Diamond & Related Materials 24 (2012) 29–33

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Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

Fabrication and fundamental characterizations of tiled clones of single-crystal

diamond with 1-inch size☆
Hideaki Yamada ⁎, Akiyoshi Chayahara, Hitoshi Umezawa, Nobuteru Tsubouchi,
Yoshiaki Mokuno, Shinichi Shikata
Diamond Research Lab., National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan

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

Available online 29 September 2011 We have developed a technique to fabricate “tiled clones”, a new type of mosaic wafers. This technique uses
“cloned” substrates, which come from an identical seed substrate. Four to eight 10 mm×10 mm “clone” substrates,
Keywords: each at most 1 mm thick, were connected to form one large wafer with a range of area of 20 mm ×20 mm-
Single-crystal diamond 20 mm ×40 mm,. These clone substrates could be connected relatively smoothly, with abnormal growth being
Crystal growth
suppressed, and the boundaries among the constituent clones were almost invisible. In addition to observation
Large wafer
of their cross sections, Raman spectra and X-ray diffraction was measured for each of these tiled clones. FWHM
Ion beam implantation
of the X-ray rocking curve was around 10–50 arcsec in the areas away from the boundaries.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Increasing power efficiency in electronics is considered extremely
important in the sustainable development of limited energy resources.
In this sense, single-crystal diamond (SCD), because of its material
characteristics such as wide band gap, high thermal conductivity,
low dielectric constant and high carrier mobility [1,2], stands out as
a material with potential to realize electronic devices with extremely
high performance.
However, compared with other semiconductor materials, processing
techniques for SCD are not well developed. For example, artificial
inch-size SCD wafers have not, as yet, been produced commercially. As
with silicon and silicon-carbide, wafer size is one of the most important
factors for the industrial use of semiconductor materials because this
directly relates to the cost of devices fabricated on those wafers.
While the wafer sizes of silicon-carbide and silicon have reached 6
and 12 in [3] in diameter, respectively, commercially available
single-crystal diamond is still no more than 10 mm. This is primarily
due to the lack of large, artificially made seed crystals. In turn, this
is due the difficulties in enlarging bulk crystals into even a 1-inch size.
Several researchers have tried to enlarge crystals by controlling the
alpha-parameter [4–6] and/or three-dimensional growths [7] in plasma
chemical vapor deposition (CVD). The former of these approaches does
☆ Presented at NDNC 2011, the 5th International Conference on New Diamond and
Nano Carbons, Suzhou, China.
⁎ Corresponding author. Tel.: + 81 72 751 9531; fax: + 81 72 751 9631.
E-mail address: yamada-diamond@aist.go.jp (H. Yamada).
not allow for the introduction of nitrogen into the feed-gas, and
therefore, the growth rate is limited to less than several μm/h. Nitrogen
is required to realize stable growth onto the {100} surfaces, but this
stops the top surface of the substrate from enlarging laterally during the
growth [7–9]. Therefore, Mokuno, et al., conducted three-dimensional
growth where the diamond is grown in several b100N directions, and
succeeded in fabricating half-inch size SCD plates. However, even using
this method, it is still not easy to obtain a 1 inch wafer, because the
growth must be maintained stably for such long times. It would take
more than 1000 h to enlarge a 10 mm substrate to 25 mm (=1 in)
under these conditions at 10 μm/h.
So-called “mosaic wafers” [10–18] may be another option, if the
sizes of the constituent SCD plates are larger than the devices to be
fabricated on such a wafer. The largest mosaic wafer in the literature
is 16 mm × 16 mm, where sixteen 4 mm × 4 mm substrates were
connected into one wafer [17,18]. However, that mosaic wafer
seems to have had pin-holes at each corner of the connected substrate
and quite obvious boundaries between the constituent SCD plates.
Furthermore, free-standing wafers made from that mosaic wafer have
always been shown to contain cracks.
In this paper, we introduce an efficient way to fabricate a mosaic
wafer and free-standing wafers that have been cloned from that mosaic
wafer [19,20]. The boundaries between the constituent SCD plates are
smooth and almost invisible. The key point of the present technique is
the use of “clones”, which are made from identical single seed substrate.
We refer to such wafers as “tiled clones” as described in the following.
The tiled clones have been characterized by using Raman spectroscopy
and X-ray diffraction.

0925-9635/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2011.09.007
30 H. Yamada et al. / Diamond & Related Materials 24 (2012) 29–33
Seed Substrate
(~10mm )
(1) Ion implantation
(2) Growth of SCD layer
(4) Repeating
the procedure
(1)-(3) for the
identical seed
substrate
(3) Etching the graphitic layer
Fig. 1. Procedure to produce clones and tiled clones [See Section 2].
2. Fabrication of “clones” and “tiled clones”
As reported in several papers/presentations [19,20], free-standing
wafers of SCD can be fabricated by the use of ion implantation. By
applying this lift-off process from a single seed substrate, we can
make “clones” of it, i.e. substrates that have the same crystallographic
characteristics as each other and the seed substrate. Connecting these
clones gave what will be referred to as tiled clones. Using this technique,
we have succeeded in fabricating tiled clones on the 1-inch scale, and
subsequently clones of this enlarged seed. Fig. 1 shows this procedure.
At first, four clone substrates are fabricated from a single seed substrate
about 10 mm× 10 mm [procedures (1–4) in Fig. 1]. This original seed
substrate has been enlarged by Dr. Mokuno [7] with an off-angle of
around 3°. These clones were aligned with each other to within less
than 500 μm manually, to make a tiled clone [procedure (5) in Fig. 1].
Then, SCD layers were grown on both sides of the tiled clone wafer.
The edges of the tiled clone were processed by laser cutting before
growth. Ion implantation [procedures (1–3) in Fig. 1] was used to
achieve the lift-off process from this tiled clone, and to give a
free-standing clone of the tiled clone [procedure (6) in Fig. 1], which
retains some characteristics of the parent. An image of a typical
free-standing clone of a tiled clone is shown in Fig. 2. As their properties
5mm
Fig. 2. An image of typical tiled clones.
(5) Connecting the (6) Applying the lift-
clones off process
are similar to the parent tiled clone, these will also be referred to as tiled
clones. The arrows in Fig. 2 indicate the locations of the boundaries
between the connected clones. Each connected clone was about
10 mm× 10 mm, which is the same as the seed substrate, and gave
a free-standing wafer around 20 mm× 20 mm. The shape of the
tiled clones was almost square, whereas, in previous works [19,20],
the resultant tiled clones have been quite irregular. From the figure,
one can see the boundaries between the connected clones are almost
invisible. In addition, the fabricated wafer has no obvious cracks.
In the above case, four 10 mm × 10 mm cloned SCD substrates
were connected to make one 20 mm × 20 mm tiled clone. However,
this is still smaller than the wafers of other semiconductor materials,
which are at least 2 in 2 to 6 in in diameter. Therefore, we connected
these 20 mm × 20 mm tiled clones into one 20 mm × 40 mm size
tiled clones as a stepping stone to further enlarged wafers. Improving
the holder shape to control distribution of the growth rate was also
investigated in enlarging the size of the tiled clones. Fig. 3(b) shows
the distribution of growth rates that were obtained on the
20 mm × 40 mm size tiled clones as shown in Fig. 3(a). Growth rates
for two cases are shown, using different holder shapes during the
growth by plasma CVD. For the case of holder type-A, a tiled clone
is placed onto a planner holder, as shown in the inset for the figure.
For the type-B holder, the tiled clone is surrounded by a wall with a
depth similar to the thickness of the tiled clone [21]. The former
gave a concave growth rate profile; the growth rate drops to 60% of
the maximum. On the other hand, in the later case, the non-uniformity
is suppressed to 10%. Here, the plasma and temperature distributions
were improved by the guide walls around the tiled clones [22] and
this improved the uniformity of the growth rate distribution.
a b
Growth rate [normalized]
holder type B
1mm 0.5 holder type A
substrate
20mm holder
20mm
0
0 20 40
length [mm]
Fig. 3. (a) An image of a 20 mm× 40 mm × 1 mm tiled clone, and (b) growth distribution
obtained for this tiled clone when testing the two types of substrate holders, which are
shown in the inset. The horizontal axis represents length from one edge of the tiled
clone, and the vertical axis represents the growth rates obtained at the indicated position.
 H. Yamada et al. / Diamond & Related Materials 24 (2012) 29–33 31

a b c
boundary
Interface boundary
20mm
Top surface Top surface
0.9mm Cross section Additive
Cross section
SCD
layers Interface
Additive
SCD
layers
Additive
Clones SCD
layers

Fig. 4. (a) A tiled clone, schematically drawn with thickness of 0.9 mm, (b) An image of the cross section of a tiled clone, and (c) polarized microscope image of the cross section of a
tiled clone. Image (c) was taken from the gray rectangle indicated in (a).

a d

10mm 10mm

b e
on the boundary on the boundary
Intentisy [normalized]
Intentisy [normalized]

0µm above/below
50 500µm above/below
the boundary the boundary

Others are measured Others are measured

in a distance farther than in a distance farther than
100µm from the boundary 100µm from the boundary

w/o boundary w/o boundary

(interior region) (interior region)
g

1330 1332 1334 1336 1330 1332 1334 1336

Raman shift [cm-1] Raman shift [cm-1]

c f
on the boundary
on the boundary
Intentisy [normalized]

Intentisy [normalized]

500µm above/below
500µm above/below the boundary
the boundary
Others are measured
Others are measured in a distance farther than
in a distance farther than 100µm from the boundary
100µm from the boundary

w/o boundary
dary
w/o boundary (interior region)
g
(interior region)

1330 1332 1334 1336 1330 1332 1334 1336

Raman shift [cm-1] Raman shift [cm-1]

Fig. 5. (a), (d) Photographs of the tiled clone. The dashed lines indicate the boundaries between the constituent clone substrates. (b), (c) Raman spectra obtained along the arrows
indicated in Fig. (a). (e), (f) Raman spectra obtained along the arrows indicated in Fig. (d). The black, blue, and other profiles are the results obtained at the boundaries, 50 μm from
the boundaries, and 100 μm or further from the boundaries, respectively.
32 H. Yamada et al. / Diamond & Related Materials 24 (2012) 29–33

3. Observations of some tiled clones Fig. 6 shows the FWHM mapping of the X-ray rocking curves.
Fig. 6(a) and (b) corresponds to the maps of the four-piece clone
To observe the cross section features of the connected clones, a [Fig. 5(a)] and the six-piece clone [Fig. 5(d)], respectively. The X-ray
tiled clone was made with a thickness of 0.9 mm and the side was beam was produced using a two-crystal, Si(022) and Ge(004),
polished as shown in Fig. 4(a). Fig. 4(b) shows an image of this monochromator and Cu-Kα radiation. The beam was used to obtain
cross section. The photo was taken inclined from the perpendicular the rocking curves for the diamond (004) reflection. For both the four
to the side surface; therefore, the top, as well as the side can be seen. and six-piece clones, the domain was divided into 1 mm × 1 mm and
The additive SCD layers on the top and bottom of the clone substrate 2 mm × 2 mm segments, respectively within which the measurements
can be seen and the interface between the original tiles is indicated were conducted. The four-piece clone [Fig. 6(a)] gave FWHM which
in the figure. were relatively small and uniform all over the area, with magnitudes
From the figure, it appears that the space at the interfaces between typically in a range of 20–80 arcsec, except at the boundary regions.
the sides of the original clones has not been fully filled with the added This magnitude is also similar to those reported for monolithic SCDs
SCD layer. Therefore, the interface of the connected clones can be [1,24]. On the other hand, the six-piece clone gave relatively large
recognized clearly. However, no obvious structure can be recognized magnitudes in the central region, close to 100 arcsec. This suggests
either above or below this interface. Therefore, the interfaces inside that it is better to reduce the number of constituent SCD plates for the
the tiled cone can only be recognized through the additive SCD layer fabrication of high quality tiled clones. As the number of constituent
above the interfaces. The clone of such a tiled clone, shown in Fig. 2, clone substrate, stress inside the resultant tiled clone increases. This
corresponds to this additive SCD layer, where the boundaries are may be the cause of the difference between these tiled clones.
also almost invisible. However, there are some structures inside
the crystal at this point as revealed by polarized microscopy of the 4. Summary
same cross section [Fig. 4(c)]. This image is taken from a 0.2 mm
thick sample which was cut from of the cross section as indicated by We have succeeded in fabricating 1-inch size tiled clones of SCD
the gray rectangle in Fig. 4(a). This image implies that dislocations by applying the lift-off process with ion implantation from a single
and/or bundles of dislocations do exist at the interfaces, and this seed crystal, in other words, by using a cloned substrate of SCD. The
causes stress inside the clones and additive SCD layers. It seems that results show that the use of these cloned substrates is very efficient. As
these stressed regions transmit a certain broadness during the growth
of the additive SCD layer. a
Fig. 5 shows the profiles of the Raman spectra which were
obtained when crossing the boundaries. The measurements were
conducted at room temperature by using a Jobin Yvon T64000 system
with a Nd:YAG laser source, operating at 532.0 nm. Two types of the
tiled clones were studied; one consisted of four clone substrates as
shown in Fig. 5(a) and the other consisted of six clone substrates as
shown in Fig. 5(d). The dashed lines in Fig. 5(a) and (d) indicate the
boundaries of the clones. Arrows indicate the lines along which the
measurements were conducted. Spectra shown in Fig. 5(b) and (e)
were the result of measurements along the horizontal arrows of
Fig. 5(a) and (d), respectively at 50-μm intervals, with Fig. 5(c) and
(f) being the corresponding vertical measurements,. The black and
blue profiles correspond to results which were measured on the
boundary and at a distance of 50 μm, respectively. In those cases,
the widths of the spectra are broad as seen in Fig. 4. The six-piece
clone [Fig. 5(d)] gives broader spectra than the four-piece clone
[Fig. 5(a)]. Furthermore, it seems that the spectra for the six-piece
clone [black and blue profiles of Fig. 5(e) and (f)] include several
shoulders. This implies that, compared with the four-piece clone,
there are relatively strong internal stresses. For the four-piece clone, b
the spectra measured along the horizontal line are broader than
those of the vertical lines. This anisotropy is probably caused by the
direction of the off-angle in the constituent clone substrates. In this
case, the direction of the off-angle is almost parallel to the vertical
arrow shown in Fig. 5(a). Because each clone tends to expand in the
direction of the off-angle, the boundary in the horizontal direction is
relatively smoothly covered. On the other hand, expansion of each
clone in the horizontal direction is expected to be relatively small.
While that is enough to cover the boundaries in the vertical direction
with the additional SCD layer, this may make the quality of the
boundaries relatively poor. At 100 μm and further from the boundary,
the profiles have almost converged for both types of tiled clones, as
shown by the profiles except for the black and blue ones in Fig. 5(b),
(c), (e) and (f). Further into the substrate, there was no significant
peak shift among the spectra. This implies that in the area beyond
100 μm is similar to that of the constituent SCD plates. The full-width–
half-maximum (FWHM) of these converged spectra, around 2 cm− 1, Fig. 6. Full-width–half-maximum maps of the X-ray rocking curves measured for the
is narrower than that reported for a hetero-epitaxially grown diamond tiled clones shown in (a) Fig. 5 (a), and (b) Fig. 5 (d). The arrows in the figure indicate
[23] and similar to those reported for monolithic SCD [24]. the boundary regions.
 H. Yamada et al. / Diamond & Related Materials 24 (2012) 29–33 33

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