Colloids and Surfaces A: Physicochem. Eng.

Aspects 522 (2017) 368–372

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Cavitation bubble dynamics and nanoparticle size distributions in

laser ablation in liquids
J. Tomko a , S.M. O’Malley a,b , Cory Trout a , J.J. Naddeo a , Richard Jimenez a ,
Julianne C. Griepenburg a , Wafaa Soliman c , D.M. Bubb a,b,∗
a
Department of Physics, Rutgers University – Camden, 227 Penn Street, Camden, NJ 08102, USA
b
Center for Computational and Integrative Biology, Rutgers University, Camden, NJ 08102, USA
c
Department of Laser Sciences and Interactions, National Institute of Laser Enhanced Science (N.I.L.E.S.), Cairo University, El-Gamaa Street, Giza 12613,
Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• The height of the liquid column is

found the strongly affect the cav-
itation bubble dynamics in laser
ablation in liquids.
• The cavitation bubble collapse time
determines the size distribution of
nanoparticles produced.
• The results are found to be in good
agreement with simulations of laser
ablation in liquids.

a r t i c l e i n f o a b s t r a c t

Article history: The influence of cavitation bubble dynamics is investigated during nanoparticle synthesis by ps laser
Received 12 January 2017 ablation of Au targets in distilled and deionized water. The height of the liquid column and the ambient
Received in revised form 3 March 2017 pressure is found to strongly influence both the maximum bubble radius and the collapse time, and
Accepted 11 March 2017
thus the nanoparticle size distribution. The bubble radius is fit to the Rayleigh–Plesset equation and the
Available online 16 March 2017
results are compared to earlier studies with ns lasers. These results are interpreted in the light of recent
computational work and the strong body of experimental evidence that shows the fundamental role the
Keywords:
central cavitation bubble plays in determining the size distribution of nanoparticles in laser ablation in
Laser ablation liquids
Nanoparticles
liquids.
Cavitation © 2017 Elsevier B.V. All rights reserved.
Colloids
Size-distribution

∗ Corresponding author at: Department of Physics, Rutgers University – Camden,

227 Penn Street, Camden, NJ 08102, USA.
E-mail address: danny.bubb@rutgers.edu (D.M. Bubb).

http://dx.doi.org/10.1016/j.colsurfa.2017.03.030
0927-7757/© 2017 Elsevier B.V. All rights reserved.
 J. Tomko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 522 (2017) 368–372
1. Introduction
Laser ablation in liquids (LAL) is a technique used to produce col-
loidal nanoparticle dispersions by focusing an intense laser beam
onto a target surface immersed in liquid. Despite a wealth of exper-
imental results (c. f . [1]), there is significantly less in the way of
theoretical/computational framework to understand the separate
influence of liquid properties, ambient conditions, materials prop-
erties, and laser parameters in LAL [2,3]. It is a very challenging
problem to computationally model as there is all the attendant
complexity of laser ablation with the added challenges of model-
ing a highly confined plasma and plume hydrodynamics in a dense
medium. When one adds the cavitation bubble dynamics that occur
immediately over the ablated laser spot, it is understandable why
computational studies lag somewhat behind experimental results.
Itina, Povarnitsyn, et al., have provided a comprehensive overview
of the first nanosecond following the arrival of a 100 fs pulse [4,5],
but it is clear that molecular dynamical simulations must be linked
with continuum models to capture the rich variety of length and
time scales present during this process. Such knowledge is key to
the control of size and shape necessary for application-related work
in this area [6].
Understanding the role of the cavitation bubble and the
target–bubble interaction during collapse appears to be key to
manipulating the size and shapes of nanostructures formed during
the LAL process [2,7]. Ibrahimkutty, Wagener, et al., have pro-
mulgated the idea that one must control the cavitation bubble
dynamics if one wishes to specify the size distribution of nanopar-
ticle produced by LAL [8,9]. Through the use of small X-ray and light
scattering, they have shown that nascent nanoparticles form within
the central cavitation bubble and that the dispersity index of the
particles is greatly influenced by the rate of collapse of the bubble.
In particular, they find that particles are re-deposited on the target
surface during ablation with a ns laser and that they can be irre-
versibly fused to produce larger aggregates in the high temperature
and pressure of the collapsed bubble. Since their measurements are
occurring within the bubble, they can obtain an accurate assess-
ment of the nanoparticle size distribution that is not influenced by
laser-nanoparticle interactions that complicate the understanding
of ex-situ analyses.
In the present work, we have either utilized a small chamber
as shown in Fig. 1 in which we have varied the ambient pressure
within the chamber from 20 kPa to 180 kPa, or we have placed the
target on an elevated platform to specify the height of the liquid
Fig. 1. Schematic of chamber used in these experiments. The camera lens is visible
in the left of the frame.
369
column over the target. The volume of liquid was kept constant
and a stir-bar was utilized to minimize screening from highly con-
centrated nanoparticles right above the target surface.
While the pressure range used in this study is admittedly nar-
row, the maximum cavitation bubble radius and the collapse time
are observed to change by a factor of more than two. This change
in bubble dynamics strongly influences the nanoparticle size dis-
tribution obtained from LAL and the results can be understood in
terms of the models that follow from the Rayleigh–Plesset equation
[10,11].
2. Results and discussion
2.1. Experimental details
The procedure for obtaining particles has been extensively
described previously [13]. Briefly, a 1064 nm laser with a 25 ps pulse
duration and 250 Hz repetition rate (Ekspla PL-2241) was focused
onto an Au target immersed in distilled and deionized (DDI) water
(R > 18 M). 4.7 mJ laser pulses with a beam waist of 100 ␮m (deter-
mined via knife-edge method) were utilized, leading to a fluence
of 20 J/cm2 . The platform was rastered to avoid excessive structur-
ing of the target. Ablation occurred for 2 min and the solutions were
immediately scanned to obtain UV–Vis spectra (Cary 20). Individual
drops of solution were placed on transmission electron microscope
(TEM) (Zeiss 902) grids where they evaporated to leave behind
nanoparticles. To obtain histograms, 400 particles were counted
for each sample with ImageJ software. Finally, images of the cav-
itation bubble were obtained in the same fashion as earlier work
[13,14].
2.2. Experimental results
2.2.1. Influence of liquid height
. If the liquid height above the target is increased as shown in
Fig. 2, we see that the nanoparticle diameter increases up until a
value of 8 mm and remains roughly constant after. As in our pre-
vious studies [13], we plot the geometric mean and the error bars
reflect the same range as a normal distribution plus or minus one
standard deviation would. While Ibrahimkutty et al. [9] argue for
the use of the mass-weighted average, we believe that the geomet-
ric mean most accurately captures the average particle size and we
do not observe enough large nanoparticles to assert the existence
Fig. 2. Nanoparticle diameter and histograms as a function of the height of the liquid
column above the target surface. All data points are obtained from TEM measure-
ments except for the first point in the back panel which was obtained by UV–Vis
fitting [12]. The lines in the back panel serve as visual guides.
370 J. Tomko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 522 (2017) 368–372
Fig. 3. (a) Bubble radius as a function of time and resulting Rayleigh–Plesset fits, (b) temperature within bubble according to the Van der Waals hard core model. Here, 2 mm
and 15 mm refer to the height of the liquid column.
of a bimodal distribution in this case. It may be that these discrep-
ancies are rooted in the fact that we are utilizing a 25 ps laser as
opposed to the ns laser in the aforementioned study. It is also pos-
sible that we utilize too low of a fluence to observe this phenomena.
Finally, it could be that the incoming laser pulse strongly interacts
with already-formed nanoparticles and reduces the average par-
ticle diameter. These possible differences will be explored more
below.
Both the mean diameter of the particles and the width of the
distribution increase with liquid height. To estimate the conditions
within the bubble we performed fitting to the Rayleigh–Plesset
equation [10] for the bubble radius as a function of time for liq-
uid column heights of 2 mm and 15 mm. These results are shown
in Fig. 3 and several salient points immediately commend them-
selves. Clearly, the bubble radius is strongly dependent on the
liquid column height for a fixed fluence. Second, for comparable flu-
ences, ps laser – produced bubbles are predicted to be much cooler
than bubbles produced with a ns laser [10] (c. f . 5000–8000 K with
20,000 K). This is at least partly attributable to the strong inverse
bremsstrahlung effect that is present for ns laser ablation in liquid.
While the calculation of the temperatures according to the hard
core Van der Waals model seems reasonable [15], the predicted
pressures are too high by at least one order of magnitude (∼1 TPa).
Conversely, if one assumes the bubble expansion and contraction
to be adiabatic, the pressure is more realistic, but the temperature
is predicted to be ∼1 K at maximum radius.
De Giacomo [15] calculates the temperature and pressure from
the actual data, but rightly notes that since the bubble dynamics
occur on the low ns scale, the temperatures are pressures are much
higher during events like collapse. Most shadowgraphy experimen-
tal apparatuses have temporal resolutions in the range of 10–50 ns.
So it seems reasonable to use the data generated from the fit in order
to calculate the temperature and pressure during collapse. The fail-
ure is not with Rayleigh–Plesset fitting, but more in our inability to
find a simple analytical model for the collapsing bubble that gives
physically reasonable results.
Explaining why the cavitation bubble radius depends on the liq-
uid column is more easily accomplished. First, given that each mm
of liquid only introduces another 10 Pa of pressure to the column,
inertial confinement is not a likely explanation, particularly when
one considers earlier results related to pressure [16,10]. Addition-
ally, the bubble pressure during its expansion phase tends to be
on the order of 103 Pa. Given the bulk modulus of water, this leads
to a volume change of the surrounding liquid well below 0.01%,
regardless of the liquid height. Correspondingly, translation of the
liquid layer should be constant for all layer heights. Finally, while
prior work has shown the effect of liquid height on fluence on
the target surface [17], other mechanisms are clearly involved in
determination of the maximum bubble height and subsequent par-
ticle distributions.
The so-called Rayleigh time is the interval between the bubble
reaching maximum radius and the eventual collapse, and it is given
as:


tc = 0.915Rmax × (1)
Pamb − Pv
where  is the density of the fluid, Rmax is the radius of the bub-
ble at its maximum, Pamb is the pressure in the fluid, and Pv is the
vapor pressure. In the experiments with varying liquid height, this
relationship is not obeyed. Something delays the collapsing bub-
ble when the liquid column’s height is low. In order to find an
explanation, we return to the plume shadowgraph images.
Examining images of the cavitation bubble and shockwaves
present during LAL experiments [18], several types of shockwaves
are observed. First, one is created by the laser ablation event and
appears after 100 ns. It is a weak shock front and moves at the
speed of sound in the liquid (∼1.5 km/s in water). This shock front
eventually reflects off of the water–air interface, and because of the
large mechanical impedance (Z = cs where ␳ is the density and cs is
the sound velocity) mismatch between these two layers, very little
sound wave intensity is transmitted into the air (T ∼ 0.001 where
T is the transmission coefficient). Virtually of the original shock-
wave is reflected back towards the target. There are also stress
waves created in the Au target that reflect off of the bottom inter-
face and propagate into the liquid after passing through the top
(metal–liquid) interface. These stress waves first make an appear-
ance approximately 700–800 ns after the arrival of the laser pulse
and they continue to be emitted from the target surface in regular
intervals thereafter. These waves are less intense than those in the
interior of the target as T ≈ 0.1 in this case.
The downwardly propagating shockwave compresses the bub-
ble, thus causing a temperature rise and a concomitant increase in
maximum radius. This delays the eventual collapse and the growth
and nucleation time of the particles. A heuristic model based upon
La Mer’s diagram [19] can be invoked to explain the dependence
of the nanoparticle size in this case. When the bubble is at its
maximum radius, the concentration is not high enough to induce
rapid homogeneous nucleation. However, upon collapse, the con-
centration rises to a value greater than the lower critical density
and particles rapidly grow. If the bubble rebounds weakly with-
out ejecting a large fraction of its mass, then the concentration
will remain above the lower critical value and allowing particles
to enlarge. In this fashion, we propose a strategy to control particle
size during LAL through external pressure modification (next sec-
tion) or and/or changes in the liquid height column above the target.
This could also help explain the differences observed between
 J. Tomko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 522 (2017) 368–372 371

Fig. 4. (a) Early time dynamics of cavitation bubble growth for 2 mm liquid height column. Upward facing arrows mark the appearance of new shock fronts. These fronts are
marked by a dashed line in the images in the inset. Downward facing arrows mark the arrival of more intense shockwaves reflected off of the air-water boundary. The delay
time of the images (ns) is indicated in blue and a 0.18 mm scale bar is indicated in red. (b) Heuristic version of LaMer’s diagram showing concentration and bubble radius and
their influence on growth. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)

particles produced with a ps laser and those formed with a ns laser.
In the ps case, the bubble rebounds one time and appears to stop
oscillating whereas in the ns case, the oscillations occur for sev-
eral more cycles. These last cycles of the bubble are much smaller
than the initial oscillation and the total lifetime can stretch over
hundreds of  s (Fig. 4).
2.2.2. Influence of ambient pressure
. The ambient pressure strongly influences the maximum cavi-
tation bubble and time of collapse. Perhaps most surprising is that
the range over which this occurs is fairly narrow. In Fig. 5b, one can
see that as the pressure is reduced, the bubble’s maximum diam-
eter increases as does the time until first collapse. In the range of
our observations, the maximum bubble radius depends linearly on
the ambient pressure while the collapse time falls off more rapidly.
In the lower panel of Fig. 5b, we fit the data to Eq. (1) to confirm
1
tc
that Rmax ∼P − 2 . We can neglect the vapor pressure at the extremely
low temperatures inside of the fully expanded bubble [10]. Just as
in the data from a liquid column, the mean particle diameter and
distribution size are found to be strongly correlated with the maxi-
mum bubble radius and collapse time. A ready interpretation of our
pressure-dependent results can also be found in the above adap-
tation of LaMer’s diagram. Here we associate the smaller bubble
volume found at high pressure with the conditions that favor rapid
nucleation and growth. Bubbles formed at lower pressure are able
to expand more and the concentration remains more in line with
the conditions for moderate growth and nucleation.
2.2.3. Comparison with earlier results
. In our earlier work, we reported the effect of laser fluence on
the average nanoparticle size and the cavitation bubble radius [13].
Here, there was a clear and strong dependence of the bubble radius
on fluence, but there was large scatter in the nanoparticle diame-
ter results. While it is difficult to directly compare the work done
here with different liquid heights and ambient pressure to earlier
work with varied fluences, it may be instructive to compare the
fluence-dependent data with the computational results of Povar-
nitsyn et al. [4,(especially Figs. 2, 4, 6, and 8)]. If we assume t1/2 –
scaling [20] between the computational results that utilize a 100 fs
laser and the experimental results obtained with a 25 ps laser in
order to compare fluences, we are able to identify low, medium,
and high fluence ranges that correspond to distinctly different ejec-
tion mechanisms. In this study, we operate solely in the “high”
fluence regime (>10 J/cm2 ). At these fluences, the computational
model predicts that a secondary molten layer forms after energy
is reflected back into the target. This is thought to lead to larger
primary particles with a bimodal distribution. We do not observe
this in our experimental results in the present work or the past.
One possible mechanism for breaking apart this secondary molten

tC
Fig. 5. (a) TEM histograms of particles made at different pressures. The back panel shows the nanoparticle diameter as a function of the cavitation bubble radius. (b) Rmax
as
a function of ambient pressure. The line is a fit to Fig. (1).
372 J. Tomko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 522 (2017) 368–372
layer could be the collapse of the cavitation bubble and the violent
secondary ejection that often follows. It could also be that we still
at too low of a fluence to clearly observe the bimodal nature of the
particles. In any event, we regard the overall agreement between
our experimental work and the earlier computational work to be
good.
3. Conclusion
The size distribution of nanoparticles formed in LAL experi-
ments can be greatly affected by the height of the liquid column
above the target and the ambient pressure. It is also found that there
is a strong correlation between the size of the cavitation bubble at
its maximum radius and the collapse time. The time required for
bubble collapse also appears to strongly influence the particle size
and we hypothesize that a heuristic model based upon La Mer’s dia-
gram might be used to help target desired nanoparticle properties
during LAL.
Acknowledgments
D. M. Bubb and S. M. O’Malley acknowledge Awards CMMI-
0727713, CMMI-0922946, and CMMI-1531783 from the National
Science Foundation and support from the Charles & Johanna Busch
Biomedical Grant Program.
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