Appl Phys A (2012) 108:81–89
DOI 10.1007/s00339-012-7016-1
Linear optical absorption and photoluminescence emission
properties of gold nanoparticles prepared by laser ablation
technique
H.S. Desarkar · P. Kumbhakar · A.K. Mitra
Received: 17 November 2011 / Accepted: 30 May 2012 / Published online: 12 June 2012
© Springer-Verlag 2012
Abstract Gold nanoparticles of average size varying be-
tween 1.1 and 3.3 nm are prepared by 1064 nm Nd:YAG
laser ablation of solid gold target kept in ethylene gly-
col medium. The measured UV-Visible absorption spectra
showed the presence of sharp absorption peaks in the UV
and in the visible regions due to the interband transition
and surface plasmon resonance (SPR) oscillations in Au
nanoparticles, respectively. The increase in linewidth of the
SPR peaks with the reduction in particle sizes is observed
due to intrinsic size effects. The prepared samples exhibit
photoluminescence (PL) emissions in the UV-Visible region
peaked at ∼354 nm due to the recombination of electrons
with holes from sp conduction band to d-band of Au. The
peak PL intensity in the sample prepared with 60 minutes of
laser ablation time is enhanced by a factor of ∼2.5 compared
to that obtained in the sample prepared with a laser-ablation
time duration of 15 minutes.
1 Introduction
Synthesis and characterization of metallic nanoparticles are
of primary importance due to their unique optical, elec-
tronic, chemical and magnetic properties, which are differ-
ent from bulk metals [1–4]. Noble metal nanoparticles are
A.K. Mitra retired from Dept. of Physics, NIT Durgapur, India.
H.S. Desarkar · P. Kumbhakar ()
Nanoscience Laboratory, Department of Physics,
National Institute of Technology, Durgapur, 713209, India
e-mail: pathik.kumbhakar@phy.nitdgp.ac.in
Fax: +91-343-2547375
P. Kumbhakar
e-mail: nitdgpkumbhakar@yahoo.com
widely used in photography, catalysis, biological leveling,
information storage etc. and different techniques have been
used so far for the preparations of noble metal nanoparticles
of varying sizes, shapes and chemical compositions [5–8].
The properties of nanoparticles are strongly dependent on its
morphology. Therefore, particular attention should be given
to the choice of its preparation. Amongst many other popu-
larly used synthesis techniques, chemical method is easy for
the preparation of metallic nanoparticles [5–8]. But there are
certain drawbacks of this method. In chemical method, syn-
thesized metallic nanoparticles become contaminated. Fur-
thermore, there are problems with colloidal purification and
agglomeration of the prepared nanoparticles. The electronic
structure, optical properties and crystallographic phases of
the nanoparticles, synthesized by chemical method are af-
fected due to the impure nanoparticles surface and the pres-
ence of capping agents [9–32]. The alteration of peak po-
sition and shape of the surface plasmon resonance (SPR)
absorption of Au nanoparticles due to the presence of the
ligands or the dispersive medium have been reported earlier
[13, 14].
Recently, laser-ablation technique has received much at-
tention for the preparation of contamination free metallic
nanoparticles [16–20]. In laser ablation, high power laser
pulses are used to evaporate matter from a target surface
such that stoichiometry of the material is preserved in this
interaction. In comparison to the chemical method, in laser-
ablation technique we need not require to add any surfac-
tants or capping agents to prepare metallic nanoparticles.
Stratakis et al. have reported the preparation of highly oxi-
dizing stable aluminum nanoparticles in absence of any cap-
ping agent by laser ablation in liquid technique [33]. They
have showed that the laser ablation with short laser pulses
in liquid compensate the high reactivity of Al with ambi-
ent oxygen and water [33]. Ablation with short laser pulses
82
due to faster quenching minimizes the formation of oxide
and hydroxide on the surface [33]. Thus we can prepare
pure nanoparticles that are useful for further applications by
laser ablation in liquid technique. Preparations of Au and
Ni nanoparticles by pulsed Nd:YAG laser ablation of cor-
responding solids have been reported, previously [16–21].
However, they have not reported the presence of UV peak
in the absorption spectra of their prepared Au nanoparti-
cles [21]. Recently Jeon and Yeh [22] have reported the ef-
fect of different laser wavelength (1064 and 532 nm) and
the effect of focusing on ablation efficiency for preparation
of nanoparticles. Prochazka et al. [23] have reported the ef-
fect of focusing conditions and laser energy on the abla-
tion efficiency and particle size of the prepared nanoparti-
cles.
However, here we have reported the preparation of Au
nanoparticles by 1064 nm Nd:YAG laser ablation of solid
gold target kept in ethylene glycol (EG) medium and ob-
served the appearance of strong and sharp interband absorp-
tion in the UV region as well as SPR absorptions in the vis-
ible region. The average size of the prepared Au nanoparti-
cles are varied between 1.1 and 3.3 nm when the time dura-
tion of laser ablation is varied between 15 and 60 minutes,
keeping the laser fluence constant at 24 J/cm2 and the pulse
duration of the input laser radiation as 10 ns. It is found
from the measured UV-Visible (UV-Vis) absorption char-
acteristics of all the samples that the SPR peak positions
and thus the average particle sizes of the prepared nanopar-
ticles are dependent on the time duration of laser ablation.
The observed results have been analyzed using the frame-
work of Mie theory and the value of scattering parameter
and bulk gold damping frequency have been extracted. It
is found that SPR linewidth increases with the decrease in
particle size due to intrinsic size effects. The effect of sur-
rounding medium on the size and SPR properties of the pre-
pared nanoparticles by laser ablation of pure gold in differ-
ent organic liquids, namely in methanol, acetone and ethy-
lene glycol, have also been studied. During this part of the
experiment the laser fluence is kept fixed at 24 J/cm2 and
Fig. 1 (a) The schematic of the
experimental set up for the
preparation of Au nanoparticles
by laser ablation. (b) Shows the
EDXA spectrum of a
representative sample prepared
with the laser-ablation time
duration of 15 minutes
H.S. Desarkar et al.
the laser ablation is done for a time duration of 15 minutes.
It is found that with the increase in refractive index of the
surrounding medium a red shift in SPR peak position is oc-
curred. Moreover photoluminescence (PL) emissions char-
acteristics of all samples have been measured and it is found
that all samples exhibit PL emissions in the UV-Vis region
peaked at ∼354 nm wavelength which is attributed to re-
combination of electrons from sp conduction band to d-band
of Au.
2 Experimental details
The experimental set up used for preparation of Au nanopar-
ticles is shown in the inset of Fig. 1a The solid gold target
used is a gold plate of ∼10 mm thick and of purity of 99 %
which is kept in a petri-dish containing 10 ml of EG. The
used source of laser radiation is a Q-switched Nd:YAG laser
emitting radiation of wavelength 1064 nm having pulse du-
ration of 10 ns and repetition rate of 10 Hz and it is focused
using a lens of focal length 30 cm. The spot size of the used
radiation at the surface of the target is ∼50 µm and the at-
target fluence is ∼24 J/cm2 . The composition of the pre-
pared colloidal particles is analyzed using a scanning elec-
tron microscope (SEM, Hitachi, S-3000 N). The formations
of nanoparticles along-with its size variation with the time of
ablation are visually noted with the variation of color of the
prepared colloids. The laser source is operated at a repetition
rate of 10 Hz and ablation time is varied between 15 and 60
minutes. The nanostructures of the samples are obtained us-
ing a transmission electron microscope (TEM, FIB-20). The
UV-Vis absorption characteristics have been measured using
a spectrophotometer (Hitachi, U 3010), and for these mea-
surements nanoparticles are kept in a quartz cuvette of path
length 1 cm. Photoluminescence (PL) emission spectra from
all the samples are collected at room temperature by using
a luminescence spectrometer (Perkin Elmer LS55) and by
keeping the nanoparticles in a four side polished PL cuvette
of path length 1 cm.
Linear optical absorption and photoluminescence emission properties of gold nanoparticles
3 Results and discussions
The energy-dispersive X-ray analysis (EDXA) spectrum of
a representative sample prepared by 15 minutes of laser-
ablation time duration is shown in Fig. 1b, which confirmed
the presence of Au as a principal element in the prepared
sample. The additional peak for Si has appeared due to the
substrate on which the sample is dried. The nanostructures
and the particle size distribution of the Au nanoparticles in
the prepared samples have been determined from TEM mi-
crograph analyses. Figures 2a (2b), 2c (2d), 2e (2f), 2g (2h),
and 2i (2j) show the TEM micrographs (the correspond-
ing particle size distributions) of the samples prepared with
laser-ablation time duration of 15, 20, 30, 45, and 60 min-
utes, respectively, and with a constant value of laser fluence
of 24 J/cm2 . Figure 2k shows the variation of the average
particle sizes (radius in nm) as obtained from the TEM mi-
crograph analyses of the prepared samples with the laser ab-
lation time. From Fig. 2k it is found that value of the particle
Fig. 2 The TEM micrographs
(the corresponding particle size
distributions) of the samples
prepared by laser-ablation time
duration of 15, 20, 30, 45, and
60 minutes are shown in a (b),
c (d), e (f), g (h), and i (j),
respectively. Figure 2k shows
the variations of the average
particle size (radius in nm) as
obtained from TEM micrograph
analysis with the laser-ablation
time duration
83
size decreases with the increase of laser-ablation time dura-
tion.
Figure 3a shows the selected area electron diffraction
(SAED) pattern of a representative sample prepared by
45 minutes of laser ablation. The values of the lattice spac-
ing (d) corresponding to the four different rings in the SAED
pattern are calculated and those are compared with the stan-
dard lattice spacing (d1 , JCPDF 04-784). The values of d
and d1 along with their respective (hkl) indices have been
summarized in Table 1. From Table 1 it is found that our
calculated values matches exactly well with those of stan-
dard value of Au which further confirmed the presence of
only Au in the prepared samples. A bright field (BF) high
resolution transmission electron microscope (HRTEM) im-
age of an isolated Au nanoparticle is shown in Fig. 3b, in
which the lattice fringes are clearly seen. The calculated
value of the distances between two adjacent planes is mea-
sured to be 0.144 nm which corresponds to (220) planes
of Au.
84 H.S. Desarkar et al.

Fig. 2 (Continued)

Fig. 3 The SAED pattern and

BF HRTEM image of a sample
prepared by 45 minutes of
laser-ablation time duration are
shown in (a) and (b),
respectively

Figure 4 shows the UV-Vis absorption characteristics of bols rectangle, hollow circle, up triangle, solid circle and
all as-prepared samples prepared with laser-ablation time down triangle correspond to the laser ablation time duration
duration varying between 15 to 60 minutes and with the of 15, 20, 30, 45, and 60 minutes, respectively. From Fig. 4
same laser fluence as used earlier. In Fig. 4, line with sym- it is seen that two absorption peaks are appeared in all the
Linear optical absorption and photoluminescence emission properties of gold nanoparticles
Table 1 The standard (JCPDS 04-784) d1 (nm) and measured d (nm)
values of lattice spacing of Au as obtained from the SAED pattern
(Fig. 3a) along-with their respective (hkl) indices
Ring 1st 2nd 3rd 4th
(hkl) (111) (200) (220) (311)
d 0.235 0.203 0.144 0.122
d1 0.235 0.204 0.144 0.123
Fig. 4 Variation of absorption spectra with the laser ablation time of
various Au nanoparticles prepared in ethylene glycol (EG) medium.
The line with symbols rectangle, hollow circle, up triangle, solid circle
and down triangle correspond to the laser-ablation time duration of 15,
20, 30, 45, and 60 minutes, respectively. The inset shows the variations
of the surface plasmon resonance (SPR) peak and UV peak absorbance
with the laser-ablation time duration
samples, one in the visible region due to the well known SPR
absorptions, which is the characteristics absorption of met-
als and another in the UV region. The appearance of sharp
and strong absorption in the UV region is an important ob-
servation in this work and it is rarely reported in the previous
studies.
From the inset of Fig. 4 it is seen that the maximum value
of SPR peak as well as that of UV absorption peak varies
with the laser-ablation time duration. It is found from the in-
set of Fig. 4 that initially with the increase of time duration
of laser ablation the UV absorption peak intensity increases
and it dominates over the SPR absorption in the sample pre-
pared with laser-ablation time duration of 20 minutes and af-
ter that it decreases rapidly and then again increase slightly
for larger values of laser ablation time duration. From the
inset of Fig. 4 it is also seen that SPR absorption peak in-
tensity increases slowly at first with the increase of laser
ablation time up to 30 minutes and then it becomes almost
constant. The peak value of the SPR absorption is propor-
tional to the concentration of nanoparticles [21] and with the
85
Fig. 5 Variations of SPR and UV peak absorption wavelengths with
the laser-ablation time duration
increasing value of laser-ablation time duration the concen-
tration of produced nanoparticles is increased, initially. As a
result the intensity of SPR peak absorption is increased. But
with the increasing value of laser-ablation time duration, the
produced nanoparticles are accumulated near the laser spot
on the metal target. When the numbers of produced nanopar-
ticles become sufficient, these nanoparticles shield the inci-
dent laser radiation. As a consequence of this, the value of
the incident laser intensity reaching the solid target is de-
creased and thus further production of the nanoparticles is
stopped. Therefore, the peak value of absorbance due to SPR
peak does not change significantly after laser-ablation time
duration of 30 minutes. The size of the nanoparticles is also
decreased with laser ablation time and it is lowest for highest
laser-ablation time duration of 60 min.
Figure 5 shows the variations of the SPR wavelengths and
the position of UV absorption peak with the time duration of
laser ablation for all the samples. It is observed that the SPR
peak position shows a gradual blue shift with the increase
of laser-ablation time duration. The blue shift of SPR peak
position is taking place due to the reduction of the size of
the prepared nanoparticles as obtained from TEM measure-
ments which are presented above and it also agrees with the
classical plasmon resonance absorption theory of metallic
colloidal particles [24, 31].
The Lorentzian line widths (in meV) of SPR peak of all
the samples have also been calculated and those are shown
in Fig. 6 with their corresponding particle size. From Fig. 6
it is observed that the linewidth increases with the decrease
in particle size thus the presence of intrinsic size effects is
confirmed [28]. With the Mie theory and the bulk dielectric
constant only a minor dependence of the SPR linewidth on
the particle size can be explained. Therefore, to explain the
experimental data of SPR linewidth we have used the modi-
fied dielectric function as given below [29]:
86
ωp2
ε(ω, d) = εib + 1 − . (1)
ω(1 + iωγd )
Here, the first term is the contribution to the dielectric con-
stant due to interband transitions and it is assumed to be size
independent and the last term is the Drude–Sommerfeld free
electron term. In the above equation, ωp is the bulk plasma
frequency and γd is the size dependent phenomenological
damping constant which is given by the following equa-
tion [24]:
Avf
γd = γ0 + . (2)
r linewidth γ0 = 283 meV which are nearly the same as re-
Here, vf is the Fermi velocity and γ0 is the damping con-
stant of bulk metal, the value of vf = 1.4 × 106 m/s, and
A is the phenomenological parameter. The above equation
Fig. 6 Variations of the SPR line width with the particle size. Symbols
are experimental points and the solid line is the theoretically fitted one
Fig. 7 Variation of absorption spectra of Au nanoparticles prepared in
different surrounding media with laser ablation time of 15 minutes; (a)
in UV-Visible region and (b) in visible region. Here, dotted, dashed
H.S. Desarkar et al.
describes the limitations on the mean-free path of the free
electrons due to the reduction of particle size. Various val-
ues of A are considered; the value of A is taken as unity, if
the scattering is considered as isotropic, it is taken as 0.74
if diffusive, zero if elastic [30]. Kreibig and Genzel have
shown theoretically that the value of A lying between 0.1
and 2 is justified considering several factors into the consid-
eration [31]. However, we have fitted our experimental data
with Eq. (2) and the experimental point (circles) along with
the theoretically fitted line is shown in Fig. 6b. From the the-
oretical fittings, the obtained value of A = 0.3 and the bulk
ported earlier [29–32].
In the process of preparation of nanoparticles by laser ab-
lation in liquid technique, the chemical modification of the
liquid may takes place due to nanoparticle-liquid interac-
tion [34]. Therefore, from the UV-Visible absorption char-
acteristics as shown in Fig. 4 as well as in Fig. 7a, one may
infer another conclusion. Namely, the UV absorption peak
can be ascribed to the thermal decomposition of ethylene
glycol that occurs both on the Au target and on generated Au
nanoparticles. This effect and the appearance of correspond-
ing absorption peak in UV region have previously been ob-
served by Kazakevich et al. under laser ablation of a bulk
brass target in ethanol [34]. In case of production of noble
metal nanoparticles by laser ablation in liquid technique the
interaction of resultant nanoparticles with the liquid as well
as with the gases dissolved in the liquid is although mini-
mized [34] but to clarify the origin of the UV peak we have
prepared Au nanoparticles in three different surrounding liq-
uids but with the same laser fluence as used earlier and with
the laser-ablation time duration of 15 minutes. For compar-
ison, UV-Vis characteristics of the samples prepared with
three different liquids are shown in Fig. 7a. Here, a dotted,
dashed dotted and dashed line corresponds to the absorption
dotted and dashed curves correspond to the methanol, acetone and
ethylene glycol medium, respectively. In the inset symbols are experi-
mental points and the solid line is the theoretical one
Linear optical absorption and photoluminescence emission properties of gold nanoparticles
characteristics of the samples prepared in methanol, acetone
and ethylene glycol medium, respectively. From Fig. 7a it is
seen that an absorption peak in the UV region at ∼269 nm
is present in the samples which are prepared in ethylene
glycol as well as in methanol. For acetone such peaks are
not visible as it absorbs strongly below 300 nm wavelength.
Also, we have prepared silver nanoparticles in ethylene gly-
col medium with the same experimental parameters but no
such absorption peak is found to be appeared (results are
not shown here) in the UV region. Therefore, it is concluded
that the absorption peak appearing at ∼269 nm is not due
to the chemical decomposition of ethylene glycol and is due
to the interband transitions in the prepared Au nanoparti-
cles. The presence of absorption peak in 200–270 nm wave-
length regions for gold nanoparticles prepared in different
solutions has been reported previously and ascribed such
transition to interband transition [35]. Also there are some
other previous reports of observation of UV peak in Au
nanoparticles and they attributed it due to interband tran-
sitions [15, 25–27, 30].
It is found from Fig. 5 that the peak value of UV peak ab-
sorption varies with the time duration of laser ablation. Also
it is found that the position of UV peak shifts in the reversed
manner as that of SPR peak with the variation of time dura-
tion of laser ablation. Again it has been noted earlier that the
average value of particle size has decreased with the increas-
ing value of time duration of laser ablation. The interband
transition in UV region has been reported in chemically pre-
pared Au and Ag nanoparticles and in Au nanoparticles de-
posited in a quartz substrate by RF sputtering [15, 25, 30].
Also shift of the UV absorption peak to shorter wavelength
with the increase in particle size of Au nanoparticles have
been reported [15]. The surfactants and capping molecules
have also been observed to influence the intensity and width
of the interband absorption peak and this phenomenon has
been successfully used for biosensor applications [26]. Also
theoretically it has been shown that interband transition con-
tributes considerably to the absorption spectra of Au and Ag
nanoparticles at UV wavelengths [27]. In the present work,
no surfactant or capping molecules have been used and so
the intense interband absorptions are observed and its in-
tensity also varies with the laser-ablation time duration. The
UV peak absorbance is found to increase up to 20 minutes
of ablation time and then it is reduced for the value of laser-
ablation time up to 30 minutes and then again it is increased.
The reduction of absorbance might have taken place due
to agglomeration of nanoparticles. The further increase of
the UV peak absorbance in the samples prepared with time
duration longer than 30 minutes has occurred due to frag-
mentation of the agglomerated nanoparticles. The electronic
energy levels are not continuous in nanoparticles unlike in
bulk materials. Rao et al. reported that due to the quantum
size effects of the careers, the energy levels are discrete and
87
this can result in a sharp and an intense absorption features
corresponding to interband transitions in nanoparticles [27].
The effect of refractive index of the surrounding medium
on the absorption spectra of the prepared nanoparticles in the
visible region is shown in Fig. 7b. From Fig. 7b it is found
that as the refractive index of the surrounding medium is
increased, SPR wavelength is red shifted. The reason of red
shift of the SPR peak with the increase in the refractive index
of the surrounding liquid medium is explained below. For
spherical metallic nanoparticles with size much less than the
wavelength of external electromagnetic wave the resonant
frequency is given by

Ω = ωP / 1 + 2εm , (3)
where ωp is the plasma frequency and εm is the dielectric
constant of the surrounding medium. Therefore, with the
increase in dielectric constant of the surrounding medium
Ω decreases i.e. the surface plasma wavelength increases.
This result clearly supports our experimental observation.
The red shift of the SPR with the dielectric constant of sur-
rounding medium can also be analyzed as follows. From the
surface plasma resonance condition we have
ε(λ) = −2εm . (4)
Differentiating Eq. (4) we get
dε(λ)/dλ = −2dεm /dλ = −4dn/dλ, (5)
where n is the refractive index of surrounding medium. Now
using the value for ε(λ) of bulk gold [36] we can easily
calculate theoretically the value of dn/dλ by using Eq. (5).
However, SPR peak positions for different values of the re-
fractive index of the surrounding medium have been calcu-
lated and the theoretical results along-with the experimen-
tal data (symbols) have been shown in the inset of Fig. 7b.
A good agreement between the theoretical and experimen-
tal results is obtained. We find that a red shift of SPR peak
position of 1 nm occurs with increase in refractive index by
0.0171. Thus if the SPR peak position in a particular solvent
is known we can easily find the SPR peak position in some
other solvent by this approach.
Photoluminescence (PL) emission are collected at room
temperature under 269 nm wavelength excitation and those
are shown in Fig. 8a for all the samples which are pre-
pared with various values of laser-ablation time duration. It
is found from Fig. 8a that all the samples exhibit PL emis-
sion in the UV-Vis region peaked at ∼354 nm. The peak
PL emission intensity increases with the increase in laser-
ablation time duration and this might be due to increase in
concentration of nanoparticles in the nanocolloid prepared
with longer ablation time duration. It is observed that al-
though the SPR peak positions shifts with the particle size
but the PL peak position remains almost unaltered, this in-
dicates that PL spectrum simply reflects the joint density
88
Fig. 8 (a) Photoluminescence spectra obtained at room temperature
from the different samples. Solid, dashed, dotted, dashed dotted and
short dotted curves correspond to the samples prepared with 15, 20, 30,
45, 60 minutes of laser-ablation time duration, respectively. (b) Energy
level diagram of Au in the vicinity of the high symmetry point L. The
of states of d-band holes and sp band electrons. A photon
of 269 nm (4.62 eV) wavelength promotes electrons from
the d2 band into the sp band well above the Fermi level.
The holes in the d-band undergo Auger scattering and hole-
phonon scattering and then the direct radiative recombina-
tion of a d-band hole with an electron in the sp band takes
place, which leads to the PL emission peaked at 354 nm
wavelength (3.51 eV). The energy diagram of bulk Au is
shown in Fig. 8b which presents the excitation and emission
transitions at 269 nm and 354 nm wavelengths, respectively.
From Fig. 8a it is also found that the peak PL intensity and
hence the quantum efficiency of PL emission increases with
the increase in the laser-ablation time duration.
It is found further that the PL peak emission intensity at
∼354 nm in the sample prepared with laser-ablation time
duration of 60 minutes is enhanced by the factor of ∼2.5
in comparison to that obtained in the sample prepared with
laser-ablation time duration of 15 minutes. Photolumines-
cence emission from noble metals in the visible and in-
frared region had been reported by several authors in the
past [36–42]. There is also report on Stokes and anti-Stokes
emission of Au nanoparticles suspended in pure methanol
and methanol solution of rhodamine 6G dye by the excita-
tion of light of wavelength of 354.6 nm [40]. Photolumines-
cence from Au surfaces and nanoparticles with the emission
wavelength maximum ranging between 500 and 590 nm has
been reported by several authors recently [38–41]. Lumines-
cence in metals is a three-step process involving photo ex-
citation of electro-hole pairs, relaxation of excited electrons
and holes, and emission from the electron-hole recombina-
tion [38, 39]. In Au, the PL emission in 500–590 nm wave-
H.S. Desarkar et al.
dashed lines show absorption transitions at 269 nm and thus holes are
created in the d2 -band. Solid line shows the PL emission of wavelength
at 354 nm due to spontaneous recombination of electrons relaxed to
the Fermi level (EF ) and holes in the d-band
length range is attributed to electronic transitions between
the sp band just below the Fermi level and the first d-band
(d1 ) in the vicinity of the point L in the Brillouin zone [43].
Previously, blue-green PL emission from silver nanowire
has been reported by us due to electron-hole recombina-
tion [44]. Also Smitha et al. reported PL emission at 332 nm
from silver nanoparticles and observed that PL peak wave-
length is independent of the particle size while the intensity
increases sharply with decrease of particle size [45]. They
attributed such PL emission to radiative recombination of an
electron from an occupied sp band with the hole [45]. There-
fore, PL emissions observed in the prepared Au nanoparti-
cles in this work are attributed to recombination of electrons
with holes in the lower energy band d2 .
4 Conclusions
In conclusion, here we have reported the preparation of un-
capped Au nanoparticles having average sizes (radius) vary-
ing between 1.1 nm to 3.3 nm by laser ablation of solid gold
target in different liquid media. The used laser radiation for
the laser-ablation experiment is Nd:YAG laser radiation at
1064 nm having pulse duration of 10 ns. The UV-Vis ab-
sorption spectra of all the samples show the presence of ab-
sorption peaks in the visible (varying between 521–526 nm)
due to SPR and in the UV (∼269 nm) region due to inter-
band transitions in Au nanoparticles. The shift of the SPR
peak wavelength taken place due to the variation in the size
of the prepared nanoparticles and the linewidth of the SPR
peaks increase with the reduction in sizes of the prepared
Linear optical absorption and photoluminescence emission properties of gold nanoparticles
nanoparticles due to intrinsic size effects. Due to the ab-
sence of any capping agent or surfactant molecules the sharp
absorption in the UV region is observed. The measured ex-
perimental data of SPR line widths are fitted with a theo-
retical expression in the framework of Mie theory and the
estimated value of bulk linewidth (γ0 ) and the phenomeno-
logical parameter A are 283 meV and 0.3, respectively. All
the prepared samples exhibit PL emissions in the UV-Vis re-
gion with a peak at ∼354 nm under the excitation of 269 nm
wavelength. The PL peak emission intensity at ∼354 nm has
been found to be enhanced by the factor of ∼2.5 in the sam-
ple prepared with laser-ablation time duration of 60 minutes
in comparison to that obtained in the sample prepared with
laser-ablation time duration of 15 minutes. The observed
PL emissions peaked at ∼354 nm have been attributed to
recombination of electrons with holes from sp conduction
band to d-band of Au.
Acknowledgements Authors are grateful to DST, Grant No. SR/
FTP/PS-67/2008, Govt. of India for the partial financial support. We
are thankful to both the reviewers for their valuable comments and sug-
gestions in improving the manuscript.
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