ISSN 1054-660X, Laser Physics, 2007, Vol. 17, No. 12, pp. 13821388.

INTERACTION OF LASER RADIATION

WITH MATTER

MAIK Nauka /Interperiodica (Russia), 2007.

Original Text Astro, Ltd., 2007.

Laser Irradiation Effects on Gold

M. Khaleeq-ur-Rahmana, K. A. Bhattia, *, M. S.Rafiquea, A. Latifa, P. Leeb, and S. Mahmoodb
a Physics

Department, University of Engineering and Technology, Lahore, 54890 Pakistan

Institute of Education, Nanyang Technological University, Singapore

b National

*e-mail: kabhatti@uet.edu.pk
Received May 29, 2007

AbstractInvestigations on the laser irradiation effects on gold are explored in terms of plasma-plume dynamics and morphological and crystallographic changes. Annealed 4N gold samples were irradiated with a
Q-switched Nd:YAG laser (53 mJ, 21 MW, 532 nm, and pulse width 68 ns) for plume dynamics using 10-ns
gated fast photography. A Q-switched pulsed Nd:YAG laser (10 mJ, 1.1 MW, 1064 nm, and pulse width 9 ns)
was used to irradiate the surface of the samples for morphological and crystallographic studies of laser-irradiated gold in a vacuum ~103 Torr. The annealed samples were exposed to 50 shots of a Nd:YAG laser (10 mJ,
1.1 MW, 1064 nm, and pulse width 9 ns). The investigation on the plume was done by using an intensified
charged-couple device ICCD-5760/IR-UV camera. The morphological investigation of the irradiated surface
was carried out by analyzing micrographs obtained using an Hitachi S 3000 H scanning-electron microscope
(SEM). The crystallographic studies of the irradiated samples were performed by analyzing the XRD patterns
obtained using an X' Pert Pro Pan Analytical X-ray diffractometer. The investigation on gated ICCD images of
the plume reveal that, at very earlier times, the plasma-plume expansion has a linear trend, whereas, at later
times, the plasma-plume expansion is nonuniform. SEM micrographs exhibit the primary mechanisms of
pulsed-laser ablation (PLA), such as hydrodynamic sputtering, thermal sputtering, exfoliation sputtering, and
splashing. The surface morphology was explained in terms of crater formation, swelling, burning, nucleation,
grain growth, and nonsymmetric heat conduction. The nonuniform thermal expansion of gold due to thermalenergy transfer is also studied by SEM micrographs, which was supported by XRD analysis. The structural
analysis on the basis of XRD shows that the composition of the irradiated samples is not disturbed even after
laser irradiation. The grain sizes also changed due to laser irradiation.
PACS numbers: 52.38.Mf, 52.38.-r
DOI: 10.1134/S1054660X07120080

INTRODUCTION
In laser ablation, most of the absorbed energy is carried off with the ejected material, so that there is little
or no thermal damage to the surrounding substrate area.
The absorption of laser radiation by solids first converts
the electromagnetic energy into electronic excitation
and, then, into thermal, chemical, and mechanical energies to cause evaporation, ablation, excitation, and
plasma formation [1]. Plasma is transient in nature with
characteristic parameters that evolve quickly and are
strongly dependent on the irradiation conditions, such
as incident-light laser intensity, laser wavelength, irradiation spot size, ambient gas composition, and ambient pressure [25]. Plume hydrodynamics can be investigated using different methods, but the easiest for
plume propagation is fast photography employing
ICCD [6, 7]. The surface morphology of laser-irradiated gold may be explored using many methods, but
SEM micrograph study is the simplest. Macrolevel
quantitative analysis of the crystllinity of laser-irradiated gold is done by studying XRD patterns obtained
from an X-ray diffractometer. Much work has been performed using the novel technique of laser ablation,
since laser ablation reveals various parameters to support material processing [810].

Ted D. Bennett et al. [11] studied the pulsed-laser

sputtering of gold at near-threshold fluences (material
removal rates <10 /pulse) using time-of-flight plume
diagnostics, scanning-electron microscopic analysis of
the surface topography, and thermal analysis of the
transient near-surface conditions. Compagini et al. [12]
studied pulsed-laser ablation of gold and silver in several liquids to obtain nanoparticle solutions using 532nm 5-ns radiation. They observed the formation of
metallic and nonmetallic particles in the nanometricsize range depending on the liquid used as the environment. Zhigilei [13] investigated the kinetics and channels of laser energy redistribution in a target irradiated
by a short 1-ps laser pulse. The energy transferred from
the excited electrons to the lattice splits into several
parts, namely, the energy of the thermal motion of
atoms, the energy of the collective atomic motions
associated with the relaxation of laser-induced stresses,
and at laser fluences above the melting threshold; the
energy transferred to the latent heat of the melting and,
then, was released upon crystallization. The fraction of
nonthread energy in the total laser-pulse energy partitioning increases with an increasing laser fluence.
The work presented in this paper describes the
plume dynamics, surface morphology, and crystallography of laser-irradiated gold. The captured images by

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1383

D
ICC

G
PT

LASER IRRADIATION EFFECTS ON GOLD

Six port
chamber
Nd:YAG
laser
Vacuum
gauge

Focusing
lens
Target

Laser induced plasma

Fig. 1. Scheme of the experimental setup.

a computer-controlled gated ICCD camera contribute

towards a better understanding of the hydrodynamics of
plume propagation obtained from gold plasma. Morphological studies explain the fundamental mechanisms of laser ablation and heat conduction. The study
of the XRD patterns leads toward a better comprehension of the structural information [1417].
EXPERIMENTAL SETUP
Gold samples were annealed under a vacuum
~106 Torr, at a temperature of 355C for a duration of
8 h. The samples were irradiated by Q-switched
Nd:YAG lasers for ICCD imaging and morphological
and structural analysis. The target was kept on a rotation to minimize the local heating and drilling. Goldplume imaging was accomplished using gated ICCD. A
digital pulse generator was used to control the delay
between the laser pulse and the imaging system. To
control the saturation for the camera light, neutral-density (ND) filters were used between the glass window of
the vacuum chamber and the ICCD camera. The other
samples were irradiated at an angle of 45 with the normal to the surface for 50 shots. The irradiated surface
was then analyzed by using SEM for surface morphology. Macroscopic structural analysis was carried out
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employing an X-ray diffractometer. The scheme of the

experimental setup is shown in Fig. 1.
RESULTS AND DISCUSSION
ICCD Imaging
Time-resolved ICCD images of the gold plume are
shown in Fig. 2 with a gating time of 10 ns. Each image
is obtained from a single laser pulse. These are twodimensional images of the gold-plasma plume that provide an orthogonal view of the plume expansion with
respect to the target surface. If the laser intensity is
above the ablation threshold of the target, then evaporation, ionization, and melting of the target material takes
place to create a plasma plume. The motion of the species present in the plume obeys forward peaking [18,
19]. The accelerated ions in the expanding plasma
plume may attain an energy value of around a few hundred electronvolts. The production of ions also
increases at high fluences as a result of the fast interaction between the laser pulse and the rapidly produced
plasma [20]. As the laser photon reaches the target surface, plasma emission immediately begins. With the
passage of time, the emission can be resolved into two
components. Light emission very close to the target

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KHALEEQ-UR-RAHMAN et al.

10 ns

20 ns

50 ns

1000 ns

1500 ns

5000 ns

Fig. 2. Time-resolved gold-plume dynamics of ICCD imaging in a vacuum.

surface is present even after 500 ns. The stationary

emission region very near to the target surface is a consequence of the gas collision between the plume
ejectants in the high-pressure region of the initial
expansion. This results in the Knudsen layer with the
ejected material along with the backward-moving
material. The second component of the plasma plume
expands very rapidly in the forward direction along the
normal to the surface of the target [21].
Initially, the plume front is found to be in a spherical
form, but, afterwards, it becomes sharpened and
expands at an extremely high rate. Normally, the
higher-energy particles are emitted closer to the normal
target surface. Plasma ions are angularly distributed

with respect to energy and charged states due to the

mutual interaction and collisions with normal atom
ions or with nanoparticles [22]. The ion flux is found to
be high in the axial direction and reduces in the radial
direction. The maximum flux and energy of the ions is
in the forward direction. This is known as forward
peaking [19, 23].
At very early stages, the plume expansion is linear
for all background gas pressures. The shock model,
given by the equation [18]
1/5 2/5

R = 0 ( E 0 / 0 ) t ,

(1)

explains the explosive release of energy at the earlier

stages of plume expansion, where 0 is a constant which
depends on Y, the ratio of the specific heat capacity of
the expanding gas, whereas, at the later stages, the drag
model, given by the equation [18]
R = R 0 ( 1 exp ( t ) )

(2)

is used to describe the plume expansion, where R0 is the

stopping distance of the plume and is the slowing
coefficient.
From the above discussion, we can say that ICCD
imaging of the plasma plume provides a significant
understanding about the dynamics of the various species present in the gold plume [24].
100 m
MAG = 300
EHT = 10.00 kV

DETECTOR = SE1
Date: 26 Jul 2005

Fig. 3. SEM micrograph of laser-irradiated gold with 50

shots of an Nd:YAG laser at a magnification of 300.

SEM Analysis
The exposure of the metal surface results in changes
in the surface morphology, hardness, and phase. Figure 3
is a SEM micrograph of irradiated gold at a 300 magnification. It shows the nonsymmetric heat conduction
and ablation of material exposed for 50 shots. The
conelike structures show hydrodynamic sputtering and
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LASER IRRADIATION EFFECTS ON GOLD

1385

120 Jul_Au

Counts

1600
900
400
100
0

30

40

50

60

70
80
Position, 2, deg

90

100

110

Fig. 4. XRD pattern of unexposed gold.

1600

129 Oct_Abl

Counts

900
400
100

30

40

50

60

70
80
Position, 2, deg

90

100

110

Fig. 5. XRD pattern of exposed gold.

splashing. The ablation of the laser-irradiated metal target explained using a dimensional hydrodynamics
model describes the absorption of laser radiation, electron-heat conduction, and electronphonon and electronion energy exchanges, which result in material
motion and expansion [14]. Asperities show cones due
to a laser effect. These cones develop on the surface due
to repetitive laser shots, where, at some points, material
ejection is fast while at some other points, it is slow.
Pulsed-laser irradiation leads to the development of a
surface topography characterized by droplet and ridge
formations and the liberation of micron-sized droplets
into the plume. The majority of the surface topography
has been studied by hydrodynamic sputtering, along
with the ejection of neutral gold atoms [11]. This nonuniform ejection develops asperities, turbulent features,
and cones. These irregularities are due to surface impurities, crystal imperfections, and the TEM modes of the
laser used for irradiation [25], since the target is irradiated with a multimode Nd:YAG laser. The Material is
also splashed out from the irradiated-zone boundary.
An indication of the resolidification of the splashed
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material is also present. All of these phenomena are in

good agreement with previous investigations [15].
XRD Analysis
The crystallographic or structural study was carried
out by the analysis of X-ray diffractometer patterns.
The XRD pattern of gold before laser irradiation shows
a homogenous and crystalline structure [26]. Eight of
the nine peaks match the standard pattern for gold. Peak
[111] at 2 = 38.231 is due to pladium impurity. A
comparison of the two patterns shows that the irradiation of gold samples causes an increase in the intensity
as indicated by the peaks at angles 44.422, 77.645,
110.842, and 115.269, whereas, for some peaks, a
decrease is also observed after the laser exposure as
shown by the peak at angles 38.231, 64.659, 81.766,
and 98.157, respectively. A plot of 2 versus the relative intensity, shown in Fig. 6, indicates that, up to an
angle of 80, the intensity shows a Gaussian fit,
whereas, afterwards, a polynomial-fit trend is observed
for the unexposed sample. At the same time, a plot

1386

KHALEEQ-UR-RAHMAN et al.

Relative intensity
100
Un-exposed
Exposed

80
60
40
20
0
30

40

50

60

70

80

90 100 110 120

2, deg

Grain size,
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
30 40 50

Un-exposed
Exposed

60

70

80

90 100 110 120

2, deg

Fig. 6. XRD pattern of 2 vs. relative intensity.

Fig. 7. XRD pattern of 2 vs. grain size.

between the same quantities for the exposed samples

represents a LorentzB fit up to an angle of 65; afterwards, a decrease and increase in the intensity is
observed. Physical aspects that can change the intensity
may include the crystal imperfections caused by nonuniform strains imposed by laser irradiation on the
samples surface. Diffraction and scattering effects can
also cause the variation in intensity. The peak [111] at
2 = 38.497 indicates the maximum intensity for the
exposed gold. When recrystallization occurs, the peaks
attain their maximum sharpness. Sometimes, the reflection from the crystal surface also causes incremental
changes in the intensity of the radiation. The thermal
stresses due to laser irradiation can disturb the lattice
vibrations of the atoms, thus causing a variation in the
intensity. Mostly, the energy absorbed by the atoms is
conducted in a nonuniform way. Thus, a change in the
intensity is observed [27, 28].
No significant change in the values of 2 is observed
in the XRD patterns of gold as shows in Figs. 4 and 5.
The grain size of the irradiated simples is calculated
by using the formula [29]

processes are the two fundamental phenomena that

mostly affect the grain size [30]. Thermal stresses also
play a vital role in the change or variation of the grain
size. The grain growth implies a redistribution of the
grain orientation by the laser irradiation of the target
material [31].

D = 0.9/B cos ,

(3)

where D is the grain size, is the wavelength of the

X rays used, B is the FWHM, and is the Braggs
angle.
All of the peaks of the exposed samples indicate a
decrease in the grain size. Figure 7 shows a monotonic
decrease in the grain size, whereas a sharp increase is
observed at the end of the graph for the unexposed sample. The other graph for the irradiated sample indicates
a monotonic increase. A rapid decrease is observed at
the start and endpoints of the graph, which is exactly
opposite when compared with that of the unexposed
sample. The hardness of the material and the recovery

Figure 8 shows that the laser irradiation on gold has

a negligible effect on the d-spacing of the sample when
plotted against the 2 values. A trend of exponential
decay of the third order is found for both the unexposed
and exposed samples. Quite weak stresses are imposed
by laser irradiation, indicating no significant disturbances in the planes of the target samples. Also, no
d-Spacing,
2.4
2.2

Trend: Exponential decay of third order

2.0
1.8
1.6
Un-exposed
Exposed

1.4
1.2
1.0
0.8
30

40

50

60

70

80

90 100 110 120

2, deg

Fig. 8. XRD pattern of 2 vs. d-spacing.

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LASER IRRADIATION EFFECTS ON GOLD

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Table 1. Peak list of unexposed gold

Peak no.

d,

2, deg

I, %

FWHM,
deg

Grain
size,

Phase

1
2
3
4
5
6
7
8
9

2
2
3
2
4
3
4

0
2
1
2
0
3
2

0
0
1
2
0
1
0

2.35404
2.20778
2.03941
1.44157
1.22934
1.17787
1.02029
0.93635
0.91198

38.231
40.876
44.422
64.659
77.645
81.766
98.157
110.842
115.269

100 = x
4
24.64
27.38
27.59
20.63
9.90
8.14
11.38

0.295

0.295
0.394
0.394
0.492
0.394
0.394
0.360

4.843

4.943
4.054
4.398
3.629
3.484
6.037
7.005

Gold
Palladium
Gold
Gold
Gold
Gold
Gold
Gold
Gold

Table 2. Peak list of exposed gold

Peak no.

d,

2, deg

I, %

FWHM,
deg

Grain
size,

Phase

1
2
3
4
5
6
7
8
9

2
2
3
2
4
3
4

0
2
1
2
0
3
2

0
0
1
2
0
1
0

2.3385
2.20111
2.02963
1.43701
1.22714
1.1750
1.01933
0.9350
0.9108

38.497
41.005
44.648
64.890
77.841
82.001
98.282
111.081
115.492

100 = x
4.4082
34.3165
18.4369
32.9474
7.5918
3.9451
22.4486
22.5706

0.394

0.590
0.590
0.590
0.590
0.787
0.590
0.960

3.629

2.473
2.711
2.94
3.031
2.622
4.04
0.720

Gold
Palladium
Gold
Gold
Gold
Gold
Gold
Gold
Gold

change occurs in the (hkl) values used to verify these

effects.
Thus, we can say that the intensity changes the
redistribution of the grain orientation and adegradation
of crystalline quality has occurred after laser irradiation
of the gold samples.

posed samples, whereas Lorentz_B fits for the plots of

the exposed sample. The grain size decreases monotonically. Negligible effects are produced by laser irradiation on the d-spacing and this follows the exponential
decay of the third order. There is no change in the [hkl]
values.

CONCLUSIONS

ACKNOWLEDGMENTS

The dynamics of the gold-plasma plume concludes

that, initially, the plume is spherical, but, later, it is
sharpened, indicating the forward peaking of the
ejected species. At earlier stages, plume expansion is
linear and obeys the shock model, whereas, at later
stages, it is nonlinear and obeys the drag model. Morphological studies show that heat conduction is nonuniform and nonsymmetric. The SEM micrograph indicates a cone formation and micron-sized particulates
are produced by repetitive laser shots. Hydrodynamic
sputtering, splashing, and redeposition are observed
along with the neutrals of gold. The XRD patterns
exhibited a variation in the intensity of the diffracted
peaks due to laser irradiation. The intensity variation
obeys a Gaussian fit and a polynomial fit for the unex-

The authors acknowledge the Higher Education

Commission of Pakistan for sponsoring this PhD
project. Also, the authors acknowledge the Government
of Punjab, Education Department, for granting study
leave to K.A. Bhatti in order to pursue PhD studies.

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REFERENCES
1. A. Latif, M. Khaleeq-ur-Rahman, and M. Shahid
Rafique, in Proceedings of the Conference on Advanced
Materials, Putrajaya, Malaysia, 2005, p. 154.
2. S. Amoruso, R. Bruzzese, N. Spinelli, and R.Velotta,
J. Phys. B 32, 131 (1999).
3. F. J. Gordillo-Vazquez, A. Perea, J. A. Chaos, et al.,
Appl. Phys. Lett. 78, 7 (2001).

1388

KHALEEQ-UR-RAHMAN et al.

4. S. S. Harilal, C. V. Bindhu, V. P. N. Nampuri, and

C.P.G. Vallabhan, Appl. Phys. Lett. 72, 167 (1998).
5. S. S. Harilal, C. V. Bindhu, M. S. Tillack, et al., J. Phys.
D: Appl. Phys. 35, 2935 (2002).
6. S. S. Harilal, C. V. Bindhu, and H. J. Kunze J. Appl.
Phys. 89, 4737 (2001).
7. S. S. Harilal and T. E. Itina, Thin Solid Films 14, 453
(2004).
8. F. Furusawa, K. Takahashi, H. Kumagai, et al., Appl.
Phys. Lett. 69, 359, (2000).
9. L. Torrisi, S. Gammino, and L. Ando, Radiation Effects
and Defects in Solids 157, 333 (2002).
10. W. Jeffery Elam and i/nucleon/back full/vol 45_2005/v
45 n 3p 199f.Pdf.
11. D. T. Bennett, P. C. Grigoropoulos, Douglas, and J.Krajnovich, J. Appl. Phys. 77, 849 (1994).
12. G. Compagini, A. A. Sealisi, and O. Puglisi, Phys. Chem.
4, 2787 (2002).
13. V. L. Zhigilei, Appl. Surf. Sci. 248, 433 (2005).
14. T. E. Itina, Thin Solid Films 14, 453 (2004).
15. C. Haseung, Int. J. Heat Mass Transf. 47, 4165 (2004).
16. D.B. Geohegan and A.A. Puretzky, Appl. Phys. Lett. 67,
197 (1995).
17. S. S. Harilal, C. V. Bindhu, and H. J. Kunze, J. Appl.
Phys. 89, 4737 (2001).
18. C. Milone, R. Ingoglia, and S. Galvagno, Gold Bull. 39,
2 (2006).

19. M. Shahid Rafique, M. Khaleeq-ur-Rahman, Aziz-ulRhaman, et al., Laser Phys. 17, 282 (2007).
20. D. B. Geohegan, Pulse Laser Deposition of Thin Films,
Ed. by Chrisey and G. K. Hubler (Wiely, New York,
1994), p. 115.
21. W. Pietsch, J. Appl. Phys. 79, 1250 (1996).
22. M. S. Rafique, M. Khaleeq-ur-Rahman, M. S. Anwar,
et al., Laser Part. Beams 23, 131 (2005).
23. A. Thum-Jaeger, B. K. Sinha, and K. P. Rohr, Phys. Rev.
63, 016405 (2001).
24. S. S. Harilal, Beau OShay, Yezheng Tao. and M. S. Tillack,
J. Appl. Phys. 99, 083303 (2006).
25. H. G. Rubahn, Laser Applications in Surface Science
and Technology (Wiley, New York, 1999).
26. B. Gakovic, M. Trtica, Zltkocevic, et al., MTAEC9, 36
(34), 1, 5 (2002).
27. M. Chand, Science of Engineering Materials, Structure
of Matter (Macmillan, London, 1981).
28. B. D. Cullity, Elements of X-rays Differaction (Edison
Wesley, London, 1978).
29. E. Mirica, G. Kowach, P. Evans, and H. Du, Cryst.
Growth Des. 4, 147 (2004).
30. W. F. Smith, Principles of Material Science and Engineering (Tokyo, 1990).
31. N. Matsunami, O. Fakuka, M. Tazawa, and M. Sataka,
Surf. Coat. Technol. 196, 50 (2005).

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