spectra. Technological methods for fabrication of a composite based on GeSi with Ag nanoparticles are demonstrated in practice.     

Ag离子注入非晶SiO2的光学吸收、拉曼谱和透射电镜研究

能量为200keV的Ag离子，以1×10¹⁶，5×10¹⁶，1×10¹⁷ cm^-2的剂量分别注入到非晶SiO₂玻璃，光学吸收谱显示：注入剂量为1×10¹⁶ cm^-2的样品的光吸收谱为洛伦兹曲线，与Mie理论模拟的曲线形状一致；注入剂量较大的5×10¹⁶，1×10¹⁷ cm^-2的谱线共振吸收增强，峰位红移并出现伴峰. 透射电镜观察分析表明，注入剂量不同的样品中形成的纳米颗粒的大小、形状、分布都不同，注入剂量较大的还会产生明显的表面溅射效应，这些因素都会影响共振吸收的峰形、峰位和峰强. 当注入剂量达到1×10¹⁷ cm^-2时，Ag纳米颗粒内部可能还形成了杂质团簇. 关键词： 离子注入 纳米颗粒 共振吸收 红移     

Au:TiO2和Au:Al2O3纳米颗粒复合膜的线性和非线性光学特性

主要从实验和理论两个方面,探讨了不同Au颗粒尺寸和不同基质对Au：TiO₂和Au：Al₂O₃复合膜线性和非线性光学性质的影响.用吸收光谱研究了Au颗粒尺寸和基质与Au复合膜表面等离子体共振带之间的关系;用皮秒Z扫描技术研究了共振和非共振情况下(激发光波长分别为532nm和1064nm),Au颗粒尺寸和基质与复合膜三阶非线性极化率的关系.基于表面等离子体共振理论和局域场增强理论对复合膜进行了分析,得到了不同Au颗粒大小和不同基质时Au复合膜的 关键词： 金属纳米颗粒 复合膜 三阶非线性 表面等离子体共振     

Microwave-induced fabrication of copper nanoparticle/carbon nanotubes hybrid material

Copper nanoparticle/multi-walled carbon nanotube (MWCNT) hybrid material could be fabricated by microwave irradiation to a suspension of MWCNTs dispersed in copper precursor with the presence of ethylene glycol. Microscopic and spectroscopic analyses could confirm the uniform dispersion of copper oxide nanoparticles hybridized on the outer surface of MWCNTs. Reduction of Cu²⁺ ions to Cu₂O and Cu nanoparticles was ascribed to functional groups which were generated after the precursor was irradiated by microwave. Sufficient irradiation time of 5 min or longer played an important role to induce the agglomeration of copper oxide nanoparticles on the MWCNT surface.     

Optical properties of Cu nanocomposite glass obtained via CuO and SnO co-doping

Prospective applications of plasmonic nanocomposites in photonic and optoelectronic devices demand innovative means of material syntheses, as well as a comprehensive understanding of the influence of material composition and processing on resulting properties. In this work, it is shown that a phosphate glass matrix prepared with stoichiometric amounts of CuO and SnO dopants by the melting technique may well be effective for the precipitation of Cu nanoparticles (NPs) upon heat treatment (HT). Optical absorption and photoluminescence (PL) spectroscopy, including emission decay dynamics, are employed in the characterization of the melt-quenched glass, and for investigating the influence of HT on material optical properties. The as-prepared material appeared highly luminescent; the data suggests contributions from both twofold-coordinated tin centers and Cu⁺ ions to light emission. The PL depends strongly on excitation wavelength; e.g. excitation at 260 nm shows a blue–white emission for which a significant contribution from tin is indicated, whereas excitation at 360 nm produces an orange emission in association with Cu⁺ ions. Thermal processing results in the chemical reduction of ionic copper via Sn²⁺ ultimately producing Cu NPs in the matrix, as evidenced by the appearance of the surface plasmon resonance around 574 nm. As a result, Cu⁺ PL decreases and the emission band shows a dip due to reabsorption by Cu NPs in resonance.     

绝缘体中金属离子注入合成纳米颗粒的理论研究

理论上提出了利用离散电子态来计算绝缘体中金属纳米颗粒Fermi能级的方法,给出了金属纳米颗粒的能级结构,并得到了依据金属纳米颗粒等离子体共振峰计算金属纳米颗粒尺寸的新公式.该理论可解释相关现象,通过实验初步验证了该理论的正确性. 关键词： 离子注入 金属纳米颗粒 绝缘体 Fermi能级     

Ion synthesis and optical properties of gold nanoparticles in an Al2O3 matrix

Single-crystal Al₂O₃(0001) and Al₂O₃(1120) substrates are implanted by 160-keV Au⁺ ions with doses from 10¹⁵ to 10¹⁷ cm^?2. Some of the implanted samples are air-annealed at 800–1200°C. The properties of the synthesized composite layers are studied by Rutherford backscattering and linear optical reflection measurements, and their nonlinear optical characteristics are examined by RZ-scanning using a picosecond Nd: YAG laser operating at a wavelength of 1064 nm. The Rutherford backscattering spectra indicate that the implanted impurity concentrates near the surface of the Al₂O₃. The formation of gold nanoparticles in the Al₂O₃ can be judged from the characteristic optical plasmon resonance band in the reflectance spectra of the samples irradiated to a dose higher than 6.0 × 10¹⁶ cm^?2. The synthesized particles are shown to be responsible for nonlinear optical refraction in the samples. The nonlinear refractive index, n ₂, and the real part of the third-order susceptibility, Rex⁽³⁾, of the composite layers are determined.     

Adsorption and photocatalytic degradation of methylene blue on Zn1−xCuxS nanoparticles prepared by a simple green method

Nanoparticles of Zn_1−xCu_xS with various dopant contents (0 ≤ x ≤ 0.15) were prepared in water by refluxing for 90 min at about 95 °C. Powder X-ray diffraction (XRD) patterns of the nanoparticles demonstrate that loading of Cu²⁺ ions does not change the crystal structure of ZnS. Scanning electron microscopy (SEM) images demonstrate that size of the nanoparticles decreases with increasing Cu²⁺ ions. UV-Vis diffuse reflectance spectra (DRS) of the nanoparticles show significant absorption in visible light region. Adsorption capacity of the nanoparticles for methylene blue (MB) increases with mole fraction of copper ions. Photocatalytic activity of the nanoparticles toward photodegradation of MB was evaluated under visible light irradiation. The results indicate that Zn_0.85Cu_0.15S nanoparticles exhibit highest photocatalytic activity among the prepared samples. Moreover, effects of refluxing time applied for preparation of the nanoparticles and calcination temperature were investigated.     

Synthesis of Cu 2 O,CuCl, and Cu 2 OCl 2 nanoparticles by ultrafast laser ablation of copper in liquid media

Copper complex nanoparticles were fabricated from bulk copper using picosecond laser ablation in water and chloroform. We found that composition of the nanoparticles was CuCl and Cu₂OCl₂ in chloroform at three different input fluences; Cu₂O in water which was confirmed from the data of EDAX, UV-Visible absorption spectra, and selected area electron diffraction pattern. We have also performed nonlinear optical studies of colloidal nanoparticles using Z-scan technique at 800 nm and ～2 ps laser pulses. Cu₂O NPs exhibited two-photon absorption at lower peak intensities while three-photon absorption was observed at higher peak intensities. Other samples exhibited two-photon absorption at all peak intensities.