Japanese Journal of Applied Physics

Vol. 44, No. 35, 2005, pp. L 1134–L 1137

#2005 The Japan Society of Applied Physics

Metal Deposition Deep into Microstructure by Electroless Plating

Nobuyuki TAKEYASU1
, Takuo TANAKA1 and Satoshi K AWATA1;2
1
Nanophotonics Laboratory, RIKEN (The Institute of Physical and Chemical Research), 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
2
Department of Applied Physics, Osaka University, Suita, Osaka 565-0871, Japan
(Received April 27, 2005; accepted July 11, 2005; published August 19, 2005)

It is generally difficult to deposit metal on an occluded part of a structure or inside a long tubular structure. In this paper, we
report an electroless plating method that is useful for metal deposition onto internal obscured regions of a complex structure,
and we show that the technique can deposit metal over a wide area. We demonstrate gold deposition inside a capillary tube
and a complex concave structure of micrometer scale consisting of polystyrene microbeads sandwiched between glass plates.
[DOI: 10.1143/JJAP.44.L1134]
KEYWORDS: electroless plating, metal coating, 3D microstructure, gold, silver, latex beads

Metal microfabrication has been actively studied and used

in various fields because of the unique optical, electrical, and
catalytic properties of the fine structures that it can
produce.1–6) The ability to simultaneously and precisely
fabricate a number of micro-objects over a wide region is
essential to the practical application of nanotechnology. In
these processes, plating methods are occasionally used for
metal deposition. Plating is a conventional method of
depositing metal onto substrates,7) and can be used not only
with conductors, but also with insulators such as plastics and
ceramics. Among known plating techniques, electroless
plating is commonly used for metal deposition on insulators
Fig. 1. Transmission spectra of gold-deposited polystyrene plate from 300
because it does not require any external electric field. to 800 nm at different reaction times.
Electroless plating is chemically performed with a solution,
and it results in a uniform metal deposition over the entire
surface area of micro-objects.8–10) With this method, it is measuring the transmission spectrum. We prepared
possible to deposit metal effectively even though the area is 0.024 M tetra-chloro auric acid (HAuCl4 ), 0.75 M sodium
limited to less than a micrometer in width.11,12) Moreover, a hydroxide (NaOH), and 0.086 M sodium chloride (NaCl) in
number of micrometer-scale metal patterns can be fabricated water as a gold ion solution, and 0.5 vol % glycerol
simultaneously over a very wide area much more easily than (C3 H8 O3 ) in water as a reduction agent. Samples were
with sputtering or vacuum evaporation, which require large, obtained by terminating the reaction at 9, 12, 15, and 18 min
complex equipment. These techniques have been long from mixing the plating solution and the reduction agent.
studied, and are used widely for metal fabrication processes. The transmission spectra were measured from 300 to 800 nm
However, it is generally very difficult, using these methods, for these samples by an absorptiometer (Shimadzu, UV-
to deposit metal on a deep or normally occluded part of a 2500PC), and are shown in Fig. 1. For reaction times of less
structure, such as the inner wall of a long tubular structure. than 9 min, no noticeable deposition of gold was observed. A
In this letter, we demonstrate electroless plating on three region with a lower transmission compared to the others was
types of structure. First, gold was deposited on the inner wall found from 500 to 600 nm; this was due to the local
of a fused-silica capillary, which is difficult to achieve by plasmon-mode resonance absorption of gold particles.13) The
other methods. Second, silver was deposited onto glass resonance absorption became more noticeable at 12 min. The
beads. Third, gold was deposited inside a complex concave total transmittance decreased as the reaction time increased,
structure formed by polystyrene microbeads sandwiched and a red shift of the absorption peak was observed as the
between glass plates. reaction time increased. This implies that the gold particle
As mentioned above, although it is generally difficult to size also increased with reaction time. A suitably reflective
coat metals onto the inside of a concave structure using other gold mirror was formed on the polystyrene substrate after
methods (such as vacuum evaporation and sputtering), with 18 min, as indicated by the fact that incident light was almost
electroless plating the plating solution containing metal ions completely reflected by the deposited gold film. Moreover,
naturally goes into the inside of even a fine, complex the deposited gold was strongly fixed to the polystyrene
structure, and therefore all surfaces contacting the plating substrate.
solution are uniformly coated with metal. As a first demonstration, gold was deposited onto the
To determine the main features of our process and to inner wall of a fused-silica capillary tube (Agilent Tech-
verify its effectiveness, we first investigated the relationship nologies, outer diameter = 0.150 mm). The tubes were
between the amount of gold deposited onto the surface of a coated with polyimide, and then the polyimide was removed
polystyrene substrate at room temperature (295 K) by from the middle of the tubes with a flame to form plating
areas for observation with the optical microscope.


E-mail address: ntakeyasu@[Link] We prepared a 100-mm-long capillary with an inner

L 1134
Jpn. J. Appl. Phys., Vol. 44, No. 35 (2005) N. T AKEYASU et al. L 1135

Fig. 2. (a) Inner wall of fused-silica capillary was coated by gold. The reddish area is the gold-coated part. The inner diameter of the
capillary tube is 50 mm. (b) Silver-coated glass beads observed by SEM. The diameter of the beads is about 100 mm.

diameter of 50 mm. In the case of glass surface, gold containing the beads was then dripped onto a glass slide. The
adhesion was much worse compared to the polymer case. beads were naturally arranged in a hexagonal pattern after
Therefore, the glass surface for gold deposition was pre- drying. Subsequently, the beads were sandwiched by another
treated by a mixed solution of 26 mM SnCl2 and 70 mM glass slide, placed in a furnace for 10 min at 388 K, which
trifluoroacetic acid in water.14) One end of the capillary was exceeds the glass transfer temperature of polystyrene
dipped in a mixed solution of the gold plating solution and (378 K), and pressed. The resulting structure is shown in
the reduction agent. The inner space of the capillary tube Fig. 3(a).
was naturally filled with the solution due to, and gold was Deformation of the polystyrene beads resulted in disk
uniformly deposited on the inner surface. The capillary tube shapes, and the flat surfaces at the top and bottom were
was removed from the solution after 30 min, rinsed, and completely attached to the slide glasses on both sides.
observed with an optical microscope (Nikon OPTIPHOTO). Because of this phenomenon, it is usually impossible to
Figure 2(a) shows a photomicrograph of a gold-coated obtain gold deposition at regions where the beads adhere to
capillary tube obtained with the optical microscope. The the slide glass. However, the PS beads do not become
inside of the capillary tube became red in color, which was completely flat; there are very small, narrow spaces between
obviously different from the color of the outer tube. This the beads, and these can be used as a template for metal
indicates that gold particles were deposited inside the patterning, as shown schematically in Fig. 3(b). The mixed
capillary tube. The gold coating was found over a length solution of the gold plating solution and the reduction agent
of several tens of millimeters. was impregnated into these spaces after the pretreatment of
Although a 50-mm capillary tube was used here, this glass surface with SnCl2 –trifluoroacetic acid mixed solu-
electroless plating method may also be useful for metal tion.14) The spaces became filled with the solution, and
coating on the interior of concave fine structures, even uniform gold deposition was readily obtained after 15 min;
though their scale is typically less than a micrometer. this is shown in Fig. 3(c).
Additionally, this method is also useful for metal coating It was previously reported that metal deposition onto a
over areas that are more than a millimeter wide. Since metal glass substrate using polymer latex beads and sputtering
deposition occurs in places where the plating solution is in resulted in the fabrication of a number of triangles arranged
contact with the substrate, a relatively large area can be in a hexagonal pattern.15) In our experiment, since metal
deposited with metal simultaneously, which is crucial for deposition was obtained at surfaces in contact with the
nanoengineering applications. plating solution, metal was able to be deposited on all the
As a second demonstration, we showed that silver could regions of the substrate underneath the polystyrene beads
be successfully deposited onto glass beads with a diameter except for the contact plane. However, areas where no
of 100 mm. For silver deposition, we prepared 0.2 M silver deposition occurred were also found; these may be caused
nitrate (AgNO3 ) in water, and 1.9 M glucose (C6 H12 O6 ) in a by the beads deforming so as to join together, forming a flat
solution of 30 vol % methanol (CH4 O) and 70 vol % water as sheet that impedes the passage of the plating solution. That
a reduction agent.9) It is relatively difficult to deposit metal is, the spaces between the aggregated beads were filled with
uniformly onto a round shape; however, a uniform silver polystyrene through the deformation, and this polystyrene
coating was readily obtained using our method. Glass formed continuous layers in these areas. The thickness of the
microbeads were mixed in a silver plating solution and deformed beads was estimated to be from 15 to 20 mm,
were gently agitated during the reaction. The beads were which was obtained by a 45 tilted SEM observation.
surrounded by the solution and silver was then uniformly On the same slide glass, another gold pattern was found,
deposited onto the beads. A scanning electron micrograph which was much finer than the one described above. A
(SEM) of the silver-coated glass beads is shown in Fig. 2(b). reflection image from the optical microscope is shown in
As a third demonstration, gold was deposited onto a finer, Fig. 4(a). A number of gold rings arranged in a hexagonal
more complex structure containing polystyrene beads (Duke pattern and irregularly connected by thin lines were found
Scientific, D ¼ 49:8  0:8 mm, 4250A). The polystyrene over a wide area. It was difficult to control the number of
beads were first dispersed in water (1.0 vol %). The water lines emerging from a ring. The inner diameter of the gold
L 1136 Jpn. J. Appl. Phys., Vol. 44, No. 35 (2005) N. TAKEYASU et al.

Fig. 3. (a) Transmission microscope image of crushed polystyrene beads. (b) Gold deposition process. The shaded part was filled by
the gold plating solution. The polystyrene beads acted as a template, and a gold pattern was obtained. (c) Transmission microscope
image of gold pattern fabricated by beads.

Fig. 4. (a) Reflection microscope image of finer gold pattern formed on glass plate. (b) Reflection microscope image of pattern formed
on the glass plate and removed from polystyrene bead layer before gold deposition. (c) SEM image of 45 -tilted polystyrene template
used for gold patterning.

rings was about 10 mm, and the distance between the centers We considered the possibility that this fine pattern was
of the rings was about 50 mm, which is almost the same as also formed as a result of spaces between the beads and the
the diameter of the spherical polystyrene beads. The size of glass slide. To confirm this, the glass slide used to compress
the inner, non deposited areas varied, although the outer the beads and the crushed beads were observed before gold
diameters were almost constant at 30 mm. Therefore, the deposition. The same pattern of rings connected by lines was
width of the gold rings was not constant, which may be due observed on the glass slide that was removed from the layer
to irregularities in the polystyrene bead template. of beads, as shown in Fig. 4(b). From this image, we
Jpn. J. Appl. Phys., Vol. 44, No. 35 (2005) N. T AKEYASU et al. L 1137

assumed that the same pattern would exist on the beads. The patterning, we believe that the most advantageous applica-
surface of the layer of beads was observed by SEM and the tion of our electroless plating may be to three-dimensional
result is shown in Fig. 4(c). The same pattern was found metal microfabrication.
there, as expected. Therefore, we can infer that the pattern
on the beads was transcribed onto the slide glass, thus acting
as a template for this patterning. The width of the lines 1) G. M. Whitesides and B. Grzbowski: Science 295 (2002) 2418.
2) Q. Guo, C. Arnoux and R. E. Palmer: Langmuir 17 (2001) 7150.
connecting each ring was found to be approximately 1 mm,
3) M. C. Netti, S. Coyle, J. J. Baumberg, M. A. Ghanem, P. R. Birkin,
which is much finer and more complex than that of the P. N. Batlett and D. M. Whittaker: Adv. Mater. 13 (2001) 1368.
previous gold pattern. It is noted that fine, complex metal 4) K. R. Brown and M. J. Natan: Langmuir 14 (1998) 726.
patterns with a scale of about one micrometer can be readily 5) F. Caruso and M. Spasova: Adv. Mater. 13 (2001) 1090.
obtained by electroless plating. 6) Z. Chen, P. Zhan, Z. Wang, J. Zhang, W. Zhang, N. Ming, C. T. Chan
and P. Sheng: Adv. Mater. 16 (2004) 417.
Looking to the future, this electroless plating method may
7) G. O. Mallory and J. B. Hajdu: Electroless Plating: Fundamentals and
be a strong tool for metal coating or metal fabrication in Applications (American Electroplaters and Surface Finishers Society,
nanoengineering applications. The advantage of this method Orlando, FL, 1990) Chap. 1.
is not only a uniform metal deposition onto surfaces of 8) S. Hrapovic, Y. Liu, G. Enright, F. Bensebaa and J. H. T. Luong:
complex structures, but also the ability to fill metal into Langmuir 19 (2003) 3958.
9) Y. Saito, J. J. Wang, D. N. Batchelder and D. A. Smith: Langmuir 19
narrow spaces of complex structures over a wide region.
(2003) 6857.
Moreover, the metal deposition can be controlled by 10) A. A. Antipov, G. B. Sukhorukov, Y. A. Fedutik, J. Hartmann,
adjusting the reaction conditions, including the concentra- M. Giersig and H. Möhwald: Langmuir 18 (2002) 6687.
tion of the plating solution and the reduction agent, the 11) P. C. Hidber, W. Helbig, E. Kim and G. M. Whitesides: Langmuir 12
temperature, and the reaction time. Therefore, these con- (1996) 1375.
12) C. J. Moran, C. Radloff and N. J. Halas: Adv. Mater. 15 (2003) 804.
ditions should be carefully optimized for the target appli-
13) T. Okamoto, I. Yamaguchi and T. Kobayashi: Opt. Lett. 25 (2000) 372.
cation, according to the desired pattern size, type of 14) V. P. Menon and C. R. Martin: Anal. Chem. 67 (1995) 1920.
substrate, and other factors. 15) J. C. Hulteen and R. P. Van Duyne: J. Vac. Sci. Technol. A 13 (1995)
Although this method can be used for fine metal 1553.