Diamond & Related Materials 63 (2016) 143–147

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Diamond & Related Materials

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

Fabrication of graphitic layers in diamond using FIB implantation and

high pressure high temperature annealing
S. Rubanov a,⁎, A. Suvorova b, V.P. Popov c, A.A. Kalinin d, Yu.N. Pal'yanov d,e
a
Bio21 Institute, The University of Melbourne, Victoria 3010, Australia
b
Centre for Microscopy, Characterisation and Analysis, The University of WA, WA 6009, Australia
c
Rhzanov Institute of Semiconductor Physics, SB RAS, 630090 Novosibirsk, Russia
d
Sobolev Institute of Geology and Mineralogy, SB RAS, 630090 Novosibirsk, Russia
e
Novosibirsk State University, 630090 Novosibirsk, Russia

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

Article history: We have used high pressure high temperature annealing (HPHT) for graphitisation of implanted layers in dia-
Received 16 July 2015 mond created by 30 keV Ga+ focused ion beam. Electron microscopy has been used to investigate the implanted
Received in revised form 27 November 2015 layers. It has been revealed that, unlike annealing at vacuum pressure, the graphitization during HPHT annealing
Accepted 27 November 2015
occurred through epitaxial growth of graphite (002) planes parallel to (111) diamond planes. High quality of
Available online 28 November 2015
graphite was confirmed by high resolution electron microscopy and electron energy loss spectroscopy.
Keywords:
© 2015 Elsevier B.V. All rights reserved.
Diamond
Ion implantation
Graphitisation

1. Introduction with predominant orientation of c-planes normal to the diamond

Ion implantation in combination with Ga focused ion beam (FIB)
technology has been successfully employed for fabrication of ultra-
thin diamond films and for fabrication of device structures in diamond
at submicron level [1–3]. Graphitization of amorphous layers in
diamond can be also used for fabricating device structures with two
structural forms of carbon: diamond and graphite. This allows synthesis
of conductive contacts/electrodes and buried conductive structures in
diamond without adding lithographic or growth processes. In this way
three-dimensional graphitic micro-channels were fabricated in single
crystal diamond [4–5]. Diamond–graphite–diamond (DGD) and
reversed graphite–diamond–graphite (GDG) heterostructures are
promising materials for optoelectronic and photonic devices, quantum
informatics (QI) and nano-electromechanical systems (NEMS). In previ-
ous work Kalish et al. [6] studied the conductivity of an implanted layer
in diamond (320 keV Xe and fluence 5 × 1014 ions/cm2) and reported
complete graphitization of the implanted layer after a 20 min annealing
at 600 °C. However, recent studies [7–8] using high-resolution electron
microscopy (HREM) revealed the partial graphitization of implanted
layers annealed at similar or much higher temperature. Vacuum
pressure high temperature annealing (VPHT) is commonly used for
graphitisation of implanted layers in diamond. TEM studies have
shown that VPHT annealing results in structural transformation of
implanted layers in diamond into nano-crystalline graphitic phase
surface [8–9]. These layers could be also chemically removed to obtain
thin diamond membranes. To avoid the formation of blisters at the sur-
face and in the volume and delamination of ultra-thin diamond films
(30–100 nm) the new method of graphitisation through high pressure
high temperature (HTHP) annealing in the vicinity of the phase equilib-
rium curve was introduced recently [10–11]. In these works the anneal-
ing was carried out at low end of HPHT conditions in the apparatus
mostly used for growth of synthetic diamond. TEM characterization
revealed that HPHT annealing of implanted (111) diamond results in
formation of highly ordered graphite with c-planes parallel to diamond
surface (diamond b 111N planes) [10–11].
FIB technique could be used as an ion implantation tool in diamond
for fabrication of buried amorphous layers and cap diamond layers with
thickness of few nanometers [12]. Also, due to FIB's small beam diame-
ter (~10 nm) it is possible to create implanted regions in diamond with
sub-micron dimensions. Thus, after cross-sectional TEM sample
preparation the thin TEM lamella could contain few regions implanted
with different fluences. In this work we have performed 30 keV Ga+
FIB implantation into (001) oriented synthetic diamond samples and
have examined the structure of the implanted regions following the
implantation and HPHT annealing using TEM.
2. Experimental methods

⁎ Corresponding author. FEI Nova Nanolab 200 dual beam FIB system was used for both the
E-mail address: sergey@unimelb.edu.au (S. Rubanov). ion implantation in single crystal (001) diamond (3 × 3 × 1.5 mm3;

http://dx.doi.org/10.1016/j.diamond.2015.11.017
0925-9635/© 2015 Elsevier B.V. All rights reserved.
144 S. Rubanov et al. / Diamond & Related Materials 63 (2016) 143–147
Fig. 1. a) HREM and b) WBDF images of the (001) diamond sample implanted with 30 keV
Ga+ ions and fluence 2 × 1014 ions/cm2.
synthetic type 1b HPHT produced by Sumitomo Electric Inc.) and the
cross-sectional TEM sample preparation. Ion implantation was carried
out with normal incidence to the diamond surface at 30 keV Ga+ ion en-
ergy and 10.7 pA beam current at room temperature. Previous study
[12] has shown the coincidence of the SRIM [13] simulated damage
profile and damage distribution in diamond after normal incidence
30 keV Ga implantation. This confirmed that the channelling effect
was negligible for this implantation conditions. The implantation areas
were several μm2 in size. The ion fluences were 2 × 1014, 4 × 1014 and
4 × 1015 ions/cm2. The peak defect density for these implantation
fluences were obtained from SRIM simulated damage profile with
displacement energy 52 eV. For highest implantation fluence the
etching depth in diamond was around 0.04 nm and Ga concentration
in implanted layer below 1.5 at.%. The implantation was conducted
using the same FIB pattern in four areas of diamond samples. Thus
four identical implantation areas separated by distance of 100 μm
were created. Two of them were used for TEM sample preparation
straight after implantation. Two other areas were used for sample prep-
aration after diamond annealing. The HPHT annealing of the implanted
sample was carried out at 1200 °C and 4 GPa for 1 h using a split sphere
multi-anvil apparatus BARS [14].
The sample was embedded in a CsCl cylinder and then loaded into a
high-pressure cell. The use of the CsCl pressure transmitting medium
provided nearly hydrostatic conditions of annealing. After ion implanta-
tion the diamond samples were coated with carbon film to avoid charg-
ing effects during TEM sample preparation. To protect created damaged
layers from any alteration during the sample preparation procedure,
~ 1 μm thick Pt stripes were deposited over the implanted areas using
FIB system e-beam deposition process. Cross-sectional TEM samples
with [110] orientation were prepared using lift-out technique,
described elsewhere [15]. To reduce the ion damage introduced into
TEM membrane during preparation process FIB milling at 5 keV (lowest
ion voltage with Nova Nanolab 200) and 80 pA beam current was used
at the final stage. This reduced the thickness of amorphous damage
layers on each side of TEM lamella down to 3.5 nm [16]. Prepared in
this way 100 nm thick TEM diamond samples contain only 7% of
amorphised carbon created during FIB milling. The TEM samples were
examined using FEI Tecnai TF20 transmission electron microscope
operated at 200 kV. Electron energy loss spectroscopy (EELS) measure-
ments were conducted in STEM mode, with a 1 nm probe beam diame-
ter, convergence semi-angle of 3.5 mrad, collection semi-angle of
16 mrad at 300 kV (Tecnai TF30) using Gatan GIF Quantum™ 965 ener-
gy filter. All TEM and EELS analyses were carried out using Gatan Digital
Micrograph software.
3. Results and discussion
Ga ion implantation induces vacancies and interstitials in diamond
by breaking some of its sp3 bonds. When the density of point defects
exceeds the amorphisation threshold (Dc) the crystal turns into amor-
phous state [6,9,16–20]. The Dc is very important for understanding
the ion-beam-induced amorphisation process in crystals. Thought the
exact defect configuration at the c–a interface in diamond is not
known, traditionally Dc is considered from the point of view of the
point defect production (vacancies) without consideration of the evolu-
tion of the generated damage and can be used as reference for different
ion implantation experiments conducted in similar conditions. In this
way the value of Dc can be obtained by measuring the position of the
leading crystalline–amorphous interface and then by reading
corresponding defect density in simulated, for example using SRIM
programme [13], damage profile. Several studies have determined Dc
in diamond [2,9,11,19–21] with reported values ranging from 1 to
9 × 1022 vac/cm3. The often used Dc value of 1 × 1022 vac/cm3 [18]
was obtained without taking into account the swelling of implanted
diamond layer which results in underestimation of Dc. The highest Dc
value of 9 × 1022 vac/cm3 [2] was obtained through measurements of
the diamond cap thickness after 2 MeV He+ implantation, annealing
at 550 °C and chemical etching. However, TEM studies have shown
partial graphitisation of implanted layer at this annealing temperature
[7,8] and the presence of the amorphous diamond-like carbon layer at
the bottom surface of the diamond cup layer after chemical etching
[8]. This could lead to overestimation of its thickness as well as overes-
timation of Dc. Also, for MeV implantation the accuracy of Dc value
obtained using this method could be low due to the combination of
poor accuracy of the low-magnification TEM measurements and the
fast rising curves of the simulated damage profiles. Some Dc values
were reported without any TRIM simulation details (displacement en-
ergy, binding energy, incident angle) and experimental errors [21].
However, some of these parameters, like displacement energy, have
strong influence on the value of Dc. For example, Spits et al. reported
for Dc the 74% and 50% of displaced carbon atoms obtained using
TRIM-92 simulation with displacement energy of 35 and 55 eV corre-
spondingly. Apparently, the SRIM simulated Dc values should be report-
ed together with simulation details. Also, in some reports small number
of ions was used in TRIM simulations which resulted in oscillated shape
of damage plots and in additional uncertainty in Dc determination
[19–21]. Recently the Dc value of 2.8 × 1022 vac/cm3 determined using
another approach was reported [22]. This value was obtained through
the calculation of the critical strain in diamond through the measure-
ment of the plasmon energy shift in assumption of the same effective
mass of the electron in diamond and implanted amorphous layer and
linear relation of defect density and strain. Thought this value could be
closer to the true value of Dc than the Dc obtained through the SRIM
simulation, the last one can be much easier used as reference point in
different ion implantation experiments. In this paper we are using
Dc = 5.2 ± 0.4 × 1022 vac·cm−3 determined in our previous work
[16] which correlates to value of 6 ± 2 × 1022 vac·cm−3 obtained by
Hickey et al. [9]. According to this criterion diamond is transformed
into amorphous state when every third carbon atom is displaced from
its lattice site. Diamond is metastable with respect to graphite at room
temperature and pressure. During ion implantation some of the broken
diamond sp3 bonds could be rearranged into more stable graphitic sp2
bonds.
Fig. 2. a) Bright field and b) WBDF images of diamond sample implanted with fluence of
4 × 1014 ions/cm2.
 S. Rubanov et al. / Diamond & Related Materials 63 (2016) 143–147
Fig. 3. a) HREM image of region implanted with fluence of 4 × 1014 Ga+ ions/cm2; b) FFT from implanted region; c) FFT from un-implanted diamond and d) EELS of carbon K-edge taken
from implanted region.
Bright field TEM study of the region of the diamond samples
implanted with fluence of 2 × 1014 ions/cm2 (peak defect density
~2.5 × 1022 vac·cm−3) do not show any amorphisation (Fig. 1a). How-
ever, implanted region was clearly visualized in g-3g weak beam dark
field (WBDF) image with diffraction vector g = [2–20] shown in Fig. 1b.
The reason for the contrast observed in WBDF image is related to the
(2-20) lattice distortions due to strain. This area of distorted crystal lat-
tice is visible as a brighter band in Fig. 1b. The density of point defects
here is below Dc but large enough to cause local distortion of the dia-
mond lattice.
Fig. 2a demonstrates bright field cross-sectional image of implanted
region with fluence of 4 × 1014 ions/cm2 (peak defect density ~5 × 1022
vac·cm−3). The implanted layer has brighter contrast comparing to un-
implanted diamond due to the presence of amorphous clusters. Also di-
amond cap layers remain crystalline near sample surface similar to that
observed previously [16].WBDF image of this region is shown in Fig. 2b.
There are two distorted diamond layers visible as bright bands and a
darker layer in between.
A high-resolution image of the implanted region is shown in Fig. 3a.
The (111) atomic planes are seen in the implanted layer between two
heavily damaged diamond interfaces. The thickness of this region was
found to be ~7 nm. This partially amorphised layer contains amorphous
and crystalline clusters. Some of the amorphous clusters are marked by
white arrows in Fig. 3a. Fig. 3b and c shows Fast Fourier Transformation
(FFT) patterns of implanted region and bulk un-implanted diamond, re-
spectively. Halo is seen around central spot in Fig. 3b. This confirms the
presence of amorphous phase in the implanted region. Apparently the
defect density of ~ 5 × 1022 vac·cm−3 in the central part of the im-
planted layer just exceeds Dc and amorphisation occurred. EELS were
taken from different points of this partially amorphised layers. Typical
K-edge spectrum is shown in Fig. 3d. Carbon materials with sp2 bonds
have strong π⁎ peak at 285 eV. The absence of this peak indicates that
despite of the partial amorphisation carbon atoms are mostly sp3 bond-
ed in this area. Also FFT in Fig. 3b shows elongation of spots
Fig. 4. a) Bright field image and b) HREM image with FFT on the inset of implanted layer with Ga fluence of 4 × 1015 ions/cm2; c) corresponding EELS spectrum of carbon K-edge.
145
corresponding to diamond (111) atomic planes into direction normal
to the sample surface. This elongation indicates extension of the dia-
mond lattice into [002] direction. The positions of the elongated spots
and corresponding spots in un-implanted diamond (Fig. 3c) were mea-
sured in reciprocal space using Gatan Digital Micrograph software, then
converted to the normal space. The diamond lattice extension in the
partially amorphous layer was calculated to be up to ~8%.
The cross-sectional bright field and HREM images of diamond im-
planted with fluence of 4 × 1015 ions/cm2 (Fig. 4) show that the defect
density exceeded the amorphisation threshold and implanted region
is amorphous. The swelling of the amorphous damage layer is evident
(Fig 4a). As a result of swelling and corresponding density reduction it
is not possible to obtain the peak defect density for this implantation
fluence from SRIM damage profile in diamond. HREM image of im-
planted region with corresponding FFT in inset is shown in Fig. 4b. It
confirms full amorphisation of the implanted layer. EELS of carbon K-
edge with π⁎ peak shown in Fig.4c indicates the presence of both sp2
and sp3 bonding in the implanted region. The swelling has been attrib-
uted to diamond's sp3 bond conversion to sp2 bonds with significant de-
crease in density. The positive step height between unimplanted and
implanted regions could be a result of Poisson ratio effect which arises
from the biaxial compressive stress in the plane of the implanted layer
[23]. Using a mass calculation the density of the amorphous layer was
determined to be 2.32 g/cm3 (75% sp2).
TEM study of diamond samples after HPHT annealing did not show
any changes in structure of region implanted with lowest fluence.
HREM image of partially amorphised region (implantation fluence
4 × 1014 ions/cm2) after HPHT annealing is shown in Fig. 5a. No traces
of graphitization were found. However, amorphous clusters became
more clearly visible with sharp amorphous–diamond interfaces along
(111) atomic planes in the annealed sample when compared with the
sample before annealing. Though the HPHT annealing was conducted
under conditions of graphite stable region according to P, T phase dia-
gram of carbon, the lack of sp2 bonds prevents the graphitization process.
146 S. Rubanov et al. / Diamond & Related Materials 63 (2016) 143–147
Fig. 5. HREM images of implanted regions in diamond after HPHT annealing: a) Ga fluence of 4 × 1014 ions/cm2; b) Ga fluence of 4 × 1015 ions/cm2 layer; c) carbon K-edge of graphitized
layer shown in b).
HREM image of region implanted with Ga fluence of 4 × 1015 ions/
cm2 after HPHT annealing is shown in Fig. 5b. Transition of amorphous
damage layer into graphitic state is evident. Graphite c-planes are clear-
ly visible and are parallel to diamond (111) atomic planes. FFT with
spots corresponding to diamond (111) and graphite (002) atomic
planes is shown in the inset. The arrangement of these spots also con-
firms good epitaxial relation of diamond and graphite. EELS of carbon
K-edge is shown in Fig. 5c. The fine structure of carbon K-edge is similar
to the structure reported for single-layer graphene [24] which also indi-
cates high quality graphitic layer. The graphite–diamond interface is
rather sharp. Diamond {111} atomic planes and graphite {002} atomic
planes have similar density of carbon atoms. The ratio density of graph-
ite to the density of diamond is close to 2/3. In the graphite–diamond
interface shown in Fig. 5b two {002} planes of graphite match up with
three {111} planes of diamond. This is in agreement with the
minimisation effect of interface strain energy reported for epitaxial
growth of diamond on graphite [25]. Vacuum pressure annealing in
reported temperature range of 550–1400 °C results in the formation of
nanocrystalline graphitic phase with c-planes predominantly oriented
perpendicular to the surface [3,8–9]. This correlates with thermody-
namic calculations which predict that a biaxial compressive stress pre-
sented in implanted layers will orient the graphitic particles with their
c axis perpendicular to the stress field [6]. Further studies and theoreti-
cal modelling still have to be performed to understand the process of
graphitisation of the ion implanted layers in diamond during high pres-
sure high temperature annealing.
4. Conclusions
The effect of fluence on ion implanted diamond structure has been
studied by electron microscopy imaging and spectroscopy techniques.
It has been found that FIB ion implantation with different fluences
results either in formation of partially amorphous or fully amorphous
layers. Partially amorphous layers contain amorphous and crystalline
clusters. The lattice extension in these crystalline clusters achieved
~ 8% in the direction normal to the diamond surface. HPHT annealing
of implanted diamond samples results in graphitization of continues
amorphous layers. Unlike annealing at vacuum pressure, the graphitiza-
tion during HPHT annealing occurred through epitaxial growth of
graphite (002) planes parallel to (111) diamond planes. High quality
of graphite was confirmed by high resolution electron transmission
microscopy.
Prime novelty statement
High pressure high temperature (HPHT) annealing (1200 °C, 4 GPa)
using a split sphere multi-anvil apparatus BARS has been carried out for
the first time for structural transformation of 30 keV Ga focused ion
beam (FIB) implanted layers in (001) single crystal diamond. HPHT
annealing of implanted diamond samples results in epitaxial graphitiza-
tion of continuous amorphous layers. Unlike commonly used annealing
at vacuum pressure, the graphitization during HPHT annealing occurred
through epitaxial growth of graphite (002) planes parallel to (111)
diamond planes. High structural quality of graphite was confirmed by
high resolution transmission electron microscopy imaging.
Acknowledgments
This work was supported by the Australian Research Council under
Linkage Infrastructure, Equipment and Facilities programme (LE
130100090).
References
[1] N.R. Parikh, J.D. Hunn, E. McGucken, M.L. Swanson, C.W. White, R.A. Rudder, D.P.
Malta, J.B. Posthill, R.J. Markunas, Single-crystal diamond plate liftoff achieved by
ion implantation and subsequent annealing, Appl. Phys. Lett. 61 (1982) 3124–3126.
[2] P. Olivero, et al., Characterisation of three-dimensional microstructures in single-
crystal diamond, Diam. Relat. Mater. 15 (2006) 1614–1621.
[3] B.A. Fairchild, P. Olivero, S. Rubanov, A.D. Greentree, F. Waldermann, R.A. Taylor, I.
Walmsley, J.M. Smith, S. Huntington, D.C. Gibson, D.N. Jamieson, S. Prawer,
Fabrication of ultrathin single-crystal diamond membranes, Adv. Mater. 20 (2008)
4793–4798.
[4] P. Olivero, G. Amato, F. Bellotti, S. Borini, A. LoGiudice, F. Picollo, E. Vittone, Direct
fabrication and IV characterization of sub-surface conductive channels in diamond
with MeV ion implantation, Eur. Phys. J. B 75 (2010) 127.
[5] F. Picollo, D. Gatto Monticone, P. Olivero, B.A. Fairchild, S. Rubanov, S. Prawer, E.
Vittone, Fabrication and electrical characterization of three-dimensional graphitic
microchannels in single crystal diamond, New J. Phys. 14 (2012) 053011.
[6] R. Kalish, A. Reznik, S. Prawer, D. Saada, J. Adler, Ion-implantation-induced defects in
diamond and their annealing: experiment and simulation, Phys. Status Solidi (a)
1974 (1999) 83.
[7] S. Rubanov, B.A. Fairchild, P. Olivero, A.D. Greentree, D.N. Jamieson, S. Prawer, TEM
characterisation of nanofabrication process in a single crystal diamond, AMTC Lett.
1 (2008) 252.
[8] S. Rubanov, B.A. Fairchield, A. Suvorova, P. Olivero, S. Prawer, Structural transforma-
tion of implanted diamond layers during high temperature annealing, Nucl. Inst.
Methods Phys. Res. B 365 (2015) 50–54.
[9] D.P. Hickey, K.S. Jones, R.G. Elliman, Amorphization and graphitization of
single-crystal diamond — a transmission electron microscopy study, Diam. Relat.
Mater. 18 (2009) 1353.
[10] V.P. Popov, V.A. Antonov, L.N. Safronov, I.N. Kupriyanov, Y.N. Pal'yanov, S. Rubanov,
Fabrication of ultra-thin diamond films using hydrogen implantation and lift-off
technique, AIP Conf. Proc. 1496 (2012) 261.
[11] V.P. Popov, A.K. Gutakovskii, V.A. Antonov, S.N. Podlesnyi, I.N. Kuprianov, Y.N.
Palyanov, A. Rubanov, High-quality single-crystal diamond–graphite–diamond
membranes and devices, Int. J. Nanotechnol. 12 (2015) 226.
[12] S. Rubanov, A. Suvorova, Ion implantation in diamond using 30 keV Ga+ focused ion
beam, Diam. Relat. Mater. 20 (2011) 1160.
[13] J.F. Zeigler, J.P. Biersak, SRIM2008Available from: http://www.srim.org2008.
[14] Y.N. Palyanov, Y.M. Borzdov, A.F. Khokhryakov, I.N. Kupriyanov, A.G. Sokol, Effect of
nitrogen impurity on crystal growth processes, Cryst. Growth Des. 10 (2010)
3169–3175.
[15] L.A. Giannuzzi, J.L. Drown, S.R. Brown, R.B. Irwin, F.A. Stevie, Applications of the FIB
lift-out technique for TEM specimen preparation, Microsc. Res. Tech. 41 (1998)
285–290.
[16] S. Rubanov, A. Suvorova, The study of the FIB induced damage in diamond, Microsc.
Microanal. 17 (2) (2011) 700.
 S. Rubanov et al. / Diamond & Related Materials 63 (2016) 143–147
[17] L.A. Christel, J.F. Gibbons, T.W. Sigmon, Displacement criterion for amorphisation of
silicon during ion implantation, J. Appl. Phys. 52 (1981) 7143–7146.
[18] C. Uzan-Saguy, V. Richter, S. Prawer, Y. Lifshitz, E. Grossman, R. Kalish, Nature of
damage in diamond implanted at low temperatures, Diam. Relat. Mater. 4 (1995)
569–574.
[19] C. Uzan-Saguy, C. Cytermann, R. Brener, V. Richter, M. Shaanan, R. Kalish, Damage
threshold for ion-beam induced graphitisation of diamond, Appl. Phys. Lett. 67
(1995) 1194–1196.
[20] R.A. Spits, J.F. Prins, T.E. Derry, A determination of the critical damage density
required for “amorphisation” of ion-implanted diamond, Nucl. Inst. Methods Phys.
Res. B 85 (1994) 347.
[21] E.K. Nshingabigwi, T.E. Derry, S.R. Naidoo, J.H. Neethling, E.J. Olivier, J.H. O'Connell,
C.M. Levitt, Electron microscopy profiling of ion implantation damage in diamond:
dependence on fluence and annealing, Diam. Relat. Mater. 49 (2014) 1–8.
147
[22] B.A. Fairchild, S. Rubanov, D.W.M. Lau, M. Robinson, I. Suares-Martinez, N. Marks,
A.D. Greentree, D. McCulloch, S. Prawer, Mechanism for the amorphisation of
diamond, Adv. Mater. 24 (2012) 2024–2029.
[23] D.G. McCulloch, D.R. McKenzie, S. Prawer, Compressive stress induced formation of
preferred orientation in glassy carbon following high-dose C+ implantation, Philos.
Mag. A 72 (1995) 1031.
[24] R.F. Egerton, EELS in the Electron Microscope, Springer-Verlag, New York Inc, 2011.
[25] W.R.L. Lambrecht, C.H. Lee, B. Segal, J.C. Angus, Z. Li, M. Sunkara, Diamond nucleation
by hydrogenation of the edges of graphitic precursors, Nature 367 (1993) 607–610.