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High-efficiency plasma surface modification of graphite-encapsulated magnetic nanoparticles

using a pulsed particle explosion technique

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2014 Jpn. J. Appl. Phys. 53 010205
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SELECTED TOPICS IN APPLIED PHYSICS

Japanese Journal of Applied Physics 53, 010205 (2014)

Interactions between Plasmas and Nano-Interfaces

http://dx.doi.org/10.7567/JJAP.53.010205

High-efciency plasma surface modication of graphite-encapsulated magnetic nanoparticles

using a pulsed particle explosion technique
Teguh Endah Saraswati1,2, Shun Tsumura3, and Masaaki Nagatsu1
1

Graduate School of Science and Technology, Shizuoka University, Hamamatsu 432-8561, Japan
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Surakarta 57126, Indonesia
3
Graduate School of Engineering, Shizuoka University, Hamamatsu 432-8561, Japan
2

Received July 17, 2013; accepted September 22, 2013; published online December 30, 2013
A high-efciency surface modication of graphite-encapsulated iron compounds magnetic nanoparticles using an inductively coupled radiofrequency plasma with a pulsed particle explosion technique was studied. A signicant increase in N 1s peak intensity in the X-ray photoelectron
spectroscopy spectra was obtained by applying a negative pulsed bias voltage of %1 kV to the substrate stage for 15 s or less at a repetition
frequency of 1 kHz and a duty ratio of 50% in ammonia plasma. The intensity of the N 1s peak and the N/C ratio of the nanoparticles treated in a
pulsed particle explosion system were 34 times higher than those of the particles treated without bias. The amino group population of
nanoparticles treated using the present technique was determined to be about 8.2 ' 104 molecules per nanoparticle, roughly four times higher than
that of particles treated without bias. The dispersion of the plasma-treated nanoparticles was signicantly improved compared with those of the
untreated and treated particles in the nonbiasing system. The surface structure analysis by transmission electron microscopy showed no
signicant damage on the structure or morphology of the treated nanoparticles, indicating that the present technique is applicable to the highefciency surface modication of magnetic nanoparticles. 2014 The Japan Society of Applied Physics

1.

Introduction

Recently, carbon-coated magnetic nanoparticles have attracted considerable interest in materials science research.
The incorporation of both metallic nanoparticles and carbon
in a stable coreshell system improves their advantageous
properties, which make them potentially applicable in various
applications such as magnetic data storage, magnetic uid,
magnetic inks,1) catalyst support,2) magnetic separation,
electrode, additives for many uses (i.e., as sintering agents
and propellants), conductive paste, conductive coating, and
biotechnological and biomedical applications.310)
Bare metallic nanoparticles have high reactivity and high
toxicity, which are limitations for realizing their practical
applications, such as instability under oxidation and degradation conditions (i.e., in acids). The other disadvantages are
their easy agglomeration and unsupported-surface structure
for providing functional group attachment for absorbing
appropriate molecules. Consequently, coating bare metalmagnetic nanoparticles with a protective shell is an
appropriate technique to overcome those limitations.
Compared with polymers and silica, carbon with the
graphite structure is a promising coating material for bioapplications because of its high stability at high temperature
and pressure, and in various chemical and physical environments (i.e., acid or base media). Moreover, the graphite shell
allows for further functionalization with specic functional
groups and biomolecules. Unfortunately, graphite-encapsulated magnetic nanoparticles conventionally prepared by
the arc-discharge method, generally disperse only in organic
solvents. This phenomenon makes them unsuitable for
bioapplications. To enhance nanoparticle biocompatibility,
surface modication processing has become a necessary
procedure before nanoparticles nd practical applications.
One of the efcient methods of surface modication
is plasma treatment, which has been commonly used for
many industrial applications. Plasma surface modication is
environmentally friendly with a short reaction time, and
provides various functional groups.11) Plasma processing can
markedly increase production if the system is optimized.

Recently, the plasma processing of magnetic materials has

drawn much attention with regard to nanoparticle surface
treatment for medical uses, such as drug delivery systems or
magnetic resonance imaging systems. There have been several
plasma reactor systems already developed for particle treatment, such as the bell jar reactor,12,13) downstream reactor,14)
rotary drum reactor,15) plasma uidized bed reactor,1618)
circulating bed reactor,19,20) plasma batch reactor,21) plasma
downer reactor,22) and plasma reactor with a mechanical
vibrator such as an electromagnet12) or a stirrer.13)
The purpose of these plasma systems is to interface
particles with plasma species. An efcient interaction
between the particle surface and the plasma is the key to
achieve the maximum surface modication. Early attempts to
improve the dispersion of pigment particles were carried out
using plasma techniques.23,24) In the case of polymer webs,
the entire surface is exposed to plasma using conventional
drum- or batch-type plasma reactors.25) However, such
plasma reactors are often unsuitable for particle materials
owing to the lack of solid mixing.26)
As described in our previous paper,27) we successfully
modied graphite-encapsulated iron compound magnetic
nanoparticles deposited on a silicon substrate with amino
groups using Ar and NH3 plasmas in successive stages. To
treat the particles homogeneously, they should be placed on
the sample stage such that they are dispersed as widely as
possible. When the placement of the particle sample is not
performed well, the uniform treatment of the entire bulk of
particles is difcult to achieve because the modication will
likely take place only on the top layers of the sample, that is,
particles inside the bulk will be less exposed to the plasma
than particles at the surface of the bulk.
To enhance the interaction between the particles and the
plasma, a modied setup is required. We consider that the
particle explosion technique enables an enhanced surface
interaction between the particle samples and the plasma
species. Therefore, in the present study, we developed a
plasma reactor for particle treatment to explode the particles
inside the chamber by a negative pulsed biasing of the sample
stage during the plasma processing.

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Fig. 1. (Color online) Schematic view of experimental setup: (1) quartz bell jar, (2) sample stage, (3) copper coil connected to the water cooling system,
(4) pressure gauge, (5) leaking valve, (6) gas inlet, (7) gas outlet connected to the turbo and rotary pump, and (8) biasing power supply. The black rectangle
represents the timeline of experimental stages during plasma processing; tp and tb represent the total time for plasma treatment and the initial time for biasing,
respectively.

2.
2.1

Experimental procedure
Nanoparticle fabrication and plasma processing
setup

Graphite-encapsulated iron compound magnetic nanoparticles

were prepared by the arc discharge method,28,29) which has
already been described in previous papers.27,30) The characteristics of the magnetic nanoparticles, such as magnetic properties or crystalline structures, have been described in a previous paper.30) Following nanoparticle synthesis, the nanoparticles are treated using a radio-frequency (RF) inductively
coupled plasma device. A schematic view of the chamber is
shown in Fig. 1. The stainless-steel chamber is 200 mm in
both diameter and height. The water-cooling copper pipe
helical antenna with a coil diameter of 100 mm and a pipe
diameter of 20 mm was wound around the quartz bell jar
(110 mm in outer diameter and 260 mm in height) mounted on
the stainless-steel chamber. The helical antenna was coupled
to an RF power generator at 13.56 MHz via a matching
network. The typical input RF power was about 80 W.
The chamber used in this work was modied by adding the
metal substrate for the sample stage inside the chamber. The
metal substrate of 10 mm diameter was attached to the center
of the glass dish placed at z = 2 cm (see Fig. 1), where
z = 0 is dened as the center of the helical antenna on its
axial axis. To conne the nanoparticles exploded by applying
bias, a glass tube with a diameter of 80 mm and a height of
60 mm was placed on the glass dish.
In the experiment, rstly, we put the particle sample (about
5 mg) on the metal substrate. The chamber was evacuated to a
base pressure of approximately 103 Pa. After the vacuum
evacuation, NH3 gas was introduced into the chamber and
kept at 50 Pa. During the plasma processing, the gate chamber
was closed to prevent the nanoparticles from owing to the
turbo pump system. The biasing conditions were as follows: a
substrate pulse biasing of 1 kV was applied at a repetition
frequency of 1 kHz and a duty ratio of 50%. The negative

pulsed bias voltage was turned on immediately after switching

the plasma on. Generally, it will take time to match the input
and reection powers before applying the pulsed bias to the
substrate. The bias time tb was varied from 0 to 60 s. After
biasing off, the plasma was kept turned on up to the desired
plasma treatment time tp of 10 min. The explosion of the
particles by applying pulsed biasing was visually observed
and recorded using a high-resolution digital camera (Nikon
D90) at a capture speed of 24 fps. The videos were then
processed using the software VirtualDub to add the timestamp
and obtain sequential images.
2.2

X-ray photoelectron spectroscopy and transmission

electron microscopy analysis

Following the plasma treatment, the samples were further

analyzed by X-ray photoelectron spectroscopy (XPS) performed using a Shimadzu ESCA-3400 with a Mg K X-ray
source and high-resolution transmission electron microscopy
(HR-TEM) performed using a JEM-2100F at an acceleration
voltage of 200 kV.
2.3

Estimation of amino group population

The amino group population of the plasma-treated nanoparticles was analyzed by the chemical derivatization method
using sulfosuccinimidyl 6-[3A(2-pyridyldithio)-propionamido] hexanoate (sulfo-LC-SPDP) according to the specic
chemical procedure.3133) The modied nanoparticles
(250 g) were suspended by bath sonication in 200 l of
10 mM sulfo-LC-SPDP in phosphate buffer saline (PBS) and
reacted for 30 min under light shielding conditions, repeating
the ultrasonication every 5 min. The treated nanoparticles
were washed three times with PBS through ultrasonication
and centrifugation and collected magnetically. The centrifugation was performed for 5 min with a gravitational force of
20,400g (14,000 rpm). The nanoparticles with sulfo-LCSPDP complexes were then reacted with 300 l of 20 mM
dithiothreitol (DTT) in PBS and reacted under light shielding

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Dispersion property
The nanoparticle dispersion before and after the plasma
treatment in both cases with and without the biasing system
was also observed. The observation was performed by
dispersing equal numbers of nanoparticles in the same
volume of distilled water by ultrasonication for about 5 min.

(a)

(c)

Intensity (arb. unit)

conditions, repeating the ultrasonication every 5 min. After a

15 min reaction, 5 min centrifugation at 20,400g (14000 rpm)
was performed and the cleavage product pyridine-2-thione
liberated from the sulfo-LC-SPDP present in the recovered
supernatant liquid, was determined by spectrophotometry
at 343 nm. The number of amino groups in 250 g of the
modied nanoparticles was quantitatively determined from
the calibration curve or by theoretical evaluation using the
extinction coefcient of pyridine-2-thione at 343 nm: 8.08
103 M1 cm1. The number of amino groups per nanoparticle
was calculated when the number of nanoparticles per gram
was 1.14 1014. This number was estimated by measuring
the ratio of the mass of the nanoparticles to their volume
under the assumption that the nanoparticles have a regular
spherical shape mainly of 20 nm diameter determined from
the nanoparticle size distribution taken by HR-TEM.27,30)

(b)

(d)

2.4

3.

Fig. 2. (a) Low- and (b) high-magnication TEM images of the graphiteencapsulated iron compound nanoparticle successfully fabricated by arc
discharge, (c) energy-dispersive X-ray spectra of the synthesized
nanoparticles, and (d) magnied image showing the interplanar distance of
graphite coating and iron core.

Results and discussion

The present study was started by preparing nanoparticle

samples by the arc discharge method. The TEM images and
EDS proles of successfully fabricated nanoparticles are
shown in Fig. 2. Using TEM, we conrmed that iron compound magnetic nanoparticles are clearly encapsulated by
graphitic carbon. This result shows good agreement with the
EDS proles of the selected particles that reveal at least three
possible phases: particles that exhibit the presence of O, Fe,
and C. The interplanar distances of the graphite lattice and
iron fringes are about 0.34 and 0.202 nm, respectively.
Following the nanoparticle fabrication, we placed nanoparticle samples (about 5 mg) on the metal substrate of the
sample holder located at the center of the glass dish. After
applying a pulse bias with a voltage of 1 kV, a frequency of
1 kHz, and a duty ratio of 50%, the particles were exploded,
as shown in the successive images in Fig. 3. These sequential
images were captured during the pulsed biasing. The rst
image (left top) in Fig. 3 shows the condition before starting
the experiment (plasma OFF). The next image shows the
situation just after turning the plasma on. Then, it generally
took time to produce a stable plasma. Until the time of
turning the bias on, the sample particles are still in the metal
stage. Plasma generation will be easily achieved if the
matching is adjusted at the desired power beforehand. The
shorter time interval for turning on the bias provides an
effective interaction between the plasma and the particle
sample because the lifetime of an NH2 radical is short (a few
microseconds).3436) The lifetime of these plasma species is
important because we used the no-ow gas condition, that is,
the chamber gate valve was closed during plasma treatment,
maintaining a pressure at 50 Pa. The negative pulsed bias
voltage was turned on about 11.4 s after turning on the
plasma. At the biasing-on time, the particles started to
explode and dropped back to the substrate stage after half
a second. After a certain biasing time (called tb), the bias
voltage was turned off, but the plasma treatment was con-

Fig. 3. (Color online) Time-sequential images of particle-explosion event

during biased-plasma processing.

tinued without biasing up to the desired treatment time tp. For

clarity, red dashed lines are added in the pictures to show
when and how the particles began to y and ended up.
In Fig. 4, we summarized the phenomenon observed in
Fig. 3 as the temporal behavior of the height changes of the

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Intensity (arb. unit)

Jpn. J. Appl. Phys. 53, 010205 (2014)

exploding particles, at tb = 15 s and tp = 3 min. The height of

the exploding particles was measured as the highest position
taken from each image frame. The inset gure shows a
magnied view of the peak area. The letters shown in Fig. 4
denote the main events. A and B represent the timer ON
and plasma ON, which correspond to the rst (0.000 s) and
second (0.417 s) images in Fig. 3, respectively. C represents
the time when the biasing was turned on, shown in the fourth
image (11.791 s) in Fig. 3. The gap between B and C
indicates the time required for the impedance matching
between the RF source and the plasma. The particles started
to explode at C, reached their maximum height at D
(12.125 s), and ended up at E (12.5 s). F represents the time
when the bias was turned off after 15 s of having the bias
turned on, and G represents the time when the plasma was
switched off after 180 s (3 min).
The explosion event is explained by the ion bombardment
mechanism. After turning on the biasing, the pulsed negative
high voltage caused a high electric eld in the sheath between
the plasma and the substrate. The existence of a high electric
eld caused the ions in the plasma to accelerate toward
the substrate where the particles were placed. Because the
particles were placed on the stage in powder form, once
the powder was bombarded by plasma ions, the particles
spontaneously popped out and exploded upwards in a very
fast manner. This phenomenon is similar to a conventional
ion sputtering event. The ion bombardment energy depends
on the difference in potential between the plasma and the
substrate (V = Vp Vsub) and is subsequently expressed as
e(Vp Vsub). In this study, if the estimated plasma potential
Vp is more or less on the order of 10 V, the ion bombardment
energy when biasing is turned on is approximately 1 keV,
estimated from a biasing voltage of 1 kV. This proposed
mechanism also enables agglomerated nanoparticles to
separate into ne particles during the explosion process. By
using a small (diameter 10 mm) metal substrate with a high
negative voltage, the particles explode and do not return back
to the substrate but fall on the glass dish area surrounding the
metal substrate owing to gravitational force. The dynamic
behavior of the particles and the forces acting on them under
biasing have been discussed in several papers,3741) which are
beyond the scope of our present paper.

Intensity (arb. unit)

Fig. 4. (Color online) Explosion height vs plasma treatment time under

experimental conditions of tb = 15 s; tp = 3 min. A: timer ON. B: plasma
ON. C: bias ON, explosion starts. D: maximum height of explosion event.
E: explosion ends. F: bias OFF. G: plasma OFF.

Fig. 5. (Color online) Comparison of N 1s XPS proles for various

plasma-treatment times (tp = 0, 1, 2, 3, 6, 8, 10, 15, and 30 min) and biasing
times (tb = 0, 2, 15, 30, and 60 s).

After the plasma treatment, the treated particles were

characterized by XPS. Figure 5 shows the data set of the
N 1s peak of the XPS proles with various biasing times tb
referred to as the C F range (see Fig. 4). The observed
N 1s peaks located at approximately 399.8 eV are considered
as a signal of the nitrogen-containing group for the amino
group, which was successfully grafted on the surface.
Figure 5 shows the N 1s spectra at different biasing times
of tb = 0 (no biasing), 2, 15, 30, and 60 s, each of which was
obtained for various plasma treatment times tp of up to
30 min. Comparing the biasing system with the nonbiasing
system (tb = 0 s), the intensity of the N 1s peak of the biasing
system (tb = 2, 15, 30, and 60 s) is signicantly increased.
For example, the intensity of the N 1s peak of the nanoparticles treated in the biasing system (tb = 15 s) is raised to
about 34 times higher than those in the nonbiasing system
(tb = 0 s) for short plasma treatment times tp of up to 3 min.
This indicates that the plasma treatment with applied biasing
had a signicant effect of increasing N 1s peak intensity.
These increases in the N 1s peak intensity are supposed to be
due to the enhancement of the efcient interaction between
the particles and the plasma species, particularly nitrogencontaining species, during an explosion event.

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N/C ratio (%)

15s

60s

30s

t b=2s
2

no bias
0

4
6
8
Treatment time t p (min)

10

Fig. 6. (Color online) Comparison of N/C atomic ratios as a function of

plasma treatment time for different biasing times.

To discuss the XPS prole in more detail, we compare the

atomic concentration of nitrogen to the atomic concentration
of carbon in terms of the N/C ratio shown in Fig. 6. The N/C
ratios of the ve data sets with tb = 0, 2, 15, 30, and 60 s are
shown in sequence on comparable scales. Each data set was
obtained for various plasma treatment times within 30 min.
Figure 6 shows that all the data sets have similar behaviors.
The N/C ratio steeply increased within a treatment time tp
range of 23 min, reached their saturation values, and then
decayed slightly thereafter. Comparing the powders with and
without a biasing event, the N/C ratios of the nonbiasing
(tb = 0 s) and biasing (tb > 0 s) systems were signicantly
different. For example, the N/C ratio of the nonbiasing system was only about 2.6% (tb = 0 s, tp = 3 min), but that
for the biasing system increased to be about 7% (tb = 15 s,
tp = 3 min), which became the maximum N/C ratio. Note
that the results of the N/C ratios indicate roughly similar
trends to those of N 1s peak intensities shown in Fig. 5. The
present results are very analogous to our previous results
of amino group introduction into the polymer surface using
low-pressure microwave NH3 plasma.42) The N/C ratio is
maximum at a short plasma treatment time of 30 s and then
decreases owing to the surface damage by ion bombardment
and/or the hydrogen etching effect as treatment time
increases.
From Figs. 5 and 6, note that the short plasma treatment
times of about 35 min are suitable for achieving the nearly
maximum N/C ratio of 6% for various biasing times
of 230 s. In the present study, we obtained almost the
same results for the maximum N/C ratio, roughly 6%
for different biasing times. These results suggest that the
powders exploded by applying the negative pulsed bias were
essential to improve the N/C of the particles.
To quantitatively evaluate the absolute values of the
number of amino groups grafted to the graphite-encapsulated
iron composite nanoparticles, we have performed a conventional chemical derivatization reaction method using sulfosuccinimidyl 6-[3A(2-pyridyldithio)-propionamido] hexanoate
(sulfo-LC-SPDP).31,32) Details of the derivatization steps are
presented in the experimental section.
For the amino group derivatization, we examined three
samples: (a) untreated nanoparticles, (b) treated particles in
the nonbiasing system (tb = 0 s; tp = 3 min), and (c) treated

Fig. 7. Amino group population of samples of (a) untreated nanoparticles

(tb = 0 s; tp = 0 min), (b) treated nanoparticles in nonbiasing system (tb = 0 s;
tp = 3 min), and (c) treated nanoparticles in biasing system (tb = 15 s;
tp = 3 min). The inset image shows the dispersion of the representative
sample.

nanoparticles in the biasing system (tb = 15 s; tp = 3 min),

shown in Fig. 7. The latter represented the sample that has
the highest N/C ratio among all the samples. The amino
group analysis gave results showing that no absorbance was
observed at 343 nm for the untreated nanoparticles, indicating
that no amino groups were grafted groups to the surface of
pristine graphite-encapsulated iron composite nanoparticles.
On the other hand, a very large number of amino groups were
obtained from the plasma-treated samples. The populations of
amino groups for the treated nanoparticles under the experimental conditions of (tb = 0 s, tp = 3 min) and (tb = 15 s,
tp = 3 min) were estimated to be about 1.9 104 and 8.0
104 molecules per particle, respectively. The present results
also indicate the efcient enhancement of amino group
modication by roughly fourfold by the negative pulsed
biasing during the NH3 plasma processing.
Furthermore, to conrm the NH3 plasma effect on the
hydrophilicity, we examined the dispersion of the nanoparticles in water, the results of which are shown in Fig. 7.
Comparing three vials with the same amount of particles (i.e.,
a, b, and c), we observed signicant differences. As shown in
Fig. 7, the dispersion of the nanoparticles is signicantly
improved after the plasma treatment. The untreated nanoparticles (a) did not disperse in water, and all of the nanoparticles remained on the top surface of the water. However,
the dispersion of the nanoparticles treated in the biasing
system (c) is better than those treated in the nonbiasing
system (b). This can be observed by looking at the dark color
of the solution, which corresponds to the dispersed nanoparticles in water. The improvement in the dispersion of the
treated nanoparticles in the biasing system is assumed to be
caused by the optimum interaction between NH3 plasma and
nanoparticles. The explosion event in the biasing system
allows the amino group to attach not only to a portion but
also to the entire nanoparticle surface. Consequently, the
hydrophilicity of the nanoparticles after plasma treatment
greatly improved because a wider surface area of the nanoparticles is available for grafting by amino groups. The amino
groups on the outmost graphite layer are likely to play a key
role in enhancing the hydrophilicity.
Figure 8 shows an illustration of the interaction of water
molecules with the aminated surface of the nanoparticles. The
grafted amino group can bind water molecules through

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Fig. 8. (Color online) Illustration of interaction between water molecules and amino group grafted onto the outmost portion of graphite layer of
nanoparticles.

Fig. 9. TEM images of plasma-treated nanoparticles observed at low and high magnications under various experimental conditions: (a) tb = 0 s; tp = 3 min;
(b) tb = 2 s; tp = 3 min, (c) tb = 15 s; tp = 3 min, (d) tb = 30 s; tp = 3 min, (e) tb = 60 s; tp = 3 min, and (f ) tb = 15 s; tp = 30 min.

intermolecular forces such as dipoledipole forces and hydrogen bonds, as shown by the yellow line in Fig. 8. The larger
number of amino groups may allocate more areas for
attracting more water molecules, which contributes to the
improvement in the dispersion property of the nanoparticles.

HR-TEM was also used to analyze the damaging effects on

the morphological and structural properties of the nanoparticles before and after plasma treatment. Figure 9 shows
images of the plasma-treated nanoparticles observed by HRTEM in low and high magnications. (a) to (f ) correspond

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to the treated nanoparticles under various (tb, tp) conditions

of (0 s, 3 min), (2 s, 3 min), (15 s, 3 min), (30 s, 3 min),
(60 s, 3 min), and (15 s, 30 min). All of the images conrm that
no damage or destruction was induced in the nanoparticle
structure after performing the plasma treatment in the
nonbiasing or biasing system. The structure of the graphite
layers was found to be stable under all the experimental
conditions. Similarly to the graphite coating, the iron compound core also remained encapsulated inside the graphite
layers even when the particles were subjected to long-term
plasma treatment, as shown in Fig. 9(f ). This result indicates
that the pulsed-biasing particle explosion technique performed in the present study is highly efcient in amino group
functionalization. Furthermore, it is also suitable for surface
modication, particularly for powder samples because of its
ability to retain the structural stability of nanoparticles.
4.

Conclusions

The surface of graphite-encapsulated iron compound magnetic nanoparticles fabricated by arc discharge was successfully modied by a pulsed particle explosion technique. This
technique was performed by applying a high negative bias of
1 kV to the substrate stage for 260 s at a repetition frequency of 1 kHz and a duty ratio of 50% in ammonia plasma
generated using a radio frequency inductively coupled
plasma device. The intensity of the N 1s peak in the XPS
spectrum of the nanoparticles treated in the biasing system
was three to four times higher than that treated in the
nonbiasing system owing to the enhancement of the interaction between the nanoparticles and the plasma species. The
present results also indicate the efcient enhancement of
amino group modication by approximately fourfold from
about 1.9 104 molecules/nanoparticle in the case of
(tb = 0 s, tp = 3 min) to 8.2 104 molecules/nanoparticle
in the case of (tb = 15 s, tp = 3 min) by the negative pulsed
biasing during the NH3 plasma processing. Moreover, the
results also showed that the dispersion of the treated nanoparticles in biasing system was improved compared with
those of the untreated and treated samples in the nonbiasing
system.
In addition, analysis by HR-TEM showed no signicant
damage on the nanoparticle structures, indicating that the
present technique is suitable mainly for the surface modication of particle samples owing to its high efciency in
surface modication without causing any signicant change
or destruction of the structural and morphological properties.
Acknowledgments

This work was supported in part by a Grant-in-Aid for

Scientic Research (No. 2110010) from the Japan Society for
the Promotion of Science (JSPS). The authors would like to
thank Associate Professor A. Ogino of Shizuoka University
for technical assistance in the plasma chamber development
and UVvis absorption spectroscopy measurement.

1) M. E. McHenry, S. A. Majetich, and E. M. Kirkpatrick, Mater. Sci. Eng. A

204, 19 (1995).

2) L. Kong, X. Lu, X. Bian, W. Zhang, and C. Wang, ACS Appl. Mater.

Interfaces 3, 35 (2011).
3) G. Pastorin, Pharmacol. Res. 26, 746 (2009).
4) Q. A. Pankhurst, N. T. K. Thanh, S. K. Jones, and J. Dobson, J. Phys. D 42,
224001 (2009).
5) Q. A. Pankhurst, J. Connolly, S. K. Jones, and J. Dobson, J. Phys. D 36,
R167 (2003).
6) A.-H. Lu, E. L. Salabas, and F. Schth, Angew. Chem., Int. Ed. 46, 1222
(2007).
7) S. Kim, E. Shibata, R. Sergiienko, and T. Nakamura, Carbon 46, 1523
(2008).
8) A. Ito, M. Shinkai, H. Honda, and T. Kobayashi, J. Biosci. Bioeng. 100, 1
(2005).
9) C. C. Berry and A. S. G. Curtis, J. Phys. D 36, R198 (2003).
10) C. C. Berry, J. Phys. D 42, 224003 (2009).
11) C. Chen, A. Ogino, X. Wang, and M. Nagatsu, Appl. Phys. Lett. 96, 131504
(2010).
12) A. B. Garca, A. Martnez-Alonso, C. A. Leon y Leon, and J. M. D. Tascn,
Fuel 77, 613 (1998).
13) J. P. Boudou, A. Martinez-Alonzo, and J. M. D. Tascon, Carbon 38, 1021
(2000).
14) D. Shi and P. He, Rev. Adv. Mater. Sci. 7, 97 (2004).
15) V. Brser, M. Heintze, W. Brandl, G. Marginean, and H. Bubert, Diamond
Relat. Mater. 13, 1177 (2004).
16) F. Bretagnol, M. Tatoulian, F. Are-Khonsari, G. Lorang, and J. Amouroux,
React. Funct. Polym. 61, 221 (2004).
17) F. Are-Khonsari, M. Tatoulian, F. Bretagnol, O. Bouloussa, and F.
Rondelez, Surf. Coatings Technol. 200, 14 (2005).
18) M. Tatoulian, F. Brtagnol, F. Are-Khonsari, J. Amouroux, O. Bouloussa,
F. Rondelez, A. J. Paul, and R. Mitchell, Plasma Processes Polym. 2, 38
(2005).
19) S. H. Jung, S. H. Park, D. H. Lee, and S. D. Kim, Polym. Bull. 47, 199
(2001).
20) S. H. Jung, S. H. Park, and S. D. Kim, J. Chem. Eng. Jpn. 37, 166 (2004).
21) J.-W. Kim, Y.-S. Kim, and H.-S. Choi, Korean J. Chem. Eng. 19, 632
(2002).
22) C. Arpagaus, A. Rossi, and P. Rudolf von Rohr, Appl. Surf. Sci. 252, 1581
(2005).
23) T. Ihara, S. It, and M. Kiboku, Chem. Lett. 15, 675 (1986).
24) K. Tsutsui, K. Nishizawa, and S. Ikeda, J. Coatings Technol. 60, 107
(1988).
25) M. R. Wertheimer, H. R. Thomas, M. J. Perri, J. E. Klemberg-Sapieha, and
L. Martinu, Pure Appl. Chem. 68, 1047 (1996).
26) C. Arpagaus, Dr. Thesis, Swiss Federal Institute of Technology Zurich,
Zurich (2005).
27) T. E. Saraswati, T. Matsuda, A. Ogino, and M. Nagatsu, Diamond Relat.
Mater. 20, 359 (2011).
28) M. Nagatsu, T. Yoshida, M. Mesko, A. Ogino, T. Matsuda, T. Tanaka, H.
Tatsuoka, and K. Murakami, Carbon 44, 3336 (2006).
29) Y. Saito, T. Yoshikawa, M. Okuda, N. Fujimoto, S. Yamamuro, K. Wakoh,
K. Sumiyama, K. Suzuki, A. Kasuya, and Y. Nishina, Chem. Phys. Lett.
212, 379 (1993).
30) T. E. Saraswati, A. Ogino, and M. Nagatsu, Carbon 50, 1253 (2012).
31) J. Carlsson, H. Drevin, and R. Axn, Biochem. J. 173, 723 (1978).
32) G. Hermanson, Bioconjugate Techniques (Academic Press, New York,
2008) 2nd ed., p. 277.
33) B. Yoza, A. Arakaki, and T. Matsunaga, J. Biotechnol. 101, 219 (2003).
34) X.-Y. Gong, X. R. Duan, H. Lange, and A. A. Meyer-Path, Chin. Phys. Lett.
18, 939 (2001).
35) E. R. Fisher, Plasma Processes Polym. 1, 13 (2004).
36) A. Fateev, F. Leipold, Y. Kusano, B. Stenum, E. Tsakadze, and H. Bindslev,
Plasma Processes Polym. 2, 193 (2005).
37) T. Moriya, M. Shimada, K. Okuyama, and H. Setyawan, Jpn. J. Appl. Phys.
44, 4871 (2005).
38) C. M. Tico, A. Dyson, and P. W. Smith, Plasma Sources Sci. Technol. 13,
395 (2004).
39) J. Liu, D. Wang, T. C. Ma, Y. Gong, Q. Sun, J. X. Ma, and C. X. Yu, Phys.
Plasmas 6, 1405 (1999).
40) V. E. Fortov, A. V. Ivlev, S. A. Khrapak, A. G. Khrapak, and G. E. Morll,
Phys. Rep. 421, 1 (2005).
41) H. Kersten, H. Deutsch, E. Stoffels, W. W. Stoffels, and G. M. W. Kroesen,
Int. J. Mass Spectrom. 223224, 313 (2003).
42) M. Krl, A. Ogino, and M. Nagatsu, J. Phys. D 41, 105213 (2008).

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2014 The Japan Society of Applied Physics

SELECTED TOPICS IN APPLIED PHYSICS

Jpn. J. Appl. Phys. 53, 010205 (2014)

Teguh Endah Saraswati is currently a Lecturer and
Researcher in Chemistry Department, Mathematics
and Natural Sciences Faculty, Sebelas Maret University, Indonesia. She received Master of Science
degree in chemistry from Nagoya University in
2009, which was supported by Panasonic Scholarship Program. In 2012, she completed the doctoral
program, which was partly supported by Amano
Foundation Scholarship. She obtained Ph. D degree
at Nanovision Technology Department, Graduate
School of Science and Technology, Shizuoka University under the
supervision of Prof. Masaaki Nagatsu. Her research interests are inorganic
and materials chemistry, and surface modication by plasma processing.

Shun Tsumura received the B.S. and M.S. degrees in electrical engineering
from Shizuoka University in 2011 and 2013, respectively. During his
bachelor and master courses, he engaged in the study of surface modication
of magnetic nanoparticles by using an RF excited inductively coupled
plasma under the supervision of Prof. Masaaki Nagatsu.
Masaaki Nagatsu received the B.S., M.S., and Dr.
Eng. Degrees from Nagoya University in 1975,
1979, and 1985, respectively. During 1975 to 1976,
he worked for Hitachi Research Laboratory, Hitachi,
Ltd. From 1982 to 2000, he was an assistant
professor (19821989), lecturer (19901991), and
associate professor (19912000) in the Department
of Electrical Engineering of Nagoya University.
During 19871989, he worked as a visiting
researcher in University of California, Los Angeles.
In 2001, he became a professor of Department of Engineering in Shizuoka
University. He became a Director of Graduate School of Science and
Technology, Research Division in 2006 and a Dean of Graduate School of
Science and Technology of Shizuoka University since 2008. His research
eld is the plasma production and surface modication of materials for biomedical and environmental application.

010205-8

2014 The Japan Society of Applied Physics