Appl. Phys.
A 81, 639–643 (2005)
DOI: 10.1007/s00339-004-2671-5
t. okamoto1 Analytical study on metal microstructures
e. ohmura1
t. sano1,u using femtosecond laser
y. morishige2 1 Graduate School of Engineering, Osaka University, 2-1 Yamada-Oka, Suita, Osaka, 565-0871, Japan
i. miyamoto1 2 Laser Solution Division, NEC Corporation, 1120 Shimokuzawa, Sagamihara, Kanagawa, 229-1198, Japan
Received: 8 December 2003/Accepted: 4 February 2004
Published online: 2 June 2004 • © Springer-Verlag 2004
ABSTRACT We made considerations for microstructures on
chromium film observed after femtosecond laser irradiation
through an analytical study. Laser diffraction through an op-
tical system with a rectangular aperture was analyzed for the
estimation of intensity distribution at the focal point. Molecular
dynamics (MD) simulation was also performed for the exam-
ination of laser ablation of metal by taking account of the
electron–phonon relaxation. From results of diffraction calcula-
tion, it was shown that a typical surface pattern is significantly
affected by laser intensity distribution. On the other hand, it may
be estimated through the MD simulation that the porosity for-
mation evolves by cumulative pulses with energy close to the
ablation threshold and their surrounding grows to microcolumns
with volume expansion.
PACS 68.08.De; 68.35.-p
1 Introduction
In recent years, some types of microstructures
formed by pulse laser irradiation have been reported and they
have been recognized for their possibility of application to mi-
croelectronic devices [1–7]. There are some reports of surface
microstructure on silicon [1–4] or metal [5–7]. The mi-
crostructures are classified according to features into ripple,
column, cone, spike, etc. The mechanism of microstructure
formation has been thought to involve various factors such
as diffraction, polarized direction, thermohydrodynamics and
ablation. In the previous reports [1, 7], it was shown that laser
diffraction through an optical system was significant for sur-
face microstructure formation. In the reports for columns and
cone formations [2–4, 6], laser irradiation in the various ambi-
ent gases was performed and the influences of ambient gases
were investigated. For example, sharper cone was observed
after laser irradiation to silicon in SF6 , which had chemical
etching effect [2]. We carried out femtosecond laser irradi-
ation to chromium thin film on quartz substrate, so-called
chromium binary mask, in air with a rectangular aperture. The
chromium binary photomask has been used as one kind of
typical photomask. As a result, surface microstructures were
observed.
u Fax: +81-6/6879-7534, E-mail: sano@mapse.eng.osaka-u.ac.jp
Applied Physics A
Materials Science & Processing
In order to elucidate the mechanism of microstructure for-
mation, we analyzed laser diffraction through our experimen-
tal optical system with a rectangular aperture. In addition,
surface motion of metal was also analyzed by using molecular
dynamics (MD) simulation. In MD simulation, intensity dis-
tribution caused by laser diffraction was taken into account. In
the laser ablation analysis, it is required that laser pulses sim-
ultaneously interact with solid, liquid and vapor phases. Using
MD simulation for interaction of laser with materials [8–15]
is an effective approach to deal with such complex phase tran-
sitions. An analysis for chromium of the bcc structure at room
temperature requires three-dimensional (3D) simulation with
a many-body interatomic interaction potential. In order to take
into account of laser intensity distribution, it is desirable that
the size of analysis area get closer to the experimental size
of the diffractive pattern. Two-dimensional (2D) simulation,
which is useful from the viewpoint of the size of the analysis
area, is acceptable for the analysis of the material of the fcc
structure. In the present study, the 2D simulation is performed
for copper of the fcc structure. Taking copper instead of chro-
mium in the simulation is permitted on thinking macroscopic
qualitative tendency after laser irradiation. A significant char-
acteristic of the femtosecond laser is that pulse width is
shorter than the electron–phonon relaxation time. Therefore,
it is necessary to consider that electron–phonon equilibrium
is achieved after energy relaxation from electron to lattice.
The influence of electron–phonon nonequilibrium in metal
is often discussed using a theoretical approach, the so-called
two-temperature model [16]. There is a hybrid approach in-
cluding both the two-temperature model and the MD simu-
lation model [12]. We adopted another approach for the MD
simulation of femtosecond laser ablation. In the present study,
the influence of electron–phonon nonequilibrium was taken
into account in MD simulation with the assumption of a re-
laxation function. Through MD simulation, we investigated
microstructure formation on a metal surface without chemical
effects in atomic order.
2 Experiment
Our experiments were performed using a fem-
tosecond laser system. This laser oscillates with pulse width
130 fs and wavelength 800 nm. Available repetition rate is
from 1 Hz to 1 kHz. Samples are chromium film of 80 nm
thick, which is plated to a quartz substrate. The chromium film
640 Applied Physics A – Materials Science & Processing

a popular relaxation function, where ψ(t) is electron energy

eV, t is the progress time from the irradiation of laser pulse and
τ is relaxation time. From the Elsayed-Ali et al. report [19],
the relaxation time of copper is estimated to be about 4 ps. Ab-
sorbed electron energy is transferred to lattice energy, which
is the kinetic energy of atoms, according to the assumption
FIGURE 1 Optical system for our experiment: focal length of relay lens is
600 mm, that of the objective lens is 10 mm and its NA is 0.46 of the relaxation function. On the other hand, the increase of
kinetic energy of an atom is written as E(t) = ψ0 (1 − e−t/τ ).
Atoms absorb energy during laser irradiation. Therefore, ψ0
is coated with chromium oxide of 20 nm thick to prevent light is the dependence of temporal pulse shape and the location of
reflection. Laser pulses were irradiated in air through the opti- respective atoms. The total increase of kinetic energy at arbi-
cal system shown in Fig. 1. The adjustment of the aperture size trary time t is taken by integrating over the laser irradiation
enables us to control the laser focal size. We used a refractive time. The total increase of kinetic energy of respective atoms
microscope objective for the objective lens. is expressed by the following equations:
t
3 Analysis model   t−t 

0 < t ≤ tl E a (t) = ψa t  1 − e− τ dt  , (5)
Laser intensity distribution at a focal point is cal- 0
culated by general diffraction theory. We discuss molecular
tl
dynamics simulation in detail. In the present study, our analy-   t−t 

sis condition is as follows: Laser wavelength is 800 nm, pulse t > tl E a (t) = ψa t  1 − e− τ dt  , (6)
width is 130 fs, initial temperature is 300 K and the material is 0
copper. Though there is a difference in the model from actual
where E a (t) is the total increase of kinetic energy, ψa (t  ) is the
experiments, we can refer to results of MD simulation to de-
absorbed energy of respective atoms at time t  during laser ir-
rive the qualitative tendency after laser irradiation. We use the
radiation and tl is laser irradiation time. For one MD step, t ,
Morse potential between two atoms, which is given by
the functions for increase of kinetic energy of the respective

 atoms have the following forms, by taking the difference of (5)
Φij = D e−2α(rij −r0 ) − 2 e−α(rij −r0 ) , (1)
and (6):
where rij is the distance between two atoms i and j , and D = 
t+∆t
0.3429 eV, α = 1.3588 A−1 , r0 = 0.2866 nm for copper [17].  t−t 

Atomic interaction force Fij is expressed by 0 < t ≤ tl E a (t + ∆t) − E a(t) = ψa (t  ) 1 − e− τ dt  ,
t
∂Φij (7)
Fij = − . (2)
∂rij tl  t−t  
t+∆t−t 
t > tl E a (t + ∆t)−E a(t) = ψa (t  ) e− τ − e− τ dt  .
Atomic motion is described by the following Newtonian mo-
tion equation: 0
(8)
∂ 2 ri 
mi 2 = Fij . (3) As a result of our assumption, the kinetic energy of atoms
∂t j
=i continues to increase long after the laser pulse ends, like pi-
cosecond laser pulses of direct absorption.
We use the leap-frog method to solve (3) at the time step of
1 fs. 4 Results and discussion
In the laser absorption process, Lambert’s law, expressed
by (4), is assumed per atom. Then laser energy absorbed by an In order to obtain a sharp ablation edge and prevent
atom contributes to the increase of its kinetic energy [9]. damage of the quartz substrate using femtosecond laser, we
suggest an irradiating condition in which the sample material
A(z, t) = I(t) e−αz , (4) is ablated little by little with repetitive irradiation by pulses of
low-power density. Under such irradiating conditions, a typ-
where z is the direction perpendicular to the surface of ical surface feature was often obtained. Figure 2 shows SEM
the sample, I(t) is laser intensity W/cm2 , α is absorp- images of surface features obtained in the repetitive irradi-
tion coefficient and its literature value for copper is α = ation. Rather than a uniform pattern, a typical surface pattern
7.91 × 107 1/m [18] at laser wavelength 800 nm. In the was observed in the laser-irradiated area. These patterns on
present work, laser intensity is expressed by just the absorp- chromium thin film relate to laser intensity distribution by
tion energy without reflection. It was previously noted that diffraction through the optical system shown in Fig. 1. Fig-
the femtosecond laser has a pulse width that is shorter than ure 3 shows the laser intensity distribution at the focal point
the electron–phonon relaxation time. In order to take into ac- in the optical system shown in Fig. 1, which is calculated by
count this characteristic of the femtosecond laser, we assume the diffraction theory. Intensity distribution at the focal point
that the electron–phonon relaxation phenomenon in nonequi- is determined by factors such as optical configuration, focal
librium is approximately written as ψ(t) = ψ0 e−t/τ , which is size, objective lens, wavelength, etc. It is clearly observed in
OKAMOTO et al. Analytical study on metal microstructures using femtosecond laser
the results of Fig. 3 that diffractive intensity distribution is re-
lated to laser focal size. It seems to be quite reasonable to think
that a typical surface pattern in Fig. 2 is affected by intensity
distribution, as can be seen Fig. 3. The results show a char-
acteristic of the femtosecond laser that is the slight thermal
effect. Thus, it was concluded that the laser ablation feature
was significantly affected by laser-intensity distribution. We
should regard laser-intensity distribution, even if it were very
small at the diffraction pattern level, as an important factor for
precision micromachining. Combining a femtosecond laser
with the diffraction phenomena is necessary for advanced ap-
plications in micromachining.
In our experiments, microcolumns were formed after cu-
mulative pulses with energy close to the ablation threshold.
Figure 4 shows microcolumns observed by AFM. In the laser
641
FIGURE 2 SEM images of a typical surface pat-
tern ablated with some pulses: a 1 pulse, b 2 pul-
ses, c 4 pulses, d 8 pulses
irradiated area, microcolumns protrude from the original sur-
face. The protruding height shown in the surface line profile
by AFM reaches more than 100 nm, which is the initial chro-
mium film thickness. Pedraza et al. reported that the oxygen
content of the atmosphere had a large influence on the silicon
microcolumn morphology [3]. Preuss et al. showed metal mi-
crocolumns formed in vacuum [20]. We think that the mech-
anism of microcolumns formation consists of both chemical
and physical factors.
We analyzed laser ablation by irradiation of diffractive
intensity distribution like that shown in Fig. 3 using MD simu-
lation. In our analysis model without metal surface reflection,
we estimate that the laser ablation threshold is approximately
100 GW/cm2 . In the MD simulation, the ablation threshold
is determined as that when the laser energy that the droplet
FIGURE 3 Focal size dependence of laser in-
tensity distribution with optical configuration in
Fig. 1: a 7 µm focal size, b 8 µm focal size, c 9 µm
focal size, d 10 µm focal size
642 Applied Physics A – Materials Science & Processing
FIGURE 4 AFM images of microcolumns formed after 500 pulses: a area
profile, b line profile
formed from the material can be separated from the surface.
We assume the laser intensity distribution as shown in Fig. 3.
One triangle of such an intensity distribution is postulated in
the analysis area. The center in the analysis area is the highest
laser intensity and the border is the lowest laser intensity. The
intensity ratio is 4 : 3 between the top and bottom of the inten-
sity distribution. The average laser intensity is 100 GW/cm2 .
Because the surface in the horizontal direction of the analy-
sis area is given by the periodical boundary condition, we can
assume continuous intensity distribution. Figure 5 shows the
results of MD simulation. First, the surface starts moving in
picosecond order. The result of the absorption process on the
assumption of a relaxation function shows that, even if pulse
width is of the femtosecond order, surface instability occurs
in picosecond order. The time scale of MD simulation agrees
with that of an experimental report [21]. Insufficient energy
doesn’t allow atoms to eject from the surface. As a result of
such insufficient energy, porosity in the vicinity of the sur-
face and asperity are recognized. The surface feature may be
affected by various factors. If the volume expansion in mi-
crocolumns is caused by the disjunction from the substrate,
the verticality shown in Fig. 4 would not appear. But it can
be considered that an important factor of volume expansion
in microcolumns is the porosity evolution caused by cumu-
lative pulses with energy close to the ablation threshold. If
porosity formation evolved by repetitive irradiation, the sur-
face would rise higher and higher. From the facts described
above, we could conclude that microcolumns are formed after
cumulative pulses with energy close to the ablation thresh-
old. Although thermal radiation and bremsstrahlung are not
considered in the present MD simulation, it is expected that
these cooling effects provide more desirable conditions for
microcolumn formation. The mechanism due to porosity evo-
lution seems to be an important physical factor that explains
the microcolumn formation after cumulative pulses with en-
ergy close to the ablation threshold.
5 Summary
In our experiments using a femtosecond laser, sur-
face microstructures were observed in the laser-irradiated
FIGURE 5 Snap shots of MD
simulation due to irradiation
with diffractive intensity distri-
bution, when average energy is
100 GW/cm2
OKAMOTO et al. Analytical study on metal microstructures using femtosecond laser
area. It was found that a typical surface pattern on a metal sur-
face is related to the intensity distribution at a focal point cal-
culated by diffraction theory. Microcolumns protruding above
the original surface were formed after cumulative pulses, the
energy of which was close to the ablation threshold. In the
MD simulation for femtosecond laser ablation, it was as-
sumed that the electron–phonon relaxation phenomenon was
approximately expressed by an exponential function. As a re-
sult, the kinetic energy of atoms continued to increase for
a much longer duration than pulse width, and surface insta-
bility occurred in picosecond order, though laser pulse width
was below 1 ps. From the results of MD simulation, it was
shown that porosity is formed in the vicinity of the surface.
This porosity formation is caused by the insufficient energy
to remove the material from the surface. If the porosity for-
mation evolved by cumulative pulses with energy close to
the ablation threshold, their surrounding area would grow to
microcolumns.
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