Materials Transactions, Vol. 59, No. 7 (2018) pp.

1198 to 1205
© 2018 The Japan Institute of Metals and Materials

Formation of Multiscale Protrusions on Commercially Pure Titanium and

Stainless Steel by Two-Stage Sputter Etching Using Different Cathode Disks
Keijiro Nakasa1,+, Akihiro Yamamoto2, Takashi Kubo3,
Rongguang Wang4 and Tsunetaka Sumomogi3
1
High-Tech Research Center, Hiroshima Kokusai Gakuin University, Hiroshima 739-0321, Japan
2
Asahi Surface Tec LLC, Higashi-Hiroshima 739-0024, Japan
3
Department of Manufacturing Engineering, Faculty of Engineering, Hiroshima Kokusai Gakuin University,
Hiroshima 739-0321, Japan
4
Department of Mechanical Systems Engineering, Faculty of Engineering, Hiroshima Institute of Technology,
Hiroshima 731-5193, Japan

Argon ion sputter etching was applied to two types of commercially pure titanium (JIS: TP340 and 550) and a martensitic stainless steel
(JIS: SUS420J2) specimens placed on a SUS304 stainless steel cathode disk, and a second sputter etching stage was carried out by placing these
specimens on a tungsten or tantalum cathode disk. The first sputter etching formed cone-shaped protrusions with base diameters of about 3 µm
on the titanium specimens and 20­30 µm on the SUS420J2 specimen, and the second sputter etching yielded fine ridge-shaped protrusions less
than 1 µm thick on the cone-shaped protrusions. In addition, nanometer-scale fine stick-shaped protrusions were formed along the tops of the
ridge-shaped protrusions. Thus, surfaces with multiscale protrusions were obtained by two-stage sputter etching using different cathode disks.
The specimens with ridge-shaped protrusions ensured high absorptance of more than 96% of visible light. [doi:10.2320/matertrans.M2018025]

(Received January 29, 2018; Accepted April 27, 2018; Published June 25, 2018)
Keywords: sputter etching, commercially pure titanium, stainless steel, multiscale protrusion, cathode disk, light absorptance

1. Introduction
Fine protrusions of various shapes, sizes and distributions
can be formed on the surfaces of metals and alloys by sputter
etching using argon or xenon plasma.1­3) The protrusion
formation mechanisms depend on the sputter etching
conditions and the kinds of alloys used.4) In the present
research we consider two mechanisms. (1) Very fine cone-,
rod-, tube- or ridge-shaped protrusions are formed when a
specimen is sputtered by placing it on or near a cathode
disk with a lower sputter rate than that of the specimen. The
particles (atoms including ions) sputtering out of the disk
arrive at the specimen surface and gather to form clusters.
They act as masks or seeds5,6) for the formation of protrusions.
One example of such a sputtering combination is a copper
specimen and a molybdenum disk.5) This mechanism is called
the artificial seed mechanism.4) (2) Cone-shaped protrusions
with vertex angles of about 40° and base diameters of
20­50 µm are formed by the sputter etching of austenitic or
martensitic stainless steels placed on a stainless steel disk.7­9)
Very fine cone-shaped protrusions smaller than 1 µm are also
formed by the sputter etching of tool steels containing strong
carbide formation elements, such as W, V and Mo.10,11) In
stainless and tool steels, fine carbides precipitated during
sputter etching become the origins of high densities of
protrusions,7­11) i.e., not only a high temperature and high
vacancy density but also a high temperature and vacancy
density gradient existing near the surface promote the rapid
precipitation of carbides. These carbides grow perpendicular
to the surface as pillars, and cone-shaped protrusions grow
stably around the pillars. Also, on a commercially pure
titanium,4) cone-shaped protrusions with base diameters of
about 3 µm form around the precipitated titanium dioxide
+
Corresponding author, E-mail: nakasa@hkg.ac.jp
pillars. In these cases, the sputter rate of a cathode disk should
be close to or higher than that of the specimen so that the
particles sputtering out of the disk do not stick to the specimen
surface as seeds. Because the origins of these protrusions
are the precipitates near the surface of the specimen, this
mechanism is called the precipitates seed mechanism.4)
These two seed mechanisms raise the possibility of
obtaining multiscale protrusions by using two-stage sputter
etching, i.e., the formation of considerably large cone-
shaped protrusions as a first stage using the precipitates
seed mechanism followed by the formation of very fine
protrusions on the cone-shaped protrusions as a second stage
using the artificial seed mechanism.
One application of such multiscale protrusions is as a
catalyst or support for a catalytic material. Because the
multiscale protrusions have wider surface areas and more
corners or edges compared with protrusions that have
smooth surfaces, they will increase the activity and
efficiency of chemical reactions. For example, fine ridge-
shaped protrusions smaller than 1 µm absorb more than
95% of visible light within wide incident angles from 0
to 70°.11) In addition, the protrusions also absorb about
90% of near-infrared rays with wavelengths shorter than
3 µm.12) Moreover, the surface oxidation of the protrusion
promotes the absorptance of infrared rays.12) Therefore, if
oxide layers or oxide particles having high photocatalytic
ability are formed or deposited on multiscale protrusions, the
photocatalytic reaction can be promoted by high absorptance
of solar light as well as a large reaction area. This may be
an effective method of solving environmental and energy
problems.13,14)
Another possible application of multiscale protrusions is
for the formation of bioactive surfaces. It is well known
that titanium and titanium alloys have high tissue
compatibility.15,16) Various surface modifications17) are
 Formation of Multiscale Protrusions on Pure Titanium and Stainless Steel 1199

Table 1 Chemical compositions of specimens (mass%).

carried out to promote tissue compatibility, e.g., the Fe, Cr, Ni Ti

formation of protrusions18) by sputter etching, the addition Fe, Cr, Ni Ti
Ar
of meshes17) and the addition of roughness,19) as well as the Ar
Titanium
formation of an oxide layer 20) or the formation of titanium SUS304 steel specimen
oxide nanotubes21) on the surfaces of implants. On the other disk
hand, it has already been reported that sharp protrusions
decrease the survival rate of bacteria22) and that titanium
oxide nanopatterns promote this effect.23) (a) Stage 1 Magnet Copper cathode Magnet
To realize these potential modifications, in the present
research we applied two-stage sputter etching to form
multiscale protrusions on pure titanium and stainless steel W, Ta
Ti Ti
specimens. In addition, we measured the absorptance of Ar Ar
visible light to confirm that the multiscale protrusions formed Tungsten or Titanium
on the specimens exhibit the high absorptance that has been tantalum specimen
seed disk W, Ta
reported on fine protrusions of tool steel,11) e.g., more than W,
95%. Ta

2. Experimental Procedures (b) Stage 2 Magnet Copper cathode Magnet

The materials used for the experiments were two types of

commercially pure titanium (JIS: TP340 and TP550; ASTM:
Grade 2 and Grade 4) and martensitic stainless steel (JIS:
SUS420J2; AISI: Type 420). The chemical compositions of
these materials are shown in Table 1. Both of the titaniums
were supplied as 1-mm-thick sheets, and they were cut into
square specimens at 20 mm per side. The specimens were
not polished because the surfaces were smooth as received.
SUS420J2 steel was supplied as a rod with a 20 mm diameter.
It was cut into 5-mm-thick specimens, and the surface of
each specimen was polished using emery paper up to a grit of
#1000.
Figure 1 schematically shows two stages of sputter etching
applied to a titanium specimen to obtain multiscale
protrusions. Stage 1 sputter etching (Fig. 1(a)) was carried
out as follows: the specimen was placed on a 2-mm-thick
SUS304 stainless steel disk set on a copper cathode of an RF
magnetron sputtering apparatus (SP300-M; Sanvac Co.). To
obtain the highest sputter rate, the specimen was placed on
the disk corresponding to the circle range between a pair of
magnets. After the vacuum pressure fell below 6 © 10¹3 Pa,
argon gas (purity: 99.999%) was introduced and maintained
at a pressure of 0.67 Pa. Then the specimens were sputter
etched with a sputter power of 250 W for 3.6­10.8 ks. The
purpose of this process is to form cone-shaped protrusions
on the specimens.4,9) After the SUS304 stainless steel disk
was changed to a tungsten or tantalum disk, stage 2 sputter
etching (Fig. 1(b)) was carried out at 250 W for 0.9, 1.8 and
3.6 ks to form fine protrusions on the original cone-shaped
protrusions. In the present research, the disk placed on the
Fig. 1 Schematic illustration of two-stage sputter etching to form multi-
scale protrusions. Stage 1: Argon ion sputter etching of a titanium
specimen to form cone-shaped protrusions by placing the specimen on a
SUS304 disk (a). Stage 2: Sputter etching to form fine protrusions by
placing the specimen on a tungsten or tantalum seed disk (b).
copper cathode is called the cathode disk, and it is called
either the seed disk or simply the disk depending on the
protrusion formation mechanism. Also, for the SUS420J2
steel specimen, the same two-stage sputter etching was
carried out using the SUS304 steel disk and the tungsten seed
disk, respectively.
The surface morphologies of the specimens after each
sputter etching were observed by a scanning electron
microscope (SEM; JEOL, JSM-6510A), and element
analysis was carried out by using an energy-dispersive X-
ray spectrometry (EDX) method. The relationship between
the wavelength and reflectance of visible light was measured
by a spectrophotometer (NF333; Nippon Denshoku Co.).
Reflectance was calibrated by using two standard samples:
one with a reflectance of 87.8% (white standard) and one
with a reflectance of 0% (black). This apparatus is a simple
system that uses a light incident angle of 2° and a detection
angle of 45°; the measured reflectance is a little larger than
the absolute reflectance, e.g., the reflectance of a tool steel
(JIS: SKH51; AISI: M2) specimen with fine protrusions
measured by this apparatus is 3.8%, whereas the absolute
reflectance measured using a geminated ellipsoid mirror is
0.25%.11)
1200 K. Nakasa, A. Yamamoto, T. Kubo, R. Wang and T. Sumomogi

(a) (b) (c)

200μm 20μm 5μm

Fig. 2 SEM images of protrusions formed by sputter etching of a TP340 titanium specimen placed on a SUS304 steel disk at 250 W for
7.2 ks. Image (a) is a top view, and (b) and (c) are 45° inclined side views.

3. Results and Discussion

(a)
3.1 SEM images of multiscale protrusions formed by
two-stage sputter etching of TP340 specimen using
SUS304 steel and tungsten cathode disks
The present authors4) have already reported that the sputter
etching of a commercially pure titanium specimen of TP340
(hereinafter the TP340 specimen) placed on a SUS304
stainless steel cathode disk (SUS304 disk) or an oxygen-free
copper disk (copper disk) forms cone-shaped protrusions 20μm
with base diameters of 2­5 µm. Figure 2 shows such
protrusions formed by sputter etching of the TP340
specimen at 250 W for 7.2 ks on the SUS304 disk. (b)
Although more than half of the grains are covered with
cone-shaped protrusions, there remain many grains on which
no or very few protrusions form due to the crystal orientation
dependency of protrusion formation.4) As is schematically
shown in Fig. 1(a), during the stage 1 sputter etching
process, all of the constituent elements of the SUS304 disk
and titanium specimens, including Fe, Cr, Ni, and Ti atoms, 5μm
are sputtered, and a small portion of these atoms that collide
with argon particles (atoms and ions) rebound and arrive
on the specimen surface. As we also reported,4) the shapes Fig. 3 SEM images of ridge-shaped protrusions formed by sputter etching
of a TP340 titanium specimen placed on a tungsten disk at 250 W for
and sizes of cone-shaped protrusions formed on the TP340
7.2 ks. Image (a) is a top view and (b) is a 45° inclined side view.
specimen are almost the same regardless of whether the
SUS304 disk or the copper disk is used, but EDX analyses
show no detectable Fe, Cr, Ni, or Cu elements on these the surface is densely covered with ridge-shaped protrusions
specimens. This means that the constituent elements of the with deep grooves, and the ridges are less than 500 nm wide.
SUS304 and copper disks were unable to become seeds for The tops of the ridges are not flat but feature nanometer-sized
the protrusions because the sputter rates of these atoms are stick-shaped protrusions. Similar dense ridges are observed
smaller than that of the Ti atom, i.e., these atoms are on the specimen sputter etched at 250 W for 3.6 ks, although
sputtered away even if they can stick to the specimen surface. the ridges are a little narrower. According to the EDX area
Thus, SUS304 and copper disks cannot serve as seed disks analysis of a 90 µm © 60 µm region of the specimen shown
for titanium specimens. On the other hand, no cone-shaped in Fig. 3, a tungsten amount of 3.87% is detected. This
protrusions were formed by sputter etching of a high-purity means that the protrusion formation mechanism in this case
(99.9%) titanium containing only 0.031% oxygen placed on corresponds to the artificial seed mechanism,1,4,5) i.e., as
the copper disk.4) This means also that the Ti atoms that shown in Fig. 1(b), a small portion of sputtered tungsten
are sputtered from the TP340 specimen and then return to atoms arrive and stick to the surface of the specimen. They
the specimen surface are not the origin of the cone-shaped gather to form clusters by surface diffusion, and the clusters
protrusions. Considering these results, the present authors become seeds or masks for the formation of the ridge-shaped
have concluded that the origin of the cone-shaped protrusion protrusions. Thus, the tungsten disk is the seed disk for the
formed by sputter etching of the TP340 specimen containing TP340 specimen.
0.11% oxygen placed on the SUS304 and copper disks It is difficult to determine the shape and distribution of
is titanium dioxide4) precipitated near the surface of the the tungsten clusters from EDX analysis, but if the tungsten
specimen corresponding to the precipitates seed mechanism, atoms gather as sphere-shaped clusters, cone-shaped
as explained above. protrusions rather than ridge-shaped protrusions would be
Figure 3 shows SEM images of the TP340 specimen formed beneath the clusters. The formation of ridge-shaped
sputter etched at 250 W for 7.2 ks on the tungsten disk. All of protrusions suggests that the tungsten particles have migrated
 Formation of Multiscale Protrusions on Pure Titanium and Stainless Steel
(a)
100μm
(c)
10μm
Fig. 4 SEM images of protrusions formed by sputter etching of a TP340 titanium specimen placed on a SUS304 steel disk at 250 W for
7.2 ks followed by sputter etching of the specimen on a tungsten disk at 250 W for 3.6 ks. Images (a) and (b) are top views, and (c) and
(d) are 45° inclined side views.
to form line-shaped clusters as stable shapes in the midst of
three simultaneous actions: argon ion sputtering of titanium
substrate, the sputtering of tungsten clusters themselves, and
the adhesion of tungsten atoms to the surface. According to
Fig. 3(a), the shape and direction of the ridge line differ from
grain to grain, which means that the sticking of tungsten
particles depends on the crystal orientation. Once the sputter
etching of the titanium matrix around the line-shaped clusters
progresses, newly arriving tungsten particles stick only to the
tops of the ridges. The formation of stick-shaped very fine
protrusions on the ridge suggests that the sticking of tungsten
particles is not homogeneous and that the ridge itself is
sputtered irregularly. Further sputter etching eventually forms
deep grooves among the ridge-shaped protrusions.
Although there is a possibility that the cone-shaped
protrusions in Fig. 2 are also formed during the sputter
etching of the specimen on the tungsten seed disk, no such
protrusion is observed in Fig. 3. This suggests that the ridge
forms so rapidly that the growth of cone-shaped protrusions
should be prevented even if the precipitation of titanium
dioxide pillars occurs.
Figure 4 shows SEM images of the TP340 specimen
sputter etched at 250 W for 7.2 ks on the SUS304 disk
followed by additional sputter etching at 250 W for 3.6 ks
with the specimen on the tungsten seed disk. By this two-
stage sputter etching, the very fine ridge-shaped protrusions
shown in Fig. 3 form not only on the cone-shaped
protrusions (e.g., region A in Fig. 4(b)) but also on the
grains on which cone-shaped protrusions do not form at the
first stage (the region B). The EDX area analyses of Fig. 4(b)
show that the tungsten contents in these areas are almost
the same. Thus, after the second stage of sputter etching,
triple-scale protrusions coexist: cone-shaped protrusions and
flat surfaces around the cones on a micrometer scale, ridge-
shaped protrusions on the cones and on the regions around
1201
(b)
W䠖2.89%
B A
W䠖2.55% 10μm
(d)
5μm
the cones on a submicrometer scale, and fine stick-shaped
protrusions along the tops of the ridges on a nanometer scale.
A comparison of Figs. 2 and 4 shows that the sharpness
and height of a cone-shaped protrusion are decreased by the
second-stage sputter etching. This means that the tungsten
particles landing on cone-shaped protrusions do not remain
permanently but are also sputtered away from the surface of
the cone.
3.2 SEM images of multiscale protrusions formed by
two-stage sputter etching of the TP550 specimen
using SUS304 steel and tantalum cathode disks
Figure 5 shows SEM images of the TP550 specimen
sputter etched at 250 W for 3.6 ks on the SUS304 disk.
Despite the shorter sputter etching time of 3.6 ks, the cone-
shaped protrusions are denser but smaller than those of the
TP340 specimen sputter etched for 7.2 ks (Fig. 2). This is
because the higher oxygen content of the TP550 specimen
relative to the TP340 specimen (0.32% vs. 0.11%) promotes
the precipitation of a larger number of titanium dioxides,
leading to the formation of cone-shaped protrusions.
However, it was difficult to form dense protrusions
covering all of the surface even when the sputter etching
time was prolonged to 10.8 ks.
Figure 6 shows an SEM image after the sputter etching of
the TP550 specimen at 250 W for 0.9 ks on the tantalum disk.
Very fine and deep holes with inside diameters smaller than
500 nm are densely formed. This suggests that the tantalum
particles arriving on the surface aggregate into ring-shaped
clusters rather than into line-shaped clusters and that they
become the seeds or masks to form holes. The surfaces of
ridges around the holes are rather flat, and there seem to be
no distinct stick-shaped protrusions on the ridge-shaped
protrusions as observed for the TP340 specimen sputter
etched on the tungsten seed disk (Fig. 3).
1202 K. Nakasa, A. Yamamoto, T. Kubo, R. Wang and T. Sumomogi

(a) (b) (c)

200μm 20μm 5μm

Fig. 5 SEM images of protrusions formed by sputter etching of a TP550 titanium specimen placed on a SUS304 steel disk at 250 W for
3.6 ks. All the images are 45° inclined side views.

Figure 7 shows SEM images of the surface of the TP550

2μm
Fig. 6 SEM images of protrusions formed by sputter etching of a TP550
titanium specimen placed on a tantalum disk at 250 W for 0.9 ks. The
image is a 45° inclined side view.
specimen sputter etched at 250 W for 7.2 ks on the SUS304
disk followed by sputter etching of the specimen on the
tantalum seed disk at 250 W for 1.8 ks (Fig. 7(a) and (b))
and 3.6 ks (Fig. 7(c) and (d)), respectively. Many holes are
formed both on and around the cone-shaped protrusions; i.e.,
double-scale protrusions are formed. The cone is shorter and
its top rounder than those formed by the sputter etching of the
TP340 specimen on the tungsten seed disk at the same sputter
etching time of 3.6 ks (compare Fig. 7(c) and (d) to Fig. 4).
Similar double-scale protrusions have already been formed at
a shorter sputter etching time of 0.9 ks.
EDX area analyses showed that the tantalum proportions
on the specimens are 1.25% for the sputter etching time of
0.9 ks, 3.38% for 1.8 ks, and 3.29% for 3.6 ks. These values
are similar to those of the TP340 specimen sputter etched on
the tungsten disk, i.e., 0.65­1.51% for 0.9 ks, 2.72% (average
value) for 3.6 ks (Fig. 4) and 3.87% for 7.2 ks (Fig. 3).
Although the amounts of adhered tantalum and tungsten
are almost the same, the resultant flatness and surface
morphology of the cone-shaped protrusions are different.

(a) (b)

10μm 5μm

(c) (d)

10μm 5μm

Fig. 7 SEM images of protrusions formed by sputter etching of a TP550 titanium specimen placed on a SUS304 steel disk at 250 W for
3.6 ks followed by sputter etching of the specimen on a tantalum disk at 250 W for 1.8 (a, b) or 3.6 ks (c, d). All images are 45° inclined
side views.
 Formation of Multiscale Protrusions on Pure Titanium and Stainless Steel
3.3 SEM images of multiscale protrusions formed by
two-stage sputter etching of the SUS420J2 specimen
using SUS304 steel and tungsten cathode disks
Figure 8 shows an SEM image of the SUS420J2 specimen
sputter etched at 250 W for 10.8 ks on the SUS304 disk.9)
Cone-shaped protrusions are formed, similar to the cases of
the TP340 and TP550 specimens. However, the protrusions
are more than ten times larger than those of the TP340 and
TP550 specimens and there are fine protrusions around the
cones. Although the protrusions are not very dense, their
distribution is rather homogeneous and is independent of
crystal grains. The cone-shaped protrusions originate from
the precipitation of chromium carbides,9) which corresponds
to the precipitation of titanium dioxides in the TP340
specimen.4)
Figure 9 shows SEM images of the SUS420J2 specimen
sputter etched at 250 W for 10.8 ks on the SUS304 disk
followed by the sputter etching at 250 W for 1.8 ks on the
50μm
Fig. 8 SEM images of protrusions formed by sputter etching of a
SUS420J2 steel specimen placed on a SUS304 steel disk at 250 W for
10.8 ks. The image is a 45° inclined side view.
(a) W: 3.51%
20μm
(c)
20μm
Fig. 9 SEM images of protrusions formed by sputter etching of a SUS420J2 steel specimen placed on a SUS304 steel disk at 250 W for
10.8 ks followed by sputter etching of the specimen on a tungsten disk at 250 W for 1.8 ks. Images (a) and (b) are top views, and images
(c) and (d) are 45° inclined side views.
1203
tungsten disk. Similar to the case with the TP340 specimen,
fine ridge-shaped protrusions with stick-shaped protrusions
form densely all over the surface. Because EDX analysis
detected a 3.51% proportion of tungsten in the area shown
in Fig. 9(a), the tungsten clusters are the seeds of the ridge-
shaped protrusions in this case as well. However, unlike the
case with the TP340 and TP550 specimens, in this specimen
the cone almost maintains its original height and sharpness.
The ridges and sticks are more complex in shape and they are
smaller than those observed on the TP340 specimen (Fig. 4).
3.4 Visible light absorptance of multiscale protrusions
One of the important functions of fine protrusions is their
high absorptance of visible and infrared light.11,12) The
multiscale protrusions formed on the TP340 and SUS420J2
specimens cover the wavelengths of ultraviolet light,
visible light, and near-infrared rays. Figure 10 shows the
relationships between wavelength and absorptance of
visible light obtained for the TP340 specimens with various
protrusions, where absorptance ¡ was calculated from
measured reflectance R (¡ = 100-R). Specimen D with
multiscale protrusions (Fig. 4) and specimen C with only
ridge-shaped protrusions (similar to those shown in Fig. 3,
but with a sputter etching time of 3.6 ks) each reveal an
absorptance of more than 97%, much larger than those of
as-received specimen A and as-sputter-etched specimen B
(Fig. 2). The reason for the high absorptance of specimens C
and D with fine ridge-shaped protrusions is the moth-eye
effect, i.e., the light that has entered the space among
protrusions repeats the reflection on the protrusion wall and
is absorbed without getting outside. The 97% absorptance
will be almost an upper limit value considering that the
absolute absorptance is larger than that measured with the
spectrophotometer used in the present research.11)
(b)
5μm
(d)
5μm
1204 K. Nakasa, A. Yamamoto, T. Kubo, R. Wang and T. Sumomogi
䕦 D: Sputter etched 䖃 E: Sputter etched on
on SUS304 disk + SUS304 disk + on W disk
on W disk + oxidation
䕕 C: Sputter-etched on W disk
B: Sputter etched
on SUS304 disk
TP340 titanium
A: As-received
Fig. 10 Relationships between wavelength and visible light absorptance
of a TP340 titanium specimen. A: The as-received specimen without
protrusions. B: A specimen sputter etched at 250 W for 7.2 ks placed on a
SUS304 steel disk. C: A specimen sputter etched at 250 W for 3.6 ks
placed on a tungsten (W) disk. D: A specimen sputter etched on a SUS304
steel disk followed by sputter etching of the specimen placed on a W disk
at 250 W for 3.6 ks. E: Specimen D oxidized at 773 K for 1.8 ks in air.
Although the absorptance of ultraviolet (UV) and near-
infrared light was not measured on the present protrusions,
the absorptance of these lights will still be large. For
example, the absorptance of infrared rays of the sputter-
etched SUS316 stainless steel and the SKH2 tool steel
with ridge-shaped protrusions is more than 90% within the
wavelength of 3 µm.12) The fact that the absorptance of the
multiscale protrusions at 400 nm is about 98% (Fig. 10),
combined with the fact that the minimum width of a ridge is
near 300 nm (Fig. 4), means that the multiscale protrusions
will absorb a large amount of UV-A light (wavelength 400­
315 nm), which is the main part of the UV light contained in
solar light. Specimen E was prepared by heating specimen D
in air at 773 K for 1.8 ks to form titanium oxide on the
surface. The absorptance of this specimen is a little larger
than those of specimens C and D, especially at a longer
wavelength. The reason for this is the additional absorptance
of titanium or tungsten oxide due to electron transition, as
has also been observed for the oxidized protrusions of tough
pitch copper and phosphor bronze.12)
Figure 11 shows the relationships between the wavelength
and absorptance of visible light obtained for the SUS420J2
specimens. Also in this case, the visible light absorptance of
specimen D with multiscale protrusions (Fig. 9), or that of
specimen C with only ridge-shaped protrusions, is more
than 96%, much larger than that of the as-sputter-etched
specimen B (Fig. 8).
Although the light absorptance of the surface with
multiscale protrusions formed on the TP340 and SUS420J2
specimens is almost the same as those of the surfaces with
only ridge-shaped protrusions, the total surface area and the
numbers of reaction sites of the former are much larger than
those of the latter. The combination of high visible light
absorptance and a large number of reaction sites of multiscale
protrusions can be applied to promote a photo-catalytic
reaction by oxidizing the titanium specimens, although it is
essential that the titanium oxide layer itself has high photo-
䕕 C: Sputter etched on W disk
䕦 D: Sputter etched on SUS304 disk
+ on W disk
SUS420J2 steel
B: Sputter etched on
SUS304 disk
Fig. 11 Relationships between wavelength and visible light absorptance of
a SUS420J2 steel specimen. B: A specimen sputter etched at 250 W for
10.8 ks placed on a SUS304 steel disk. C: A specimen sputter etched at
250 W for 1.8 ks placed on a tungsten (W) disk. D: A specimen sputter
etched on a SUS304 steel disk followed by sputter etching at 250 W for
1.8 ks placed on a W disk.
catalytic ability. The multiscale protrusions of SUS420J2
steel can be used as catalyst supports for the deposition of
high chemical- or photo-catalytic thin film or nanoparticles.
4. Conclusions
Argon ion sputter etching was applied to two types of
commercially pure titanium specimens (JIS: TP340 and 550)
and to a martensitic stainless steel (JIS: SUS420J2) specimen
placed on a SUS304 stainless steel cathode disk, and an
additional sputter etching was carried out by placing these
specimens on a tungsten or tantalum cathode disk. The results
obtained are as follows.
(1) The first sputter etching process formed cone-shaped
protrusions with base diameters of about 3 µm on the
TP340 and TP550 titanium specimens and of 10­30 µm
on the SUS420J2 specimen. The second sputter etching
of the TP340 and SUS420J2 specimens on the tungsten
disk formed fine ridge-shaped protrusions less than
500 nm thick on the cone-shaped protrusions. In
addition, nanometer-sized fine stick-shaped protrusions
formed along the tops of the ridge-shaped protrusions.
The second sputter etching of the TP550 specimen
on the tantalum disk formed fine holes with inside
diameters smaller than 500 nm. Thus, multiscale
protrusions were obtained by two-stage sputter etching
using different disks.
(2) The formation of cone-shaped protrusions in the first
sputter etching stage was due to the precipitates seed
mechanism, i.e., the origins of the protrusions were
the precipitated titanium dioxides in the TP340 and
TP550 specimens and the precipitated chromium
carbides in the SUS420J2 specimen. Ridge-shaped
protrusions or fine holes formed on the cone-shaped
protrusions due to an artificial seed mechanism, i.e.,
the tungsten or tantalum particles coming from the disk
gathered to form line-shaped or ring-shaped clusters on
the specimen surface and acted as seeds or masks.
 Formation of Multiscale Protrusions on Pure Titanium and Stainless Steel
(3) The TP340 and SUS420J2 specimens with multiscale
protrusions exhibited a high visible-light absorptance of
more than 96%.
Acknowledgments
This work was supported by JSPS KAKENHI Grant
Number JP 16K06780. We greatly appreciate the guidance
provided by Dr. A. Terayama and Mr. N. Fuyama of
Hiroshima Prefectural Technology Research Center regarding
the use of SEM and of the EDX apparatus. We also express
our gratitude to Mr. Y. Yoshikawa and Mr. Y. Mikami of
Hiroshima Kokusai Gakuin University for their assistance in
preparing the samples.
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