CHINESE JOURNAL OF ANALYTICAL CHEMISTRY Volume 38, Issue 2, February 2010 Online English edition of the Chinese language

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Cite this article as: Chin J Anal Chem, 2010, 38(2), 149152.

RESEARCH PAPER

Investigation of Morphology and Structure of Poly(ethylene glycol)-Coated Silver Nanowires by Electron Microscopy
HUANG Li-Jian, WANG Er-Kang*
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Abstract:

In this study, poly(ethylene glycol) (PEG)-coated silver nanowires (SNWs) have been hydrothermally prepared at a very

slow rate, in which PEG was used as both a mild capping agent and a weak reductant. The as-prepared SNWs have been characterized using scanning electron microscope and transmission electron microscope (TEM), which showed that the SNWs are usually longer than 100 m and their diameters (each SNW has a uniform thickness) vary mainly in the range of 80300 nm. Surprisingly, some of these SNWs connected by their two ends to form some close-looped SNWs, which has not been previously reported. The existence of close-looped SNWs supports the mechanism that nanowires can evolve from fusion of some nanoparticles and/or shorter nanorods. Careful TEM characterization and selected area electron diffraction revealed that the SNWs kept a fivefold twinned structure, which was inconsistent with some previous observations that a long-time incubation would lead to the disappearance of this twin structure. This study demonstrates the situation that further investigation is still needed for understanding the structure transformation of SNWs. Key Words: Silver nanowires; Electron microscopy; Structure characterization; Fivefold twinned structure

Introduction

In recent years, nanostructured metal materials have stimulated extensive researches due to their unique physical properties and their potential application in chemical or biological analysis[13] and nanodevices[4,5]. Some progresses have been made in these researches, however, further investigations are still needed for better understanding and control of the structure and morphology of these materials. One example is the silver nanowires (SNWs), which have aroused extensive researches in the past decade. Many preparation methods have been developed to prepare SNWs, of which morphologies and structures have been well studied. For instance, Xia et al[6,7] applied the so-called polyol method[8] to prepare SNWs and found that their SNWs had a fivefold twinned structure with rotational symmetry. Using glucose as the reductant, Li et al[9] adopted a hydrothermal method to prepare SNWs that bore the same twinned structure

but smaller average diameter; they found that the fivefold twinned structure of their SNWs could transform into other relatively irregular structures after long-time incubation. For both the above-mentioned methods, poly(vinyl pyrrolidone) (PVP) was used as the capping agent, and some other water-soluble polymers, such as poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG), can also be used as the capping agent for SNWs preparation. For example, Qian et al[10] used PVA as the capping agent in their hydrothermal synthesis and obtained some single-crystal structured SNWs with relatively large average length and diameter; Xie et al[11] obtained some single-crystal structured thin SNWs with coarse surface using PEG and ferrocene as the capping agent and reductant, respectively. Zhang et al[13] also used PEG as the capping agent but adopted glucose as the reductant, which led to the formation of twin-structured SNWs. For all the above preparations, PVP, PVA, and PEG were used as the capping agent, and the reduction of silver ions relied on given

Received 22 November 2009; accepted 27 December 2009 * Corresponding author. Email: ekwang@ciac.jl.cn This work was supported by the National Natural Science Foundation of China (No. 209350037), the national basic research program of China (973 program, No. 2010CB933600) and the fund from Changchun Institute of Applied Chemistry. Copyright 2010, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved. DOI: 10.1016/S1872-2040(09)60020-7

HUANG Li-Jian et al. / Chinese Journal of Analytical Chemistry, 2010, 38(2): 149152

reductants. As a matter of fact, these capping agents themselves can also serve as the reductant by means of their relatively weak reducing powers. In this study, PEG was used to demonstrate that SNWs can be prepared using the weak reducing power of capping agents themselves, and the morphology and the structure of the as-prepared SNWs were carefully investigated.

stainless steel autoclave and heated at 170 C in an oven for 3 days. The as-prepared sample contains some white or gray fluffy precipitates, which were collected by centrifugation and washed with ammonia and water to remove unreacted AgCl, KCl, the excess PEG and other impurities produced during the preparation process.

3 2
2.1

Results and discussion

Morphology characterization

Experimental
3.1 Instruments and reagents The inset of Fig. 1A shows the optical image of a SNW sample, of which the silver component has been testified by the EDS characterization (Fig.1E). As revealed by the SEM image in Fig.1A, the sample is composed of many SNWs, some silver particles and a few silver plates. The SNWs are usually longer than 100 m and their diameters (each SNW has a uniform thickness) vary mainly in the range of 80300 nm. Surprisingly, some SNWs in our sample were not only curved but also connected by their two ends, forming some closed loops (Fig.1B). Though these loops were different in size and shape (Fig.1), each loop was composed of one uniform SNW. To the best of our knowledge, it is the first time that such closed loops of SNWs are reported to be prepared using a chemical method. It should be pointed out that the content of SNWs, especially those looped ones, varied from one sample to another, but the average diameter and the length of SNWs remain almost unchanged. As a comparison, other molecule-weighted PEGs have also been applied in SNW preparation. It was found that usage of PEG 400 led to formation of more particles whereas usage of PEG 10000 or PEG 600000 decreased the content of looped SNWs, which should be attributed to the different adsorption behavior of these PEG molecules. 3.2 Structure characterization

X-ray diffraction patterns (XRD) were obtained on a Bruker D8 Advance diffractometer (Bruker AXS Inc., USA) using Cu K radiation. Transmission electron microscope (TEM) images were captured on a H-8100 (Hitachi, Ltd., Japan) or a JEM-2010 (JEOL Ltd., Japan), both operated at an accelerating voltage of 200 kV. Scanning electron microscope (SEM) images were captured on a Philips XL 30 environmental SEM (FEI Co., USA) operated at an accelerating voltage of 15 kV. Silver nitrate (AgNO3, Shanghai Chemical Reagent Co. Ltd., China), Potassium chloride (KCl, Beijing Chemical Works, China) and PEG 2000 (Tianjin Tiantai Fine Chemicals Co. Ltd., China) were used without further purification and were diluted in water to 0.5 M, 1.0 M and 0.05 g mL1, respectively, to make some stock solutions. The water used in all experiments was twice-distilled water. 2.2 SNW preparation

The preparation of SNW is simple, in which only three domestic reagents, i.e. PEG 2000, AgNO3 and KCl, were used. The ultimate concentrations of PEG 2000, AgNO3 and KCl reagents were 253, 8.35 and 8.35 mM (the concentration of PEG was calculated according to its repeating unit), respectively. Under stirring, some aqueous solutions of these three reagents, in turn, were mixed in a vitreous cylinder, in which certain amount of water was added beforehand to keep the total volume at 18 mL. Once the KCl solution was added, milky colloid solution of AgCl was formed in the vitreous cylinder, and then the colloid solution of AgCl with the vitreous cylinder was sealed in the 45-mL Teflon liner of a

To investigate the structure of the SNWs, XRD and TEM characterizations were also performed. Figure 2 shows the XRD pattern of a SNW sample, in which all the diffraction peaks can be indexed to face-centered cubic silver (JCPDS, 04-783), and no peaks from impurities are found. Figure 3A shows the TEM image of the SNWs sample, which confirmed

Fig.1 Some SEM images of SNWs (AD) and EDS analysis (E). Inset in (A): optical image of a SNW sample

HUANG Li-Jian et al. / Chinese Journal of Analytical Chemistry, 2010, 38(2): 149152

the uniform diameters of the SNWs. The stripes in other TEM images (Figs.3B and 3D) demonstrate that these SNWs bear some stacking faults in the axial direction. According to previous studies[6,13,14] on PVP-coated SNWs, these stacking faults may result from a fivefold twinned structure of SNWs. For further recognition of the structure of these SNWs, selected area electron diffraction (SAED) analysis was also carried out. Figures 3C and 3E show the corresponding SAED patterns collected on the SNW in Figs.3B and 3D, respectively. Each pattern contains at least two sets of spots, proving that these SNWs have a twinned structure. The TEM observation on a microtomed SNW sample indicate that the SNWs have a pentagonal profile (inset in Fig.3A), which confirms that these SNWs possess a fivefold twinned structure. 3.3 Comparison with other SNWs

observations[9,10] that a long-time incubation would lead to the disappearance of this twin structure. This situation indicates that the structure evolution of SNWs may be more complicated than we had expected and further investigation is still needed to be carried out.

Conclusion

Compared with PVP-coated SNWs, these PEG-coated SNWs have larger average length and diameter, which should be attributed to weaker affinity of PEG on silver surface. The weak affinity of PEG leads to its low coverage on silver surface, which is favorable for silver atoms to deposit onto the SNW surface, as a result, the average diameter and length of the PEG-coated SNWs became large. Furthermore, the relatively low coverage of PEG on silver are also favorable for the fusion of some nanoparticles or nanorods, which, according to the results in some previous researches[15,16], is another kind of formation mechanism for SNWs and herein may also account for the formation of closed loops of SNWs. These PEG-coated SNWs underwent a long-time hydrothermal incubation but still bear a fivefold twinned structure, which is inconsistent with some previous

SNWs have been prepared with a hydrothermal method using PEG as both the capping agent and the reductant. The morphology and the structure of this SNWs sample have been carefully investigated, and the results indicate that these SNWs have relatively large average diameter and length and a fivefold twinned structure. To our surprise, some of these SNWs connected by their two ends to form some close-looped SNWs, which has not been previously reported. PEG has a relatively low coverage on SNWs, making it easy for other molecules to approach, which is favorable for chemical enhancement for surface-enhanced Raman scattering, thus it may be used in Raman analysis.

Fig.2 XRD pattern of a SNW sample

Fig.3 TEM images of some SNWs (A, B and D) and corresponding SAED patterns (C and E). Inset in (A): TEM image of a microtomed sample

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