Interaction of high-power laser pulses with glasses containing implanted metallic nanoparticles

Sodium calcium silicate glasses with Ag⁺ implanted ions are studied. The ion implantation conditions are as follows: the energy is 60 keV, the dose is 7×10¹⁶ cm⁻², and the ion current density is 10 μA/cm². Ion implantation provides the formation of a composite layer that incorporates silver nanoparticles in the surface region of glass. The size distribution of nanoparticles over the depth in the composite layer is strongly nonuniform. The effect of a high-power pulsed excimer laser on the composite layer is investigated. It is found that, under laser irradiation, the size of silver nanoparticles in the implanted layer decreases but the size distribution of nanoparticles over the depth remains nonuniform, even though it becomes slightly narrower compared to that observed prior to irradiation. The experimental results are interpreted in terms of the effects of the melting of glass and metallic particles on a nanosecond scale. __________ Translated from Fizika Tverdogo Tela, Vol. 43, No. 11, 2001, pp. 2100–2106. Original Russian Text Copyright ? 2001 by Stepanov, Popok, Hole, Bukharaev.     

Ion synthesis and laser annealing of Cu nanoparticles in Al2O3

Al₂O₃ samples with Cu nanoparticles, synthesised by ion implantation at 40 keV with a dose of 1×10¹⁷ ion/cm² and a current density from 2.5 to 12.5 μA/cm², were annealed using ten pulses from a KrF excimer laser with a single pulse fluence of 0.3 J/cm². The copper depth distribution, formation and modification of metal nanoparticles under the ion implantation and laser treatment were studied by Rutherford backscattering (RBS), energy dispersive X-ray (EDX) analysis, atomic force microscopy (AFM) and optical spectroscopy. It was found that laser annealing leads to a reduction in the nanoparticle size without diffusion of metal atoms into the bulk. The change in particle size and the possibility for oxidation of the copper particles are examined in the framework of Mie theory. Calculations presented show that under excimer laser treatment, Cu nanoparticles are more likely to be reduced in size than to undergo oxidation. Received: 19 April 2001 / Accepted: 7 November 2001 / Published online: 23 January 2002     

Laser and Thermal Modification of Silver–Ion Implanted Glasses

We investigate sodium–calcium silicate glasses implanted with 60 keV Ag⁺ ions with a dose of 3·10¹⁶ cm^–2 at an ion current density of 10 A/cm². As a result of the ion implantation, a composite layer with silver nanoparticles is synthesized in the region near the surface. However, this layer is characterized by high nonuniformity in the size distribution of these particles over the depth of the layer. Subsequent pulsed laser irradiation in combination with equilibrium heat treatment makes it possible to modify this composite layer, improving the uniformity in the size distribution of the nanoparticles. This is particularly promising for the improvement of the technology of obtaining nonlinear optical materials. To control the parameters of the layers obtained we suggest a method based on an analysis of the optical reflection and transmission spectra measured on the side of the implanted and opposite surfaces of glass samples.     

Optical properties of metal nanoparticles synthesized in a polymer by ion implantation: A review

Polymer composite layers irradiated by 30-keV Ag⁺ ions with doses from 3.1×10¹⁵ to 7.5×10¹⁶ cm^?2 and an ion current of 4 µA/cm² are investigated. The composites were examined using Rutherford backscattering (RBS), transmission electron microscopy (TEM), and optical spectroscopy. As follows from electron microscopy and electron microdiffraction data, ion implantation is a promising tool for synthesizing silver nanoparticles in the surface region. The optical density spectra taken of these composites demonstrate that the silver nanoparticles exhibit unusually weak plasma resonance. The formation of silver nanoparticles in layers carbonized by ion implantation is considered. Based on the Mie theory, optical extinction spectra for silver particles in the polymer and carbon matrices are simulated and optical spectra for complex silver core-carbon sheath nanoparticles are calculated. The physics behind the experimental optical spectra of the composite is discussed.     

Synthesis and optical properties of silver nanoparticles in ORMOCER

Experimental results on synthesis of metal nanoparticles in ORMOCER by ion implantation are presented. Silver ions were implanted into organic/inorganic matrix at an accelerating energy of 30?keV and doses in the range of 0.25?10¹⁷ to 0.75?10¹⁷?ion/cm². The silver ions form metal nanoparticles, which demonstrate surface plasmon absorption at the wavelength of 425?C580?nm. The nonlinear absorption of new composite materials is measured by Z-scan technique using 150?fs laser pulses at 780?nm wavelength. ORMOCER matrix shows two-photon nonlinear absorption, whereas ORMOCER with silver nanoparticles demonstrates saturated absorption. Some optical applications of these composite materials are discussed.     

Laser Annealing of SiO2 Glass with Copper Nanoparticles

Composite layers formed in SiO₂ by implantation of 50keV Cu⁺ ions with a dose of 8·10¹⁶ cm^–2 at an ion current density of 10 A/cm² have been investigated. It is shown that ion implantation carried out under the chosen conditions allows one to synthesize copper nanoparticles in the surface region of a dielectric. The exposure of composites to highpower pulses of an excimer krypton laser at a wavelength in the SiO₂ transmission region has been investigated. In the absence of effective optical absorption by a glass substrate, the dynamics of the change in the structure of the layer with metallic nanoparticles is determined by the number of laser pulses. It has been established that at the initial stage of pulsed irradiation fragmentation of the largest nanoparticles occurs followed by the inverse process of their agglomeration as a result of slight heating of the glass matrix; further exposure to the laser irradiation leads to an effective accumulation of energy in the particles and, as a consequence, to their melting and dissociation into small clusters and individual atoms.     

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.     

Optical reflection from dielectric layers containing metal particles formed by ion implantation

Dielectric layers with silver nanoparticles, which are synthesized in a soda-silicate glass by implantation of 60-keV ions with a dose of 7.0×10¹⁶ Ag⁺/cm² at an ion current density of 10 μmA/cm², are analyzed. The depth of silver distribution was measured by Rutherford backscattering. Data on optical characteristics of composite layers were obtained from the transmission spectra and from the reflection, which were measured both from the side of an implanted glass surface and from the unimplanted side. To calculate reflection spectra, a multilayer plane-parallel film structure was considered, which was modeled on the basis of the matrix method using complex Fresnel coefficients. Dielectric functions of separate layers were determined using the Maxwell-Garnet theory of an effective medium. A qualitative agreement between the experimental and the model optical spectra was obtained taking into account a nonuniform depth distribution of metal nanoparticles in a composite material.     

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     

A study of the nonlinear refractive index in amorphous Ge–As–S layers and nanocomposites with gold nanoparticles

Nonlinear refractive indices of simple and composite chalcogenide glasses with gold nanoparticles are measured by the Z-scan method using a femtosecond Ti:sapphire laser with a central wavelength of 800 nm and a pulse duration of 40 fs. It is shown that introduction of nanoparticles into thin layers of amorphous GeS₂, As₃₀Ge₂₀S₅₀, and As₃Ge₃₅S₆₂ leads to a decrease in the total nonlinear refractive index due to additional absorption of femtosecond laser radiation without efficient excitation of localized plasmons outside the resonance region. For example, the nonlinear refractive index decreases with addition of gold nanoparticles from 16.1 × 10^–12 to 13.0 × 10^–12 cm²/W for GeS₂, from 3.9 × 10^–12 to 3.2 × 10^–12 cm²/W for As₃₀Ge₂₀S₅₀, and from 5.8 × 10^–12 to 4.7 × 10^–12 cm²/W for As₃Ge₃₅S₆₂.     

Three-dimensional structuring of sapphire by sequential He+ ion-beam implantation and wet chemical etching

We present a method for the selective two- and three-dimensional patterning of sapphire using light ion-beam implantation to generate severe lattice damage to depths exceeding 1 μm and subsequent selective wet chemical etching of the damaged regions by hot H₃PO₄. C-cut sapphire crystals were implanted through contact masks using ion fluences of 1×10¹⁶ to 5×10¹⁷ He⁺/cm² and energies up to 400 keV. The etching process is characterized by a high selectivity and a rate of approximately 19 nm/min. Whereas an implantation that produces a continuously damaged pathway results in complete etching from the surface, sole in-depth implantation using only high-energy ions leads to under-etching of the crystalline surface layer. By a combination of these processes we have fabricated three-dimensional structures such as channels and bridges in sapphire. Received: 14 October 2002 / Accepted: 15 October 2002 / Published online: 26 February 2003 RID="*" ID="*"Corresponding author. Fax +41-21/693-3701, E-mail: aurelian.crunteanustanescu@epfl.ch     

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.     

飞秒激光作用下金掺杂硅酸盐玻璃的光致晶化研究

研究了金掺杂硅酸盐玻璃在飞秒激光辐照和热处理作用下的光致晶化行为，分析探讨了其机理和激光辐照条件的影响.吸收光谱测试表明玻璃内部析出金纳米颗粒. 金纳米颗粒掺杂玻璃在近共振纳秒脉冲作用下显示了强的光限幅效应, 且改变飞秒激光诱导参数可改变该复合玻璃的光学非线性. 关键词： 光致晶化 飞秒激光 金纳米颗粒 硅酸盐玻璃 光限幅     

Influence of ion-irradiation parameters on defect formation in silicon films

It is shown that unlike bulk silicon, for which amorphization is observed at an irradiation dose of 5 × 10¹⁶ ion/cm², thin silicon films on sapphire are amorphized at lower critical doses (10¹⁵ ion/cm²). An undamaged surface layer remains when the silicon films are irradiated with Si⁺ ion beams. Its thickness depends on the current density of the incident beam. Rutherford backscattering studies show that annealing at 950°C improves the crystallinity of the irradiated silicon film. Annealing of the films at 1100°C leads to mixing of the silicon-sapphire interface.     

Investigation of the nonlinear optical characteristics of composite materials based on sapphire with silver, copper, and gold nanoparticles by the reflection Z-scan method

The nonlinear optical characteristics of silver, copper, and gold nanoparticles synthesized in a sapphire matrix by ion implantation are studied. The measurements are performed by the RZ-scan method with optical reflection at the radiation wavelength of a picosecond Nd:YAG laser (λ = 1064 nm). The nonlinear refractive indices and the real parts of the third-order nonlinear susceptibility of the composites are determined. It is shown that the nonlinear refraction in the samples is caused by the Kerr effect.     

Synthesis of periodic plasmonic microstructures with copper nanoparticles in silica glass by low-energy ion implantation

Ion implantation was used to locally modify the surface of silica glass to create periodic plasmonic microstructures with Cu nanoparticles. Nanoparticles were synthesized by Cu-ion irradiation of the silica glass at the ion energy of 40 keV, dose of 5×10¹⁶ ions/cm² and current density of 5 μA/cm². This procedure involves low-energy ion implantation into the glass through a mask placed at the surface. Formation of nanoparticles was observed by optical spectroscopy and atomic force microscopy. The presented results clearly demonstrate how the low-energy ions can be used for the fabrication of photonic microstructures on dielectric surfaces in a single-step process.     

Silver nanoparticles produced by PLD in vacuum: role of the laser wavelength used

In this work we report the results of investigation of silver (Ag) nanoparticles prepared on a silica substrate by laser ablation. Our attention was focused on the mean diameter, size distribution and optical absorption properties of nanoparticles prepared in vacuum by using different laser wavelengths. The fundamental wavelength and the second, third, and fourth harmonics of a nanosecond Nd:YAG laser were used for nanoparticles fabrication. The corresponding values of the laser fluence for each wavelength were: 0.6 J/cm² at 266 nm, 0.8 J/cm² at 355 nm, 2.8 J/cm² at 532 nm, and 2 J/cm² at 1064 nm. The Ag nanoparticles produced have mean diameters in the range from 2 nm to 12 nm as the nanoparticles’ size decreases with the decrease of the wavelength used. The presence of the Ag nanoparticles was also evidenced by the appearance of a strong optical absorption band in the measured UV-VIS spectra associated with surface plasmon resonance (SPR). A redshift and widening of the absorption peak were observed as the laser wavelength was increased. Some additional investigations were performed in order to clarify the structure of the Ag nanoparticles.     

Stimulation of secondary negative ion emission by implantation of alkaline ions into the surface layer of a solid followed by heating

A new method of stimulating secondary negative ion emission is suggested that is based on implantation of alkaline ions into the surface layer of a solid with subsequent heating to a temperature providing optimal coverage of the surface (about half a monolayer) by activator (alkaline) ions. It is shown that, by appropriately selecting the implantation dose (10¹⁸–10¹⁹ cm⁻³) and surface temperature (500–900°C), one can reach such a degree of coverage of the sample surface by activator ions that its work function eφ becomes minimal: 1.9 eV for molybdenum and 2.1 eV for copper. It is found that, with the implantation (irradiation) dose and surface temperature chosen properly, one can, by means of outdiffusion of cesium atoms, achieve such a degree of surface coverage that remains unchanged during the continuous sputtering of the surface by a cesium ion beam.     

Spatial distribution of defects produced by boron ion implantation of silicon

A simple technique for the study of the spatial distribution of the damage produced by ion implantation of silicon has been developed. The damage depth distribution for 40 keV boron ions in silicon has been studied at irradiation doses from 7 × 10¹¹ to 3.9 × 10¹⁴ ions/cm² and the relative defect peak depth R _d/R _p = 0.85 determined. An increase of layer conductivity as the surface part of the implanted layer is removed has been revealed. This effect is caused by the presence of radiation defects in the surface region of the layer. The “electrical” cluster diameter is about 28 A and the overlapping cluster dose is close to 1 × 10¹³ ions/cm².     

Determination of migration of ion-implanted Ar and Zn in silica by backscattering spectrometry

It is well known that the refractive indices of lots of materials can be modified by ion implantation, which is important for waveguide fabrication. In this work the effect of Ar and Zn ion implantation on silica layers was investigated by Rutherford Backscattering Spectrometry (RBS) and Spectroscopic Ellipsometry (SE). Silica layers produced by chemical vapour deposition technique on single crystal silicon wafers were implanted by Ar and Zn ions with a fluence of 1–2?×10¹⁶ Ar/cm² and 2.5?×10¹⁶ Zn/cm², respectively. The refractive indices of the implanted silica layers before and after annealing at 300°C and 600°C were determined by SE. The migration of the implanted element was studied by real-time RBS up to 500°C. It was found that the implanted Ar escapes from the sample at 300°C. Although the refractive indices of the Ar-implanted silica layers were increased compared to the as-grown samples, after the annealing this increase in the refractive indices vanished. In case of the Zn-implanted silica layer both the distribution of the Zn and the change in the refractive indices were found to be stable. Zn implantation seems to be an ideal choice for producing waveguides.