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Materials Letters 61 (2007) 3522 – 3525

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Growth and quantum confinement in AgI nanowires


Ivana Lj. Validžić, Ivana A. Janković, Miodrag Mitrić, Nataša Bibić, Jovan M. Nedeljković ⁎
Vinča Institute of Nuclear Sciences, P.O. Box 522, 11001 Belgrade, Serbia and Montenegro
Received 10 November 2006; accepted 23 November 2006
Available online 13 December 2006

Abstract

Silver iodide nanowires were synthesized in W/O microemulsions by using cyclohexane/Triton X-100/n-pentanol system. Most likely,
surfactants form rod-like aggregates that can serve as template for growth of two dimensional nanomaterials. It was found that the length of the
AgI nanowires increases as a function of aging time, while the diameter decreases. Final length of the AgI nanowires is several microns, while the
diameter is smaller than 3 nm. Morphological changes are accompanied by optical and structural changes. Large blue shift of excitonic peak from
bulk value at 420 to 326 nm was observed as a consequence of the size quantization effect. Decrease of diameter is followed by the amorphization
of AgI nanowires.
© 2006 Elsevier B.V. All rights reserved.

Keywords: AgI; Nanowires; Size quantization effect; Nanomaterials; Semiconductors; Microemulsions

1. Introduction using poly(ethyleneimine) to inhibit particle growth [16].


Recently, Xu et al. [17,18] synthesized AgI NWs in reverse
Compared to bulk materials, nano-scale materials exhibit large micelles, but unfortunately they did not investigate their optical
specific surface area and size-dependent quantum confinement properties. Their work was a starting point for the further
effects. Nano-scale materials often have distinct electronic, investigations described in this paper. We used a synthetic
optical, magnetic, catalytic and thermal properties. Over the procedure described in Ref. [17] and in addition followed
past few years, significant efforts have been made in order to morphological, structural and optical changes upon aging. We
synthesize various 0D, 1D and 2D nano-scale materials, i.e., found that the length of the AgI NWs increased as a function of
quantum dots, wires and wells [1–9]. Above mentioned structures aging time, while, on the other hand, the diameter became
have attracted considerable attention due to the promising smaller reaching the quantum size domain. Those changes are
fundamental properties for utilization in electronic and photonic accompanied by optical changes. We observed a large blue shift
applications [10,11]. On the other hand, the recent availability of of the excitonic peak from bulk value at 420 to 326 nm due to
semiconductor nanocrystals with anisotropic properties (rods and the size quantization effect. To the best of our knowledge this is
wires) has renewed interest in understanding how shape affects the first example of 2D confinement in the case of AgI
their electronic and optical properties [12,13]. Systematic nanoparticulates. Also, decrease in diameter is accompanied by
research of dots, rods and wires provides possibility to explore the amorphization of AgI NWs.
the transition from simple 3D to 2D confinement, over quantum
rods, i.e., anisotropic quantum dots. The synthesis of uniform 2. Experimental
nanorods and nanowires (NWs) and their assembly into well
defined structures are currently a major challenge. All chemicals (silver nitrate, potassium iodide, cyclohexane,
So far, AgI quantum dots have been prepared in acetonitrile Triton X-100, n-pentanol and ethanol) were of the highest
using polybrene as a stabilizer [14,15], and in aqueous solution purity available, and they were used without further purifica-
tion. The AgI NWs were prepared by rapid mixing of two
⁎ Corresponding author. Tel.: +381 112458222; fax: +381 112447382. separate microemulsions containing AgNO3 or KI, as described
E-mail address: jovned@vin.bg.ac.yu (J.M. Nedeljković). elsewhere [17]. Briefly, each microemulsion contained 0.46 g of
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.11.114
I.Lj. Validžić et al. / Materials Letters 61 (2007) 3522–3525 3523

py (TEM) using Philips EM 400 microscope operated at


120 kV. The samples for TEM measurements were prepared by
dissolving one droplet of microemulsion in 2 ml of ethanol. The
obtained samples were placed on C-coated Cu grids.
The X-ray diffraction (XRD) measurements were carried out
on a BRUKER D8 ADVANCE diffractometer in theta/theta
reflection geometry with parallel beam optics achieved by
multilayer Göbel mirror, which is suitable for the examination
of liquid samples. Diffraction data for structure analysis were
collected in 2θ range from 10° to 80° with steps of 0.05° and
10 s counting time per step.
3. Results and discussion

When two separate W/O microemulsions containing AgNO3 and KI


were mixed together an appearance of yellowish color due to the
formation of AgI can be observed. The obtained mixture becomes clearer
with aging. Absorption spectra of the AgI in W/O microemulsion (0.01 M
AgI, [I−]/[Ag+] = 3) as a function of aging time are shown in Fig. 1.
Immediately after preparation absorption spectrum showed typical
features of bulk AgI with the excitonic peak at 420 nm [19]. Aging of
AgI sample induced blue shift of excitonic peak from its bulk position at
Fig. 1. Absorption spectra of AgI NWs in W/O microemulsion as a function of 420 to 326 nm. The excitonic peak at 326 nm became more pronounced
aging time (0.01 M AgI; [I−]/[Ag+] = 3). as a function of aging time and it stopped to change after approximately
one month. It is important to emphasize that samples with lower
concentration of AgI (0.003 and 0.005 M AgI) showed completely the
n-pentanol, 3.37 g of Triton X-100, 7.64 g of cyclohexane and same optical behavior (spectra not shown). The only difference is longer
1 g of water, and consequently the molar ratio between water time needed to reach equilibrium when the excitonic peak at 326 nm
and surfactant was ω = [H2O]/[Triton X-100] = 11. Molar ratio stops to change; thus, the lower the concentration of Ag+ and I−
between iodide and silver ions was constant in all experiments precursor ions in W/O microemulsions, the longer the time to reach
([I−]/[Ag+] = 3) while concentrations of iodide and silver ions equilibrium. The increase of band gap energy of 0.85 eV can be
were in the range from 0.009–0.03 M to 0.003–0.01 M, attributed to the size quantization effect that arises from the confinement
respectively. Silver and iodide concentrations were calculated of charge carriers in the finite volume of small AgI particles.
per aqueous phase. For the sake of clarity, we kept the molar So far, an increase of band gap energy for AgI quantum dots has
ratio between reactants and composition of W/O microemulsion been observed by Mićić et al. [14,15] and Mulvaney [16], as well as by
Meisel et al. [20] in pulse radiolysis study. They reported position of
as in Ref. [17], while the initial concentrations of the reactants
the excitonic peak at 303 [14], 315 [15], 323 [16] and 334 nm [20] for
were different.
AgI quantum dots with average diameter of 25, 23, 30 and 32 Å,
Absorption spectra of AgI NWs in W/O microemulsions respectively. Knowing from TEM measurements (see further in the
were measured using a Perkin Elmer Lambda 5 UV–VIS text) that prepared AgI nanoparticulates are in the form of NWs and
Spectrophotometer. using effective mass approximation model for 2D confinement we
Microstructural characterization of AgI NWs at different estimated that the diameter of AgI NWs which corresponds to the
aging times was performed by transmission electron microsco- excitonic peak at 326 nm should be 23.6 Å. It should be pointed out

Fig. 2. Typical TEM images of the AgI NWs (0.01 M AgI; [I−]/[Ag+] = 3) synthesized in W/O microemulsion: (A) immediately after preparation, and (B and C) after
one month of aging.
3524 I.Lj. Validžić et al. / Materials Letters 61 (2007) 3522–3525

containing the excess of I− ions, formation of β-AgI crystals primarily


takes place [21], and the corresponding most intensive diffraction
peaks of this phase are indicated in Fig. 3.
The fact that very tiny wires can have amorphous nature is supported
in the literature. For example, InP nanorods 30 Å in diameter showed
weak crystallinity [22], while Niu et al. [23] reported that 3 nm in
diameter Si NWs were part-crystalline. On the other hand, Liang et al.
[24] prepared SiOx NWs that were amorphous, while Jiang et al. [25]
found that tiny amorphous silver particles aggregate into wires.
The formation mechanism of AgI NWs is proposed as follows. It is
known that the wet aggregates of the hexane/Triton X-100/n-pentanol
system are non-spherical [17]. We believe that rod-like W/O microemul-
sion aggregates serve as a template for the initial formation of short AgI
NWs. We exclude “end-to-end” growth mechanism [26] as a possible
way for further growth of AgI NWs, because a significant decrease in the
diameter was observed during the aging process. It is known that when in
Fig. 3. The XRD patterns of the AgI NWs (0.003 M AgI; [I−]/[Ag+] = 3) from W/ aqueous solution the amount of I− ions exceeds that of Ag + ions, and
O microemulsion: (A) immediately after preparation, and (B) after one month of complex species such as AgI 2 −, AgI 3 2−, Ag 2I6 4−, Ag3I5−8 , etc., can be
aging. formed [27,28]. In the dynamic equilibria between complex species and
AgI solid, the dissolution–precipitation process takes place and we
that effective mass approximation model overestimates the increase in believe that the length of AgI NWs increases at the expense of a decrease
the band gap energy in the strong confinement region. in diameter. This conclusion is in accordance with the fact that the most
TEM image of the AgI NWs (0.01 M AgI, [I−]/[Ag+] = 3) recorded active surface states are those with the largest curvature.
immediately after preparation is shown in Fig. 2A. The AgI NWs are in
nanometer size domain with length between 400 and 600 nm and
diameter between 20 and 30 nm. 4. Conclusions
It should be mentioned that the AgI NWs with larger diameter
(N 50 nm) are also present, but their population is negligible. In order to In this paper we report the 2D confinement of AgI
correlate optical changes with morphology of the AgI NWs, TEM nanoparticulates. The AgI NWs prepared using a simple synthetic
measurements were performed after one month of aging (Fig. 2, B and C), method described in Ref. [17] were the starting material and in
when absorption spectra stopped to change. It can be noticed that the AgI
addition we followed morphological, structural and optical
NWs became longer and slimmer with aging. Now, the length of the AgI
NWs is up to a few microns, while the diameter is a few nanometers
changes upon aging. It was found that the length of the AgI
(aspect ratio N 200). There are two reasons why precise estimation of NWs increases as a function of the aging time, while the diameter
diameter is very difficult. First, we could not avoid the presence of decreases. In other words the AgI NWs become slimmer during the
detergent in the sample, since any trial to remove it led to change of aging process and their diameter reaches the quantum size domain.
morphology. Second, the AgI NWs have a tendency to array in parallel to The morphological changes are followed by optical changes and a
each other and to form bundle-like aggregates (Fig. 2, B and C). Many large blue shift of the excitonic peak from bulk value at 420 to
discrete silver particles can be observed along AgI NWs, and their 326 nm was observed as a consequence of size quantization
formation was induced by the interaction of AgI with electron beam. We effects. Also, we proposed that the growth mechanism is based on
used diameter of Ag particles for rough estimation of the diameter of AgI the dissolution–precipitation process. We believe that the length of
NWs. We are certain that the diameter of AgI NWs is smaller than 3 nm, AgI NWs increases at the expense of a decrease in diameter.
which is in reasonably good agreement with calculations based on
effective mass approximation model. Samples with lower concentration
(0.003 and 0.005 M AgI) showed the same morphological behavior. It is
Acknowledgment
important to emphasize that difference in diameters between the AgI
NWs that we observed and reported in Ref. [17] is most likely due to Financial support for this study was granted by the Ministry
different initial concentrations of reactants. Even the diameter of as- of Science and Environmental Protection of the Republic of
prepared AgI NWs that we observed is approximately 1.5–1.7 times Serbia (Project 142066).
smaller than the smallest diameter reported in Ref. [17].
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