Interface influence on the surface plasmon resonance of Ag nanocluster composite

Ag nanoclusters embedded in silica matrix were formed by ion implantation to different doses. The intensity of surface plasmon resonance absorption enhances with the increasing of the implanted dose, but decreases at dose higher than 1×10¹⁷ ions/cm² due to the surface sputtering effect. The lattice distortion of nanoclusters has been observed using a high-resolution transmission electron microscope. The positions of the resonance peaks are red-shifted after the samples were annealed in oxidizing atmosphere at elevated temperatures. The red shift is mainly attributed to the interactions of Ag nanoclusters with diffused oxygen and nanovoids.     

Controlling the morphology of Ag nanoclusters by ion implantation to different doses and subsequent annealing

Ag ions were implanted at 200 keV into silica with nominal doses ranging from 5x10(16) to 2x10(17) ions/cm2. We find that nanovoid-containing Ag nanoclusters form in the implanted samples with doses higher than 1x10(17) ions/cm2. When the dose is increased to 2x10(17) ions/cm2, the nanovoids gradually shrink and form a sandwiched nanocluster-nanovoid-nanocluster structure. The evolution of sandwiched nanoclusters during annealing was observed by in situ transmission electron microscopy experiments. Potential mechanisms for the formation and evolution of the irradiation-induced nanovoids and the sandwiched structure nanoclusters with increasing doses are discussed. The structural optimization of the sandwiched structure nanoclusters was performed by molecular mechanics calculations.     

Ag-Cu离子注入玻璃后不同气氛退火的光吸收研究

采用MEVVA源（metal vapor vacuum arc ion source）引出的强束流脉冲Ag,Cu离子先后注入到SiO₂玻璃，x射线光电子能谱仪（XPS）分析显示Ag，Cu大多仍为金属态，有部分氧化态Cu存在.透射电镜观察分析和光学吸收谱都表明在衬底中形成了纳米合金颗粒.结合有效媒质理论，得到模拟的光学吸收谱，与实验结果基本符合，较好地验证了以上结论.样品退火后颗粒发生分解，分解的颗粒在氧化气氛下被氧化，且有部分向样品表面蒸发；在还原气氛下氧化态元素被还原并成核生长.故 关键词： 离子注入 纳米颗粒 退火 光学吸收率     

Formation of metallic nanophases in silica by ion beam mixing. Part II: cluster formation

2 matrix by ion-beam mixing of SiO₂/Ag multilayers is studied via Rutherford backscattering spectrometry, optical absorption, and transmission electron microscopy experiments. In a first step, irradiation with MeV heavy ions transforms the continuous Ag layers into a string of micrometer-sized Ag inclusions. This mechanism can be attributed to lateral segregation of metallic atoms induced by irradiation. In a second step, the Ag inclusions are broken up by incoming ions and Ag nanoclusters are formed by agglomeration of mobile Ag atoms. The latter mechanism is likely due to a combination of ballistic mixing and radiation-induced segregation or radiation-enhanced diffusion processes. The size of the metallic nanoclusters formed depends also on the irradiation temperature. Received: 27 October 1997/Accepted: 3 February 1998     

Nonlinear optical properties of Cu nanoclusters by ion implantation in silicate glass

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 1 × 10¹⁷ ions/cm² has been studied. The microstructural properties of the nanoclusters were analysed by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 nm and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. The mechanisms responsible for the nonlinear response were discussed. Absolute third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 2.1 × 10⁻⁷ esu at 532 nm and 1.2 × 10⁻⁷ esu at 1064 nm, respectively.     

Third-order nonlinear optical response of Cu/Ag nanoclusters by ion implantation under 1064 nm laser excitation

The evolution of nanoclusters in sequentially ion-implanted Cu/Ag into silica glasses has been studied. The doses for implantation (×10¹⁶ ions/cm²) were 5Cu/5Ag, 5Cu/10Ag and 5Cu/15Ag, respectively. The microstructural properties of the nanoclusters are characterized by optical absorption spectra and transmission electron microscopy (TEM). Fast nonlinear optical refraction and nonlinear optical absorption coefficients were measured at 1064 nm of wavelength using Z-scan technique. Results in this project indicate that different optical nonlinearities could be selectively obtained at the near-infrared region of 1064 nm of wavelength by changing the metal ingredient percentage in silica.     

Crystalline quality of 3C-SiC formed by high-fluence C-implanted Si

Carbon ions at 40 keV were implanted into (1 0 0) high-purity p-type silicon wafers at 400 °C to a fluence of 6.5 × 10¹⁷ ions/cm². Subsequent thermal annealing of the implanted samples was performed in a diffusion furnace at atmospheric pressure with inert nitrogen ambient at 1100 °C. Time-of-flight energy elastic recoil detection analysis (ToF-E ERDA) was used to investigate depth distributions of the implanted ions. Infrared transmittance (IR) and Raman scattering measurements were used to characterize the formation of SiC in the implanted Si substrate. X-ray diffraction analysis (XRD) was used to characterize the crystalline quality in the surface layer of the sample. The formation of 3C-SiC and its crystalline structure obtained from the above mentioned techniques was finally confirmed by transmission electron microscopy (TEM). The results show that 3C-SiC is directly formed during implantation, and that the subsequent high-temperature annealing enhances the quality of the poly-crystalline SiC.     

Formation of metal nanoparticles in silica by the sequential implantation of Ag and Cu

Spherical-like nanoparticles have been formed by sequentially ion-implanting Ag/Cu into silica glasses. During sequential Ag/Cu ion implantation, the diameter of Cu nanoparticles is increased and the average Ag nanoparticle diameter is decreased with increasing Cu ion dose. The evolution of nanoparticles is characterized by grazing incidence X-ray diffraction, extended X-ray absorption fine structure spectroscopy and transmission electron microscopy. Nanovoids in the nanoparticles are formed by sequential ion implantation. PACS 61.72.Ww; 61.46.-W     

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     

MeV Al+ and Al2+ ions implantation in Si(100): surface roughness and defects in the bulk

This paper deals with the implantation of high-energy (1.0–3.0 MeV) atomic and molecular Al⁺ ions in Si(100) to a fluence of 5×10¹⁴ Al atoms/cm² at room temperature. The molecular effect, i.e. the increase of the displacement yield compared with the sum of the atomic yields, and the damage formation as well as defect behaviour after annealing have been investigated. A detailed experimental study has been made of the evolution of extended secondary defects which form during thermal anneals of Al⁺ or Al₂ ⁺ irradiated silicon. The samples have been examined using combined Rutherford backscattering and channeling experiments together with transmission electron microscopy observations. The surface structure of the implanted wafers has been measured by atomic force microscopy. The results for the implantation-induced roughness at the Si surface, resulting from Al⁺ or Al₂ ⁺ irradiation at the same energy/atom, total atomic fluence, flux rate, and irradiation temperature, are presented and discussed. Received: 19 August 1999 / Accepted: 20 October 1999 / Published online: 23 February 2000     

Observation of ε′-Ag17 Mg54 phase induced by plasma immersion ion implantation

This paper provides a confirmation of the effectiveness of the recently suggested ab initio approach to the theoretical prediction of phase transformations which may be induced in metallic alloys by metal plasma immersion and ion implantation processing. The approach is based on an assumption that at certain concentrations of the implanted species, the relaxation of the exited electronic state of the implanted structure should be accompanied by the rearrangement of atoms leading to the formation of a new phase. Recently, on the basis of density functional theory calculations of the energetic characteristics of the electronic subsystems of the implanted Mg–Ag system, it was predicted that concentrations of the implanted Ag ions within the range from ～18 to 23 at% Ag, favor transition to the phase ε′-Ag₁₇Mg₅₄. Our transmission electron microscopy observations and electron diffraction analysis of the Mg-based alloy subjected to the implantation of Ag ions at dose of ～5×10¹⁵ ion/cm² confirmed that the formation of the ε′-Ag₁₇Mg₅₄ phase indeed takes place.     

Formation and microstructural investigation of Ag-Cu alloy nanoclusters embedded in SiO2 formed by sequential ion implantation

We report on the formation of alloy nanoclusters in silica by Ag/Cu ion sequential implantation. The formation of alloy nanocluster has been evidenced by optical absorption spectra, selected area electron diffraction and energy dispersive X-ray spectra. The microstructure characters of nanoclusters have been studied by high resolution transmission electron microscopy. The lattice distortion of some nanoclusters has been observed. A model has been given to explain the distortion. Some defects (partial dislocation, stacking faults) have been found in nanoclusters.     

Gettering of implanted Au in MeV?C implanted Si

The gettering behavior of 1 MeV?C implantation induced defects for Au (1.5 MeV, 2.2×10¹⁵ cm^-2), implanted into FZ Si(111), has been investigated using Rutherford backscattering spectrometry and cross-sectional transmission electron microscopy. The gettering efficiency of the C implanted layer has been studied as a function of C dose, annealing temperature and time. For a C dose of 2×10¹⁶ cm^-2, a 2 h anneal at 950 °C has been found to result in a gettering efficiency going beyond ?90%. Thermal stability of the gettered Au in the C implanted layer has subsequently been investigated over a temperature range of 950–1150 °C using isochronal annealing. The gettered amount has been found to be stable up to 1050 °C beyond which there is a release. We have observed nanovoids in the C implanted layer surrounded by ?-SiC precipitates along with patches of a-SiC. Up to about 1050 °C, these nanovoids act as efficient gettering centers beyond which they seem to release the trapped Au. Four distinct regimes in annealing temperature with different mechanisms for Au gettering have been observed.     

Observation of ferromagnetism at room temperature for Cr ions implanted ZnO thin films

Single crystalline ZnO films were grown on c-plane GaN/sapphire (0 0 0 1) substrates by molecular beam epitaxy. Cr⁺ ions were implanted into the ZnO films with three different doses, i.e., 1 × 10¹⁴, 5 × 10¹⁵, and 3 × 10¹⁶ cm⁻². The implantation energy was 150 keV. Thermal treatment was carried out at 800 °C for 30 s in a rapid thermal annealing oven in flowing nitrogen. X-ray diffraction (XRD), atomic force microscopy, Raman measurements, transmission electron microscopy and superconducting quantum interference device were used to characterize the ZnO films. The results showed that thermal annealing relaxed the stress in the Cr⁺ ions implanted samples and the implantation-induced damage was partly recovered by means of the proper annealing treatment. Transmission electron microscopy measurements indicated that the first five monolayers of ZnO rotated an angle off the [0 0 0 1]-axis of the GaN in the interfacial layer. The magnetic-field dependence of magnetization of annealed ZnO:Cr showed ferromagnetic behavior at room temperature.     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Formation and Shape Transition of Nanostructures on Si(100) surfaces after MeV Sb Implantation

We have studied the formation of nanostructures on Si(100) surfaces after 1.5 MeV Sb implantation. Scanning Probe Microscopy has been utilized to investigate the ion implanted surfaces. We observe the formation of nanostructures after a fluence of 1×10¹³ ions/cm². These surface structures are elliptical in shape with an eccentricity of 0.86 and their major and minor axes having dimensions of about 11.6 nm and 23.0 nm, respectively. The area of the nanostructure is 210 nm²at this fluence. Although the nanostructures remain of elliptical shape, their area increase with increasing fluence. However, after a fluence of 5×10¹⁴ ions/cm² a transition in shape of nanostructures is observed. Nanostructures become approximately circular with an eccentricity of 0.19 and a diameter of about 30.1 nm. At this fluence we also observe a large increase in the area of the nanostructures to 726 nm². Surface morphology and surface roughness of the ion implanted surfaces has also been discussed.     

Immobilization of silver nanoparticles on silica microspheres

The silver nanoparticles (Ag NPs) have been immobilized onto silica microspheres through the adsorption and subsequent reduction of Ag⁺ ions on the surfaces of the silica microspheres. The neat silica microspheres that acted as the core materials were prepared through sol–gel processing; their surfaces were then functionalized using 3-mercaptopropyltrimethoxysilane (MPTMS). The major aims of this study were to immobilize differently sized Ag particles onto the silica microspheres and to understand the mechanism of formation of the Ag nano-coatings through the self-assembly/adsorption behavior of Ag NPs/Ag⁺ ions on the silica spheres. The obtained Ag NP/silica microsphere conglomerates were characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy-dispersive spectroscopy (EDS). Their electromagnetic wave shielding effectiveness were also tested and studied. The average particle size of the obtained Ag NPs on the silica microsphere was found that could be controllable (from 2.9 to 51.5 nm) by adjusting the ratio of MPTMS/TEOS and the amount of AgNO₃.     

Effects of Helium and Oxygen Common Implantation in Silicon Wafer

Defect engineering for SiO2 precipitation is investigated using He-ion implantation as the first stage of separation by implanted oxygen （SIMOX）. Cavities axe created in Si by implantation with helium ions. After thermal annealing at different temperatures, the sample is implanted with 120 keV 8.0 ×1016 cm 2 0 ions. The Q ion energy is chosen such that the peak of the concentration distribution is centred at the cavity band. For comparison, another sample is implanted with O ions alone. Cross-sectionM transmission electron microscopy （XTEM）, Fourier transform infrared absorbance spectrometry （FTIR） and atomic force microscopy （AFM） measurements are used to investigate the samples. The results show that a narrow nano-cavity layer is found to be excellent nucleation sites that effectively assisted SiO2 formation and released crystal lattice strain associated with silicon oxidation.     

Investigation of helium implantation induced blistering in InP

 Four-inch InP wafers were implanted with 100 keV helium ions with a dose of 5×10¹⁶ cm⁻² and subsequently annealed in air in the temperature range of 225-400°C in order to determine the blistering kinetics of these wafers. An Arrhenius plot of the blistering time as a function of reciprocal temperature revealed two different activation energies for the formation of surface blisters in InP. The activation energy was found to be 0.30 eV in the higher temperature regime of 300-400 °C and 0.74 eV in the lower temperature regime of 225-300 °C. The implantation induced damage was analyzed by cross-sectional transmission electron microscopy, which revealed a band of defects extending from 400-700 nm from the surface of InP. The damage band was found to be decorated with a large number of nanovoids having diameters between 2 and 5 nm. These nanovoids served as precursors for the formation of microcracks inside InP upon annealing, which led to the formation of surface blisters.     

The optical properties of planar waveguides in LiB3O5 crystals formed by Cu implantation

A planar optical waveguide has been formed in a LiB₃O₅ crystal using 6.0 MeV Cu⁺-ions with a dose of 1 × 10¹⁵ ions/cm² at room temperature. Possible propagating modes were measured at a wavelength of 633 nm using the prism-coupling method. The refractive index profiles of the waveguide were reconstructed by an effective refractive index method and the beam propagation method was used to investigate the properties of the propagation modes in the formed waveguide. The results suggest that the fundamental TE₀ and TM₀ modes may be well-confined and propagate a longer distance inside the waveguide. The implantation process was also simulated using the transport of ions in matter code (TRIM), which indicates that the nuclear energy deposition may be the main factor for the refractive index change.