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Journal of Luminescence 128 (2008) 16351640 www.elsevier.com/locate/jlumin

Photoluminescence from colloidal silver nanoparticles

Aiping Zhanga,, Jinzhi Zhanga, Yan Fangb
a

College of Sciences, Experimental Center of Basic Sciences, North China University of Technology, Beijing 100144, PR China b Beijing Key Lab for Nano-photonics and Nano-structure, Capital Normal University, Beijing 100037, PR China Received 3 August 2007; received in revised form 10 March 2008; accepted 13 March 2008 Available online 25 March 2008

Abstract Highly luminescent singles of Ag sol with gradual changes were detected when adjusting the granularity and concentration of particles. It can be deduced that these Ag sols, composed of a large amount of silver nanoparticles and clusters, may have their surface energy bands alterable, which might be caused by the interactions between particles. A model that describes the shift of energy band is proposed, and it can be understood as the hybridization of elementary plasmons when interactions occur between particles. Besides, both hybridization and absorption-rescattering mechanisms were proposed to explain the changeable phenomena of photoluminescence with different concentrations. r 2008 Elsevier B.V. All rights reserved.
Keywords: Photoluminescence; Silver nanoparticles; Hybridization

1. Introduction The physical properties of noble metal nanoparticles have been widely studied for several years, in parallel to the efforts that have been devoted for the understanding of their elaboration and their nature [15]. Besides the extensive use for biological labeling [68] and their ability to promote surface enhanced spectral phenomena [911], it was discovered that noble metal nanoparticles display intense light emission and it is expected to yield new insights into the practical applications in optical devices and in biology. In the case of silver, it was reported that neutral nanoparticles emit light in rare gas matrix at cryogenic temperature under photoactivation or electroactivation, and this photoluminescence was attributed to sp to sp-like transitions, analogous to intraband transitions in bulk silver [1214]. Besides, some observations had been attributed to photoreduction processes at the interface between metallic silver and silver oxide [15,16], and other investigations carried out in solid-state materials assigned the luminescence to be from charged silver congeries [17,18]. However, the exact mechanism about how the
Corresponding author. Tel./fax: +86 10 88803271.

E-mail address: ncutalex@126.com (A. Zhang). 0022-2313/$ - see front matter r 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jlumin.2008.03.014

inuencing factors of photoluminescence work are still unclear up to now, which always makes the repetition and explanation of some spectral experiments difcult. Luminescence from noble metal nanoparticles from experiments has received only a limited amount of attention, because most of the emission processes always have very low efciency [19,20] and have not proved to be important technologically nowadays [2123]. In a simple model of a semiconductor, a transition across the energy gap between the valence band and the conduction band will leave too much energy for a phonon to dissipate, and thus it will be radiative if it is allowed. In noble metals, the conventional point on the rarity of luminescence is also quite simple: noble metals do not have band gaps, and the nonradiative decay can proceed all the way back down to the ground state, making luminescence exceedingly improbable [22,23]. Complementary to bulk metal, nanoparticles have large surface, are a more complex system, and their luminescence often reects the interaction that affects electronhole recombination [2426]. In most cases, the involvement of silver clusters in the vicinity of the surface in the luminescence process is hypothesized to be important. But it is still unclear what mechanisms and structural or environmental factors are responsible for the emission signals, though these must be considered very

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important to understand the properties of noble metal particles. This study discusses some of these problems by investigating the photoluminescence of Ag sol with a regulated change of their granularity and concentration. Of particular interest is the interaction between nanoparticles, for which the spectral changes are interpreted in terms of hybridization on the surface that leads to the formation of new surface energy bands. Besides, the changes of intensities and emission centers with their concentrations reduced step-down proved that two emission mechanisms may exist in Ag sol when considering photoluminescence. 2. Experimental 2.1. Materials Silver nitrate (AgNO3, A.R.) and sodium citrate (Na3C6H5O7, A.R.) from Beijing Chemical Company were used as received without further purication. All the other chemicals used in the experiments were analytical grade reagents, and deionized water was used for solution preparation. 2.2. Preparation of Ag sols The Ag sol was prepared according to a modied procedure developed by Lee and Meisel [27]. A 90 mg AgNO3 sample was dissolved in 500 mL deionized water and the solution was heated to boiling. In all, 9 mL of a 1% solution of Na3C6H5O7 was added drop by drop to the boiling solution with vigorous stirring, and then the solution was held at boiling for a further 10 min with
400000
330 2.5 2.0 1.5 1.0 0.5 0.0

constant stirring. Finally, a gray Ag sol was obtained, which was found to be stable for several weeks. Centrifugal separation of Ag sol was done by applying a TDL-50B centrifugal separator. After the centrifugal separation at 1800 r/m for 10 min, the solution was separated into ve average layers from top to bottom articially.

2.3. Apparatus and measurements The transmission electron micrograph (TEM) images were taken with a H-600 TEM detector (Hitachi) after placing several drops of Ag sol on NiCu grid. The photoluminescence was recorded on a Fluorolog-3 spectrometer (Jobin Yvon) and UVvis absorption on a UV2401PC (Shimadzu) UVvisible spectrometer. All these

Hybrid energy band SIBE1

Primary energy band

Primary energy band

Hybrid energy band SIBE2

Fig. 2. An energy-level diagram describing the hybridization of surface energy bands resulting from the interaction between primary energy bands. The newly formed energy bands are called superamolecular interface energy bands (SIBE1, SIBE2).

360000 320000 280000 Intensity (a.u.) 240000 200000 160000 120000 80000 40000 0 200 300

Absorption Intensity (a.u.)

410

400 590

600 Wavelength/nm

800

400

500 600 700 Wavelength/nm

800

900

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Fig. 1. The emission (lex 220 nm) and absorption (inset gure) spectra of fresh-prepared gray Ag sol.

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spectral measurements were carried out at room temperature on a spectrophotometric 1 1 cm quartz curette cell, and the emission spectra were received with the excited wavelength xed at 220 nm, recorded from 220 to 900 nm.

3. Results and discussion Gray Ag sol, prepared by a classical chemical deoxidization method, showed a characteristic plasmon resonance absorption band centered at 410 nm (as can be seen from inset of Fig. 1) and consisted of mostly globularity nanoparticles, in diameters of 2080 nm from TEM. Fig. 1 presented the photoluminescence of fresh-prepared gray Ag sol, which exhibited a sharp and strong peak near 330 nm and a broadened band between 500700 nm. It is known that a nanoparticle, whose diameter is much smaller than the wavelength of light, will respond as a dipole in an optical eld. With this dipole limit, the absorption and emission of nanoparticles should primarily coherent with their surface excited energy bands or the surface active sites [28,29]. Several mechanisms have been proposed to explain the luminescence of metallic nanoparticles, most of which indicate the photoelectron at the surface energy states absorbs light at its plasmon resonance frequency strongly, then part of the absorption energy transfers into heat energy (for example, vibration collision)

Hybrid states SIBE2 energy

Hybrid states SIBE1

increase of the number of interacting particles

Fig. 3. The changes of hybrid energy bands with the increase in the number of particles.

Fig. 4. The TEM images of silvernanoparticles of different layers after centrifugalization. (a)(e) represent the rst to the fth layer separately from top to bottom after being centrifugalized at 1800 r/m for 10 min.

800000
Absorption Intensity (a.u.)

700000 600000 500000 400000 300000 200000 100000 0 300 400

330

412

406

Intensity (a.u.)

e a a e 520

0 300 400 500 600 Wavelength/nm 700 800

500 600 Wavelength/nm

700

800

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Fig. 5. The emission and absorption (inset gure) spectra of different layers of Ag sol after centrifugalization. (a)(e) represent the rst to the fth layer separately from top to bottom after being centrifugalized at 1800 r/m for 10 min.

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and part radiates in light near the wavelength of absorption with its emission intensity greatly owing to this process of absorption rescattering [9,2022]. However, the results from our experiments, as can be seen from Fig. 1, showed a different phenomenon: the emission near the resonance absorption wavelength (410 nm) is so weak that it can be totally neglected in whole photoluminescence spectrum; meanwhile, another two strong bands staying apart at both sides of 410 nm were observed. The strong emission band that approximately occurred at 330 nm should be assigned to neither ligand-to-metal charge transfer nor metal-toligand charge transfer and can probably be assigned to the AgAg interactions, which have been found by other authors [5,3033]. Therefore, a viewpoint of hybridization was deduced to explain the unusual photoluminescence in our case.

There are strong molecular forces (including induction, dispersion and tropism forces) between metallic nanoparticles [32,33]. By means of those forces, the hybrid energy band of nanoparticles may alternate from primary energy bands to form new superamolecular interface energy bands (SIEBs) with one turned to a lower energy and the other to a higher one, as can be depicted in Fig. 2. The shift of plasmon energy bands will depend on the coupling strength and the energy gap between primary ones. Besides, considering the photoelectrons for formation of SIEBs are not in ground state only, but follow the Boltzmann distribution law, the SIEBs will become broader and broader with the increase of interactions caused by the concentration rais of nanoparticles, which is schematically depicted in Fig. 3. From the hybridization assumption, it was described that the primary plasmons of metallic

300000 150000 0 400000 300000 200000 100000 0 600000 400000 200000 0 1200000 800000 400000 0 1200000 800000 400000 0 1600000 1200000 800000 400000 0 800000 600000 400000 200000 0 300000 200000 100000 0 160000 120000 80000 40000 0 100 200

330 550 660

Intensity (a.u.)

410

300

400

500 600 Wavelength/nm

700

800

900

1000

Fig. 6. The emission spectra of different concentrations of Ag sols. From (A) to (I), the concentration was gradually reduced to half of its near former by adding into isopyknic deionized water.

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nanoparticles will be changed by the interactions between these free ones, leading to mixing, splitting, and shifts of the plasmon energies, and this hybridization assumption can be used to describe the variations of the surface energy bands of metallic nanoparticles sensitive to their dispersibility and granularity. The size of silver nanoparticles after the centrifugal separation procedure was measured according to the statistical analysis of a large number (100150) of particles from TEM (as shown in Fig. 4). The average diameters of particles were measured as 35, 47, 52, 68 and 76 nm, respectively, corresponding to the rst to the fth layer from top to bottom. The UVvis absorption spectra (inset of Fig. 5) of these ve sols showed a gradual red shift of the maximum absorption wavelength with the increasing of grain size, which agrees with the classical plasmon resonance absorption theory of metallic colloidal particles. The ratio of surface atoms can increase along with the decrease of particle diameter [34], and the interactions between particles may become stronger, leading to a stronger hybridization effect and a bigger energy gap between SIEBs. As a result, two emission bands assigned to SIEBs may have a synchronous shift to red and blue individually, which can be considered to both a prediction and a good explanation for our experiments. As seen from Fig. 5, with the decrease of grain size, the 330 nm emission bands had a little blue-shift with its intensity increased, and, at the same time, the 520 nm band shifted to the longwavelength with its intensity decreased gradually. Fig. 6 showed the photoluminescence of gray Ag sol with its concentration decreased step down by adding deionized water. It is clear that two bands centered at 330 and 550 nm were observed separately with different prole and intensity at high concentration (Fig. 6A, B). When the concentration of sol decreased gradually, these two bands shifted closer and closer and nally combined to be a new band centered near 410 nm (Fig. 6E), and all the subsequent emission spectra presented a xed center at 410 nm with similar prole. In this whole process, the emission intensity increased sharply at rst and then fell down step by step. These regular changes can be well explained in the presence of hybridization assumption, i.e., the 330 and 550 nm bands can be assigned to the SIEBs and their intensities may be intensively inuenced by the decrease of interactions between particles due to the decrease of concentration, leading to the decrease of emission intensity. In addition, the position of the newly appeared emission band at 410 nm is much close to the plasmon resonance absorption of gray Ag sol, and this band represented a similar decreased trend as the plasmon absorption when the concentration was reduced; thus, this 410 nm emission band was assumed to be from the absorption-rescattering mechanism. Therefore, it indicates that two distinct emission mechanisms may be existing in the whole concentration experiments and a strong hybridization effect may determine the photoluminescence of Ag sol at high concentration, while at low concentration the

absorption-rescattering mechanism may be more appropriate to explain the changes of photoluminescence. 4. Conclusion In conclusion, highly photoactivated luminescences of Ag sol with changeable phenomena for different concentration and granularity were detected. A model describing the changes of photoluminescence is proposed, which can be understood as a hybridization assumption between primary plasmon energy bands, and in the presence of this assumption the spectral changes observed, including both different grain sizes and different concentrations, can be well interpreted. Besides, the integrated use of the newly deduced hybridization and the traditional absorptionrescattering mechanisms can afford a clear and selfconsistent explanation when considering the spectral changes of Ag sol with different concentrations. Acknowledgments The authors are grateful for the support of this research by the National Natural Science Foundation of China and Natural Science Foundation of Beijing. References
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