ARTICLE IN PRESS Physica B 353 (2004) 92–97 www.elsevier.com/locate/physb Metal alloy and monoelemental nanoclusters in silica formed by sequential ion implantation and annealing in selected atmosphere F. Rena,b, C.Z. Jianga,b,, H.B. Chenc, Y. Shia, C. liua, J.B. Wanga,b a Department of Physics, Wuhan University, Wuhan 430072, China Center for Electron Microscopy, Wuhan University, Wuhan 430072, China c State Key Laboratory for Superlattices and Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing 100083, China b Received 25 August 2004; received in revised form 3 September 2004; accepted 5 September 2004 Abstract The preparation of metal alloy and monoelemental nanoclusters in silica by Ag, Cu ion sequential implantation and annealing in selected oxidizing or reducing atmosphere is studied. The formation of metastable Ag–Cu alloy is verified in the as-implanted samples by optical absorption spectra, selected area electron diffraction and energy dispersive spectrometer spectrum. The alloy is discomposed at elevated annealing temperature in both oxidizing and reducing atmospheres. The different effects of annealing behaviors on the Ag–Cu alloy nanoclusters are investigated. r 2004 Elsevier B.V. All rights reserved. PACS: 61.46.+W; 61.72.Ww; 78.67.Hc; 61.16.C; 81.05.Bx Keywords: Ion implantation; Nanocluster composites; Alloy; Annealing 1. Introduction The metal nanocluster composite is a promising candidate of optical switch, which is a key device in all-optical communication, because of the large Corresponding author. Department of Physics, Wuhan University, Wuhan 430072, China. Tel.: +86 27 68752567; fax: +86 27 68752569. E-mail address: [email protected] (C.Z. Jiang). third-order nonlinear susceptibility and picosecond nonlinear response times. As ion implantation is a useful technique to obtain nanocluster composite materials [1], noble metals implanted in sequence may form multicomponent metal nanoclusters in silica glass. The composition of the metal nanoparticles and then both the linear and nonlinear optical prosperities of the composites can be controlled by the implantation [2,3]. The metal vapor vacuum arc (MEVVA) ion source, 0921-4526/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.physb.2004.09.005 ARTICLE IN PRESS F. Ren et al. / Physica B 353 (2004) 92–97 which provides large current and broad beams of metal ions, is suitable for high dose ion implantation. In this paper, Ag–Cu metastable alloy nanoclusters are prepared by sequential ion implantation with a MEVVA source. The effects of annealing on the metal nanocluster composite glass at different temperatures in oxidizing or reducing atmosphere are studied. The remarkable difference between the annealing behaviors in different atmospheres indicates that the electronic structure and the optical characteristics of the nanoclusters can be tailored by implantation and annealing. 93 velengths from 900 to 200 nm. The absorption spectra for all samples were measured with an unimplanted sample in the reference beam. 3. Results and discussion 3.1. XPS spectra Fig. 1 shows the XPS Ag3d and Cu2p spectra of the as-implanted sample. XPS results show that Ag3d5=2 binding energy is 368.2 eV, which is attributed to the metal state of Ag in the composite. The Cu2p3=2 spectrum can be deconvoluted into two spectra with peaks at 932.7 and 2. Experiment Ag and Cu ions were sequentially implanted into silica glass at room temperature with a MEVVA implanter. The ion flux densities of Ag and Cu were both about 1 mA/cm2 and the doses of Ag and Cu were both 5 1016 ions/cm2. The extracted voltages of Ag and Cu were 43 and 30 kV, respectively. Then the projected ranges for Ag and Cu in silica were similar and the ion ratio of Ag/Cu was 1. The valence states of Ag and Cu in the composite were investigated by X-ray photoelectron spectroscopy (XPS), which were measured in a Kratos XSAM800 spectrometer operated in fixed retarding ratio or fixed analyzer transmission mode using Mg Ka1,2 (1253.6 eV) excitation. Transmission electron microscopy (TEM) observations were finished with a JEOL JEM 2010 (HT) and a JEOL JEM 2010FEF (UHR) equipped with an EDAX energy dispersive X-ray spectrometer (EDS). Both the microscopes were operated at 200 kV. Selected area electron diffraction (SAED), bright field (BF) and dark field (DF) imaging techniques were used to determine the crystal structure, size distribution, and shape of nanoclusters. The implanted samples were then heated to different temperatures from 300 to 800 1C, with a rate of 1 h per step at an interval of 100 1C in either oxidizing (air) or reducing (30% H2+70% Ar gas mixture, gas pressure 20 Pa) atmosphere. Optical absorption spectra were recorded at room temperature using a UV–VIS dual-beam spectrophotometer with wa- Fig. 1. Ag3d (a) and Cu2p (b) XPS spectra of the Ag/Cu implanted sample. ARTICLE IN PRESS 94 F. Ren et al. / Physica B 353 (2004) 92–97 933.7 eV, corresponding to Cu–Cu and Cu–O bonds, respectively. So Cu carries both the metal and the +2 oxidation states in the as-implanted sample. During the process of implantation, the implanted ions and the host atoms compete for the oxygen in the SiO2 matrix. The free energy for the formation of SiO2 is lower than that for the formation of the silver oxides. However, the free energy of formation of CuO is also low, so Ag is expected to be preserved in metallic form, while a part of Cu is in oxidation form. 3.2. Formation of Ag–Cu alloy nanoclusters Fig. 2(a) is the TEM image of implanted sample, which indicates that spherical particles have been formed. SAED for the as-implanted samples is shown in Fig. 2(b). The SAED pattern shows rings that are typical of crystalline clusters with mutual random orientation. The SAED pattern can be indexed according to a single face-centered-cubic (FCC) phase with a lattice constant of 0.39670.002 nm. This value is not consistent with the experimental values of the pure bulk phases of either Ag (aAg ¼ 0:4079 nm) or Cu (aCu ¼ Fig. 3. Energy dispersive X-ray spectra for a large nanocluster. 0:3608 nm), which indicates that an intermetallic Ag–Cu alloy may have been formed. The composition of larger clusters is further examined by EDS. The spectrum shown in Fig. 3 indicates that there are both Ag and Cu elements in the same nanoclusters, which provides another evidence for the formation of Ag–Cu alloy nanoclusters [4,5]. A possible mechanism of the formation of alloy is related to the enhanced diffusion of Cu in small Ag clusters, just like adding Cu to Ag with the heat generated by the implantation, where high local temperatures is achieved [2,6,7]. Cu ion implantation will create a lot of displacement cascades in the formed Ag nanoclusters. Molecular dynamic simulation on the displacement cascade has suggested that during the thermal spike of the cascade formation, the temperature in the cascade core can be extremely high and atoms inside the displacement cascade may achieve a ‘liquid-like state’ [8]. The Ag–Cu metastable alloy may be formed, as the cooling rate of collision cascade is sufficiently high (1014 K/s) [9,10]. There is no ordered phase for Ag–Cu alloy, so these nanoclusters are indeed Ag–Cu solid solution. 3.3. Influence of annealing in oxidizing atmosphere on nanoclusters Fig. 2. (a) TEM and (b) SAED image for the Ag/Cu sequentially implanted sample. The linear absorption for noninteracing spherical colloids with diameters less than l/20, is described by Mie scattering theory in the electric ARTICLE IN PRESS F. Ren et al. / Physica B 353 (2004) 92–97 95 dipole approximation [11] and is given by a¼ 18ppn3 2 ; l ð1 þ 2n2 Þ2 þ 22 (1) where a is the absorption coefficient, ðlÞ ¼ 1 þ i2 is the dielectric constant of the metal, p is the volume fraction of the metal particles and n is the index of refraction of the dielectric host. The absorption is expected to exhibit a peak at the surface plasmon resonance (SPR) frequency for which the condition 1 þ 2n2 ¼ 0 is met. The SPR frequency depends explicitly on metal cluster constitution, size, volume faction, shape, and dielectric function of matrix. So changing the composition of composite or the size of clusters will change the SPR spectra. Fig. 4(a) shows the optical absorption spectra of the samples before and after annealing in air from 300 to 800 1C. For the optical absorption spectrum of the as-implanted sample, the position of SPR peak is at 442 nm, which lies between that of pure Ag (410 nm) and Cu (560 nm) nanoclusters. Therefore, it indicates that intermetallic Ag–Cu alloy nanoclusters have been formed instead of two separated Ag and Cu nanoclusters, which on the contrary would give rise to double-peaked spectroscopy [6]. When the as-implanted sample was annealed in air, the SPR peaks shift rapidly toward shorter wavelength and approaches the SPR peak position of pure Ag nanoclusters with the increase of annealing temperature to 400 1C. This means that alloy nanoclusters have been discomposed and Ag monoelemental clusters are formed, whereas Cu migrates toward the surface of the sample, where it is oxidized. Four mechanisms may be responsible for this alloy dissociation and the formation of larger Ag clusters. Firstly, the Ag–Cu metastable alloy is not stable and easy to decompose at elevated temperature [12]; secondly, the solubility of Cu in Ag is low, so Cu will escape from the alloy clusters after annealing; thirdly, oxygen permeates in the sample and reacts strongly with Cu, enhancing the Cu diffusion out of the alloy clusters and migration toward the sample surface; fourthly, the migration of oxygen in-depth also increases Ag mobility [13]. Fig. 4. Optical absorption spectra of the Ag/Cu sequentially implanted sample annealing in (a) oxidizing or (b) reducing atmosphere. The sharpening of SPR peaks shows that the sizes of nanoclusters became larger with the increase of annealing temperature. But the intensity of the SPR peaks weakens at higher annealing temperature, which may be due to the break of the already presented large Ag clusters and the reduction of Ag cluster number because Ag diffuses atomistically into the substrate or move toward the surface, where it evaporates. This will also lead to the decrease of Ag radius at temperature higher than 600 1C. ARTICLE IN PRESS 96 F. Ren et al. / Physica B 353 (2004) 92–97 3.4. Influence of annealing in reducing atmosphere on nanoclusters For the samples annealed in reducing atmosphere, the SPR peaks also shift toward that of the pure Ag clusters. However, a shoulder peak appears at 567 nm at 500 1C, approaching that of pure Cu clusters. The two absorb bands become sharper and more intense in the subsequent annealing. Therefore, Ag–Cu alloy is also decomposed and Ag clusters are formed with temperature lower than 500 1C. With the further increase of annealing temperature, Cu ions in oxidation state are reduced by H2 and aggregate to form Cu nanoclusters together with the existed Cu atoms in metal state, which brings about the SPR peak of Cu. This was confirmed by the SAED patterns of the sample annealed in reducing atmosphere. Fig. 5 is the TEM, BF and SAED images of the sample directly annealing in reducing atmosphere at 800 1C for 1 h. The SAED pattern displays two sets of diffraction rings characteristic of FCC Ag and Cu. 4. Conclusion Metastable Ag–Cu alloy and monoelemental nanoclusters have been formed by Ag and Cu sequential ion implantation in SiO2 matrix and annealing. In the case of annealing in air, Ag–Cu alloy is discomposed; Cu migrates to the surface of the sample and oxidizes. Ag nanoclusters are formed due to weak oxygen–silver interaction. For the sample annealed in reducing atmosphere, the Ag–Cu alloy discomposes into Ag and Cu nanoclusters. Acknowledgments The authors would like to thank Professor J.N. Gui for useful discussions. This work was partially supported by the National Natural Science Foundation of China (No. 10005005, 10205010, 10375044). References Fig. 5. (a) TEM and (b) SAED image for the sample annealed in reducing atmosphere at 800 1C. [1] P. Mazzoldi, G.W. Arnold, G. Battaglin, F. Gonella, R.F. Haglund Jr., J. Nonlinear Opt. Phys. Mat. 5 (1996) 285. [2] G. Battaglin, E. Cattaruzza, F. Gonella, G. Mattei, C. Sada, X. Zhang, Nucl. Instrum. Methods B 166–167 (2000) 857. ARTICLE IN PRESS F. Ren et al. / Physica B 353 (2004) 92–97 [3] R.A. Zuhr, R.H. Magruder III, T.S. Anderson, Surf. Coat. Technol. 103–104 (1998) 401. [4] F. Ren, C.Z. Jiang, L. Zhang, Y. Shi, J.B. Wang, R.H. Wang, Micron 35 (2004) 489. [5] R.H. Magruder III, J.E. Wittig, R.A. Zuhr, J. Non-Cryst. Solids 163 (1993) 162. [6] F. Gonella, G. Mattei, P. Mazzoldi, C. Sada, Appl. Phys. Lett. 75 (1999) 55. [7] T.S. Anderson, R.H. Magruder III, D.L. 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