Solid State Phenomena Submitted: 2020-05-01

ISSN: 1662-9779, Vol. 314, pp 197-201 Revised: 2020-06-18

© 2021 Trans Tech Publications Ltd, Switzerland Accepted: 2020-08-06
Online: 2021-02-09

Effect of Surfactant in Gas Dissolved Cleaning Solutions on Acoustic

Bubble Dynamics
SoYoung Han1,a, Nagendra Prasad Yerriboina1,b, Bichitra Nanda Sahoo1,c,
Bong Kyun Kang2,d, Andreas Klipp3,e and Jin Goo Park1,f,*
1
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, 15588,
Republic of Korea
2
BASF Company Ltd., Suwon 16419, Republic of Korea
3
BASF SE, Ludwigshafen, 67056, Germany
a
syhahn25@hanyang.ac.kr , bnag@hanyang.ac.kr , cbichitra@hanyang.ac.kr ,
d
brwon.kang@basf.com , eandreas.klipp@basf.com , fjgpark@hanyang.ac.kr

Keywords: Megasonic cleaning, EUV mask cleaning, Anionic Surfactant, Acoustic cavitation

Abstract. Megasonic cleaning is one of the promising technologies to remove the particles during
semiconductor processing. Acoustic bubble cavitation plays a key role in removing the particles. In
this work, the effect of an anionic surfactant sodium dodecyl sulfate (SDS) on a bubble in the presence
of hydrogen dissolved DIW water was studied. The bubble dynamics were observed using a high-
speed camera. It was found that with the increase of surfactant the bubble characteristics were
changed very significantly. Several parameters affecting the bubble dynamics were investigated.

Introduction
Bubble dynamics play a key role in affecting the surface cleaning in the semiconductor megasonic
wet cleaning. These bubbles can undergo a range of different behaviors. They dissolve, coalesce, or
leave the system entirely. Bubbles can also grow in size over many acoustic cycles, through a process
known as rectified diffusion [1]. The proportion of stable and transient cavitation of the bubbles will
impact the cleaning performance in the standing wave field [2]. Generally, stable cavitation is
desirable and transient cavitation is undesirable especially for the cleaning of fragile pattern structures
such as poly patterns and EUV masks. However, not only high Particle removal rate but also low
pattern damage is the highly important to use cleaning system. Thus, in order to guarantee a damage-
free yet efficient particle removal process, the bubble size distribution has to be kept around the
“active” size interval [3]. In this interval the bubbles oscillate strongly as a response to the applied
acoustic pressure [3]. So, it is important that consider the size of bubble and also bubble dynamics.
Transient cavitation usually occurs due to the coalescence of bubbles. The increase of stable
cavitation and reduction of transient cavitation can be achieved by several physical and chemical
methods [2]. The bubble characteristics can be studied well by forming standing waves during the
acoustic phenomenon [4]. At moderate acoustic powers, the bubbles smaller (larger) than resonance
size will travel up (down) a pressure gradient [5]. Since the standing-wave field can be shifted by
changing the mutual phases of driving signals, a particle trapped at the pressure node of the standing
wave field moves two-dimensionally along with the shift of the sound field. So bubble also it happens
to bubble [6]. Small bubbles trap at antinode position and large bubbles trap at node position.
Dissolving a gas such as hydrogen in the cleaning solutions will significantly enhance the acoustic
cavitation [2]. The addition of a surfactant controls the cavitation phenomenon [1]. However, no
studies are available on the effect of surfactant in H2 dissolved cleaning solutions on bubble dynamics
during acoustic cavitation. In this study, an anionic surfactant, sodium dodecyl sulfate (SDS), was
chosen to study the bubble dynamics as a function of its concentration using a high-speed camera set
up.

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198 Ultra Clean Processing of Semiconductor Surfaces XV

Experimental Procedures
The schematic of the production of hydrogen dissolved deionized water (H2-DIW) is shown in
Fig. 1. The H2-DIW for the experiments was generated by an ex-situ gas injection method with a
pressurized buffer tank. A commercial gas contactor (pHasor II, Entegris) was used for dissolving H2
into DI water. The concentration of H2 gas in DIW was controlled and was detected by a portable
type of the dissolved H2 gas analyzer (ENH-2000, TRUSTLES, Japan).

Figure 1. Schematic of the H2-DIW generation system

In this work, high-speed camera (VEO710, Phantom, USA) system (HSC) was used to study the
bubble dynamics in H2-DIW system as shown in Fig.2. The sizes and populations of the bubbles
under the ultrasonic irradiation (40 kHz) were observed. To analyze the bubble size and population,
commercial software (PCC, Phantom, USA) was used. To observe the bubbles more clearly using
high-speed camera, a standing wave condition was maintained. Oscillating bubbles can be trapped in
standing-wave-like acoustic fields that appear in ultrasonic cleaning baths. The light source,
ultrasonic bath and camera were set in a straight line for the clear observation of bubbles. Physical
properties of surfactants such as static surface tension (DCA-315, CAHN Instrument, USA) and
dynamic surface tension (K100, KRUSS, Germany) were measured.

Figure 2. Schematic of high-speed camera set up to observe the bubbles under ultrasonic
irradiation
 Solid State Phenomena Vol. 314 199

Results and Discussion

Using high speed camera set up (shown in Fig.2), the bubble characteristics were recorded at
different experimental conditions. Fig. 3 shows the images of the bubbles observed as a function of
SDS surfactant concentrations (0, 5, 10, 20, 50, and 100 ppm) at a particular instance of ultrasonic
irradiation in the presence of H2-DIW gas. It was found that the resonance size of the initially created
bubbles in the presence of dissolved hydrogen at different surfactant concentrations varied mainly in
the range of 125 to 155 µm except for a higher concentration of surfactant of 100ppm (64 µm). The
increase of bubble size at 20 ppm surfactant concentration and decrease of bubble size at 100 ppm
surfactant concentrations were observed. At 20 ppm concentration bubbles may undergo rectified
diffusion due to the partial adsorption of surfactant and at 100 ppm surfactant may adsorb completely
to inhibit the growth of the bubbles. When no surfactant was added, a higher coalescence of the
bubbles was observed. With the increase of surfactant concentration, the coalescence was reduced
significantly and at higher concentrations completely inhibited. However, the grouping of bubbles
was observed without causing coalescence. It could be expected that the surfactant might have
adsorbed on the outer surface of the bubbles preventing the bubble coalescence due to electrostatic
repulsions.

Figure 3. The bubble population and size change with the increase of SDS concentration in H2-
DIW
These results show that the surfactant concentration plays a key role on the bubble dynamics. To
check the effect of surface tension, both static and dynamic surface tensions were measured as a
function of SDS concentration and the results are shown in Fig. 4 and 5. While a great variation in
the bubble dynamics was observed, there were no significant changes in the surface tension values.
It shows that surface tension is not a key factor to affect the bubble characteristics. Further studies
are required to find a suitable mechanism for this phenomenon.
200 Ultra Clean Processing of Semiconductor Surfaces XV

Figure 4. Static surface tension measurement as a function of SDS concentration

Figure 5. Measured dynamic surface tension trends at different concentrations of SDS

Summary
Bubble dynamics were evaluated with respect to bubble size and populations as a function of
anionic surfactant (SDS) concentration. Bubbles were trapped stably at node position with the
standing wave to study their behavior. Firstly, a higher coalescence of the bubbles was observed
without surfactant and it decreased with the increase of surfactant concentration and reached a stable
size at high concentration. Though there is no much change in the static surface tension and dynamic
surface tension values, bubble characteristics were changed very differently with increasing
surfactant concentration. Depending on the cleaning target, optimization of surfactant concentration
is necessary to improve the cleaning performance.
 Solid State Phenomena Vol. 314 201

References
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[3] M. Hauptmann, et al, ECS Journal of Solid State Science and Technology 3 (2014), p. 2162-8769
[4] Alexander M. Kenis, et al, Ultrasound in medicine and biology 38, (2012), p. 99-108.
[5] S. Brems, et al, International symposium on cavitation, (2012) p. 236.
[6] H. Mitome, WCU, (2003), p.1231-1235.