Carbon 122 (2017) 276e280

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Dual phase amorphous carbon ceramic achieves theoretical strength

limit and large plasticity
Chang Liu*, Yanyan Lin, Zhifeng Zhou, Kwok-Yan Li
Department of Mechanical and Biomedical Engineering, City University of Hong Kong, Kowloon, Hong Kong, China

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

Article history: Ceramics are widely used as engineering materials due to their high strength; however, their lack of
Received 6 April 2017 plasticity is a major drawback. We report that dual-phase amorphous carbon (a-C) reveals high yield
Received in revised form strength of ~E/11 (E is elastic modulus, and E/10 is theoretical limit for ideal material) and large plasticity
23 June 2017
of ~70% at room temperature in uniaxial compression tests. To the best of our knowledge, this report
Accepted 24 June 2017
describes the first time since 2006 that the experimental yield strength has been determined to agree
Available online 26 June 2017
with the theoretical prediction. Pillars with diameters smaller than 427 nm deform homogeneously and
show plasticity comparable to that of metals. The mechanism for such unusual properties of a-C is
explored using high-resolution transmission electron microscopy (TEM) and Raman spectroscopy. The
results indicate that the near-ideal strength is ascribed to the limitation of both the size and the number
of defects with the smaller sample size. Large plasticity is accompanied by material densification and
phase transformation at compressive stress. This finding widens the possible application of strong-and-
plastic ceramic films for both biomedical and micro/nano-electromechanical systems (MEMS/NEMS).
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction growth, rather than by prohibiting crack initiation, and cannot

Ceramics generally exhibit high strength and superior wear and
corrosion resistances, making them useful in a wide range of ap-
plications, including biomedical and micro/nano-
electromechanical systems (MEMS/NEMS) [1]. The lack of plas-
ticity is the major drawback of ceramics, which is attributed to the
strong iono-covalent bonding forces that restrict the generation
and movement of dislocations [2]. The inability to accommodate
the elastic energy due to loading leads to catastrophic and unpre-
dictable failure [3]. Due to the essential roles played by ceramics in
economic development, intense research has been devoted to
improving the performance of ceramics. Sustained efforts for
innovation have resulted in the development of ceramic matrix
composites (CMC), where a ductile phase is introduced to improve
the toughness of ceramics [4]. Different materials, such as graphene
[5], metals [6], and carbon nanotubes (CNT) [7], have been applied
for CMC. After implicitly introducing abundant interfaces to deflect
cracks, the toughness of CMC can be improved. Nevertheless, such a
toughness enhancement mechanism functions by resisting crack
* Corresponding author.
E-mail address: cliu224@cityu.edu.hk (C. Liu).
promote plasticity [3]. To date, plasticity of ceramics has been ob-
tained by creating and promoting dislocations at high temperature
[8]. Plasticity at room temperature in sub-micrometer length scale
ceramics has rarely been realized.
Significant progress has been achieved in recent years in the
optimization of alloy performance [9]. For instance, the strength of
an alloy is improved by amorphization because an amorphous alloy
(metallic glass) is free from dislocations and grain boundaries [10].
It has been reported that the fracture strength of metallic glass
approaches E/50 (where E is the elastic modulus) [11]. Most
recently, Wu et al. [12] reported the fracture strength of E/20, which
is very close to the proposed ideal strength of metallic glass.
However, the long-standing dilemma of strength-plasticity trade-
off causes brittle fracture of metallic glass upon deformation for
sizes above 200 nm [13]. This drawback can be overcome by
applying a dual-phase metallic glass [14]. Numerous shear band
nuclei are formed in the soft amorphous phase and are arrested by
the hard amorphous phase, encouraging formation of multiple
shear bands and making the strong material ductile [15].
Inspired by the concept of dual phase structure for enhancing
the alloy strength and plasticity, we report an amorphous carbon
ceramic that achieves near-ideal strength (~E/11) and large plas-
ticity (~70%) at room temperature. These unique properties are

http://dx.doi.org/10.1016/j.carbon.2017.06.082
0008-6223/© 2017 Elsevier Ltd. All rights reserved.
 C. Liu et al. / Carbon 122 (2017) 276e280
achieved by a combination of a dual phase microstructure and a
phase transformation that is introduced upon deformation. A
graphite that is entirely sp2 type has low hardness and good plas-
ticity, while diamond that is sp3 type reveals strength of ~0.25 TPa
with no plasticity and fails by cleavage fracture [16]. It has also been
reported that the sp2 bonds may transform into sp3 under high
stress [17]. Hence, it is anticipated that if a carbon-based material
consists of a mixture of sp2 and sp3 phases, high strength and large
ductility could be achieved simultaneously. This carbon-based
material containing sp2 and sp3 bonds is referred to as dual-
phase-amorphous-carbon (a-C). We demonstrate two unique and
useful properties of a-C: (1) the yield strength increases from
16.6 GPa to 21.8 GPa with sample diameter decreasing from 674 nm
to 227 nm; and (2) when sample diameter is smaller than 427 nm,
the material deforms homogeneously under compressive loading
and achieves near-ideal strength without catastrophic failure. To
the best of our knowledge, this report describes the first time that
the experimental yield strength of a-C has been found to agree with
the theoretical prediction since 2006 [18]. This finding could widen
the range of possible applications of a-C ceramics for both
biomedical applications [19] and MEMS/NEMS [20].
2. Experimental methods
The 1.5-mm-thick a-C films were deposited on Si wafers in a
closed-field unbalanced magnetron sputtering (CFUBMS) system.
The deposition was conducted with the background pressure of
5
105 Pa, target power of 2 kW, and substrate bias voltage
of 140 V. Substrate bias voltage during deposition is an important
factor that affects surface morphology and structure of carbon
coatings [21e23]. In this study, a-C coatings were first deposited
with the bias voltages varying from 20 V to 200 V and then their
surface morphology was analyzed. The a-C coating deposited with
the bias of 140 V reveals a very smooth surface (average
roughness < 1 nm) without observable pinholes or defects, as
measured using atomic force microscope (not shown here);
hence, 140 V was selected to be the substrate bias voltage for a-C
deposition. The pillars for compression tests were fabricated on the
surface of a-C coated Si disk using a focused ion beam workstation
(FIB, FEI SCIOS). The pillars were prepared by top-down milling
with sequentially decreasing outer and inner diameters of the
patterns at the working voltage of 30 kV. Removal of material re-
laxes the local internal stress such that the internal stress within a
micropillar is negligible [24]. To minimize the possible surface
damage caused by the Ga ions, the FIB beam current was gradually
reduced along with decreasing pattern diameters, and the beam
current applied for the final trim was 1.5 pA. The pillar diameters
ranges from 227 nm to 674 nm, the aspect ratio (height/width) was
between 2 and 3, and the height was less than the film thickness.
Fig. 1. The pillar with initial diameter of 627 nm (taper angle < 2 ). (a) Engineering stress-strain curve, SEM images of (b) as-fabricated and (c) fractured pillar.
277
The taper angle was carefully maintained to be smaller than 2
(Fig. 1(b) and Fig. 2(b)) to provide sufficient test accuracy [25].
Uniaxial compression tests were conducted in a nanoindenter
(Hysitron’s TI950) with a 5-mm-diameter diamond flat punch tip.
Prior to pillar compression, the diamond tip was indented on a-C
matrix several times until the thermal drift was lower than 0.1 nm/
s, indicating that the nanoindenter reached a stable state. Each
compression test was calibrated by measuring the thermal drift for
20 s and compensating the compression using the determined
thermal drift [26]. A constant strain rate (~5
103 s1) was
applied for all compression tests in order to eliminate the strain
rate effect. The compression tests were conducted in the
displacement control mode, and the maximum applied load ranges
from 2000 mN to 10000 mN with varied maximum displacement.
The raw load-displacement data were used to calculate the engi-
neering stress and strain. The Young’s modulus correction formula
for a pillar was used to generate the engineering stress-strain
curves [27].
The morphology and structure of compressed pillars were
analyzed using a field emission scanning electron microscope
(FESEM, FEI Quanta 450 FEG) and a transmission electron micro-
scope (TEM, JEOL JEM-2011F). The TEM sample was prepared by
lifting out a micro-sized lamella thinned to ~20 nm and transferring
it to a Cu grid inside the FIB workstation. The phase transformation
upon compression was characterized using Raman spectroscopy
with a 514.5 nm Arþ laser (HR LabRAM) and an optical microscope
(Olympus BX41). The spectra were obtained from 500 to 2000 cm1
with the signal collection time of 10 s at the power of 50 mW; two
collections were added for final spectrum. To avoid the possible
errors in Raman spectroscopy observations, three compressed pil-
lars were examined, and three as-fabricated pillars with the same
initial size of the compressed pillars were analyzed as a reference.
The Raman spectra were fitted with Gaussian peaks to quantita-
tively evaluate the D and G band changes.
3. Results
Fig. 1 shows the typical engineering stress-strain curve of a pillar
with the diameter of 627 nm (Fig. 1(a)), as well as its SEM images
before (Fig. 1(b)) and after fracture (Fig. 1(c)). According to the
curve, elastic loading is followed by plastic deformation and work
hardening and catastrophic failure at ~70% strain. Even though the
pillar could sustain large strain and exhibits plasticity, it fails by
cracking along the load axis (Fig. 1(c)). We observed that the pillars
with initial size larger than 427 nm behave similarly. Since most
ceramics fail by cracking [1], it appears that the a-C pillars with the
diameters in the 427e674-nm range deform similar to ductile
materials and fail similar to brittle ceramics.
Surprisingly, pillars smaller than 427 nm deform
278 C. Liu et al. / Carbon 122 (2017) 276e280
(a) (b)
Fig. 2. (a) Engineering stress-strain curve of a 245-nm-diameter pillar, SEM images of (b) as-fabricated and (c) compressed pillar.
homogeneously under a uniaxial compression load. Fig. 2(a) pre-
sents the stress-strain curve of a 245-nm-diameter pillar, and
Fig. 2(b and c) show SEM images of the as-fabricated and com-
pressed sample. Different from the catastrophic failure for larger
samples, the 245-nm-diameter pillar shows the characteristics of a
ductile material. After reaching the yield point, the pillar exhibits
non-linear plasticity and work hardening. SEM image of the com-
pressed pillar (Fig. 2(c)) indicates that there is no crack either
within or on the surface of the pillar. This observation demonstrates
that the plastic deformation occurs without crack generation, and
the entire pillar rather than a localized area experiences plastic
deformation. The diameter of the pillar at the middle increases
uniformly by 54% after compression, as shown in Fig. 2(b and c).
Fig. 3 displays the yield strength of pillars as a function of their
initial diameter. With decreasing pillar size from 674 nm to 227 nm,
the yield strength gradually increases from 16.6 GPa to 21.8 GPa.
The strength-modulus (s/E) relationship is a widely accepted cri-
terion for evaluation of the fundamental mechanical properties of
materials, and the s/E of 1/10 is used for all ideal materials [28]. We
observed that the s/E is ~1/11 for a-C pillars with initial diameters
varying from 227 nm to 393 nm, indicating that these pillars have
reached near-ideal strength. The Young’s modulus obtained from
the stress-strain curve is 240 GPa, in good agreement with the
modulus determined by the nanoindentation experiments.
Schaufler et al. [29] have fabricated an a-C:H coating with the
strength of 7.3 GPa and s/E of ~1/30, and Espinosa et al. [20] have
Fig. 3. Yield strength and plasticity as a function of pillar diameter. The plasticity is
characterized according to the engineering stress-strain curves and SEM images.
(c)
also prepared ta-C with the strength (E/30) that is close to theo-
retical limit.1 By varying deposition parameters, Panwar et al.
[30e33] fabricated carbon coatings with ultra-high hardness
ranging from 30 to 40 GPa and found that the hardness/modulus
(H/E) ratio is approximately 0.1. This ratio is an important param-
eter describing the wear behavior of carbon coatings because a high
H/E usually corresponds to good wear resistance. To the best of our
knowledge, this work represents the first time that the experi-
mental yield strength of a-C has approached the theoretical results
(E/10) predicted by Fyta et al. [18]. Strikingly, our a-C pillars with
diameters smaller than 427 nm not only show near-ideal strengths
but also show large plasticity under strain (~70%), as indicated by
both stress-strain curves and SEM observations. The mechanism for
the near-ideal strength and large plasticity is discussed below.
To reveal the structural transformation upon compression, the
cross-section TEM specimen of a compressed pillar with the initial
diameter smaller than 427 nm was prepared by FIB milling and
examined using TEM. As shown in Fig. 4, the pillar remains amor-
phous after the compression, implying no deformation-induced
crystallization. Material densification inside the pillar is indicated
by the white arrows in Fig. 4(a), as identified by the darker region
compared with the a-C matrix. It is generally accepted that the
mass-thickness contrast is most important in the TEM image,
especially for amorphous materials that are free from diffraction
contrast [34]. It means that the variation in mass and thickness
results in the contrast in the TEM image, and the darker region in
the bright field TEM image originates from either a denser or
thicker area. Considering that the TEM sample is thinned to ~20 nm
using the FIB technique, we can conclude that the effect of the
variation in sample thickness is negligible, as is also confirmed by
the identical intensity in the a-C matrix. Hence, the contrast in
Fig. 4(a) reflects mass change upon deformation, and the darker
region qualitatively indicates a higher mass density. The densifi-
cation occurs inside the entire pillar, again confirming that the
entire section, rather than a localized area, undergoes plastic
deformation. The origin of the densification is discussed below. It is
noted that micro void-like defects are formed near the edge of
pillar. Unlike the other parts of the pillar, the edge not only expe-
riences uniform compressive stress during compression but also
withstands the tensile stress from the base material that surrounds
a pillar. With increasing tensile stress, the domains with short
range order shrink, and defect nucleation and growth are induced
in a-C [35]. Consequently, void-like defects are formed at the edge
under tensile stress. The HRTEM image indicates that these regions
1
Schaufler et al. [29] and Espinosa et al. [20] presented fracture strength results
in their work. Generally, fracture strength is larger than the yield strength; it is
noted that the s/E should be smaller than 1/30 when yield strength is considered.
 C. Liu et al. / Carbon 122 (2017) 276e280
Fig. 4. TEM images of compressed pillar. (a) entire pillar, (b) HRTEM image corresponding to the boxed area in (a), which reveals the structure of void-like regions. The broad halo
ring in selected area electron diffraction pattern (inset in Fig. 4(a)) illustrates the amorphous nature of compressed pillar. The brighter region in Fig. 4(b) indicates its lower atomic
density.
have a lower atomic density. The lower atomic density is suggested
by the brighter region in the HRTEM image. Since the contrast
originates from mass variation, with carbon being the only element
in a-C, the lower mass density is therefore considered the lower
atomic density in the brighter area. While void-like defects are
formed, these defects have not grown into cracks, indicating that a-
C reveals superior resistance to the initiation of cracks. These re-
sults suggest that a-C shows resistance against initiation and
propagation of cracks [4], which is in agreement with the high
strength and plasticity measured during the compression tests.
Densification in a-C is usually accompanied by a phase transition
from sp2 to sp3. To elucidate the possible phase transformation, the
compressed pillar was analyzed using Raman spectroscopy, and
compared with an as-fabricated pillar with the same initial size
(typical spectra are shown in Fig. 5). The Raman spectra consist of
overlapped D-peak (centered at ~1380 cm1) and G-peak (centered
at ~1540-1580 cm1), which is a typical characteristic of a-C coat-
ings [36]. The D peak indicates the A1g breathing mode of the sp2
atoms only in aromatic rings. The G peak reveals the E2g stretching
mode of the sp2 atoms in both aromatic rings and olefinic chains
[37]. The spectrum of the compressed pillar reveals a more intense
D peak compared to that of the as-fabricated material. The intensity
ratio between the D peak and the G peak (ID/IG) rises from 2.14 to
3.23. ID and IG are determined as the corresponding peak areas. As is
well-known, ID/IG increases with decreasing disorder [38], and the
a-C with a higher sp3 concentration has been reported to exhibit a
higher D peak intensity [37,39]. The increased ID/IG after
compressed pillar
fitting
Intensity (a.u.)
D G
as-fabricated pillar
fitting
D G
800 1000 1200 1400 1600 1800 2000
-1
Raman shift (cm )
Fig. 5. Typical Raman spectra for compressed pillar, as well as an as-fabricated pillar
with the same initial size. (A colour version of this figure can be viewed online.)
279
compression implies a transition from sp2 to sp3 and toward a more
ordered structure. During compression, the stress increases from
0 to over 10 GPa, which could explain the carbon bond alignment
[35] and the phase transition [40]. Hence, the a-C becomes more
ordered and the sp3 content is increased after the compression.
Normally, an increase in the sp3 concentration in a-C corresponds
to increasing hardness [17]. The phase transformation explains the
work hardening behavior of a-C during plastic deformation
(Figs. 1(a) and 2(a)). Furthermore, TEM analysis reveals material
densification inside an a-C pillar upon compression. The density of
graphite (entirely sp2) is 2.25 g/cm3, and that of diamond (entirely
sp3) is 3.51 g/cm3 [41]. It is anticipated that a transition from sp2 to
sp3 will lead to material densification, which is in agreement with
the TEM observation.
The near-ideal strength of the a-C micropillar could be explained
by the limitation of both dimension and number of defects with the
smaller sample size. Failure in brittle materials is initiated by crack
formation and propagation; hence, the strength of such materials is
highly dependent on their defects. It is expected that a smaller
sample with lower possibility of pre-existing defects as well as a
limitation on the defect size could possess higher strength. Ac-
cording to Griffith’s brittle fracture theory [42], the stress s
required to propagate a pre-existing defect is
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
  
s¼ 2 gE 1  n2 pc ; (1)
where g is the surface energy, E is the elastic modulus, n is Poisson’s
ratio, and c is the radius of the pre-existing defect. Hence, a smaller
specimen with smaller defect size generally results in higher crack
propagation stress, making it more difficult for the cracks to be
initiated.
It has been reported that as the stress approaches the theoretical
strength of material, the atomic bonds inside a-C are rotated to
align with the loading axis, resulting in a more ordered structure
[35]. These aligned carbon bond chains could sustain very high
stress, with molecular dynamics simulations suggesting that three
carbon-carbon chains are able to bear a stress of 10 GPa [35]. The
bond alignment also dissipates the elastic energy and accommo-
dates the imposed deformation. The denser carbon atoms due to
the phase transition are able to impede the crack growth. The
transformation of the bonding from sp2 to sp3 has been shown
using Raman spectroscopy (Fig. 5), and the resistance against crack
propagation has been demonstrated using TEM (Fig. 4(b)). Conse-
quently, the limitations of the defects, sp3 phase transformation
and crack restriction combined to promote the near-ideal strength
and high plasticity of the amorphous carbon.
280 C. Liu et al. / Carbon 122 (2017) 276e280
4. Conclusions
The dual-phase amorphous carbon (a-C) reveals near-ideal
strength (~E/11) and large plasticity (~70%). For diameters smaller
than 427 nm, the a-C pillars show plasticity comparable to that of a
metal. TEM analysis indicates that the entire pillar undergoes
plastic deformation and material densification upon compression.
Raman spectroscopy reveals in detail the phase transformation
when a pillar was subjected to deformation. The near ideal strength
of a-C is due to the limitation of both the number and size of defects
in a-C with the smaller sample size, while large plasticity is
accompanied with the material densification and sp2/sp3 phase
transformation upon compressive loading.
Acknowledgement
The authors are grateful to Dr. Ge WU in City University of Hong
Kong for the insightful discussion. The Raman tests have been
conducted in Plasma lab of City University of Hong Kong, we thank
Mr. Hao WU for assisting Raman tests.
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