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Plowing-Induced Nanoexfoliation of Mono - and Multilayer MoS2 Surfaces
Plowing-Induced Nanoexfoliation of Mono - and Multilayer MoS2 Surfaces
Alper Özoğul ,1 Felix Trillitzsch,1 Christof Neumann,2,3 Antony George,2,3 Andrey Turchanin,2,3 and Enrico Gnecco 1
1
Otto Schott Institute of Materials Research (OSIM), Friedrich Schiller University Jena, 07743 Jena, Germany
2
Institute of Physical Chemistry, Friedrich Schiller University Jena, Lessingstrasse 10, 07743 Jena, Germany
3
Jena Center for Soft Matter (JCSM), Philosophenweg 7, 07743 Jena, Germany
The surface structures resulting from scratching monolayer MoS2 on SiO2 and multilayer MoS2 using diamond
nanotips with normal forces up to 3 μN and scan velocities up to 10 μm/s in ambient conditions are compared. In
both cases the damage process initiates with normal forces of about 2 μN. As shown by postmortem AFM images
the monolayer is peeled off along the zigzag direction of MoS2 and folded in the form of flat triangular flakes.
Wrinkling and multiple folding can be associated to debris accumulation originated from the SiO2 substrate,
which is also scratched by the tip. On the multilayer MoS2 thicker chips with linear size of about 100 nm
and height of few tens of nm are rolled out. The chipping is associated to a distinct stick-slip motion of the
AFM tip with repetition period logarithmically increasing with the velocity but definitely below the chip length,
suggesting that the process occurs through a series of exfoliation events. Simple energetic considerations allow
to explain why peeled monolayers tend to fold over the untreated surface while thicker layers tend to bend and
form chips.
DOI: 10.1103/PhysRevMaterials.4.033603
FIG. 1. (a) Tapping-mode AFM image of a MoS2 monolayer (with one or two overlayers in the colored areas) after scratching with FN =
3 μN and v = 100 nm/s forth and back (two bottom lines) or FN = 3 μN and v = 1 μm/s (two top lines). (b) Lock-in topography image
corresponding to the rectangular area in (a). The inset shows a high resolution (tapping-mode) image corresponding to the rectangle. The
yellow and blue arrows indicate wrinkling and folding effects, respectively. (c) Cross-section along the white line in (b).
layers may be formed, which is a well-known outcome of III. RESULTS AND DISCUSSION
the CVD growth process [12]. A detailed description of the
A. Nanoscratching of MoS2 monolayers on SiO2
preparation process is given in [13]. The bulk sample is
commercially available natural MoS2 . Representative results of plowing wear on MoS2 islands
The optical microscopy image was taken with a Zeiss Axio on SiO2 (AFM topography images recorded after damaging)
Imager Z1.m microscope equipped with a 5 megapixel CCD are shown in Figs. 1(a) and 1(b). Note that the surface was
camera (AxioCam ICc5) in bright field operation. For optimal scratched along a direction forming an angle of about 45o
absorption contrast of the 2D material, Si substrates with with respect to the closest edge of the triangle [Ref. [10] (Fig.
300 nm of oxide layer were used. This contrast is due to S3)], which corresponds to the zigzag orientations of the Mo
interference, with the oxide substrate acting as a spacer, as and S atoms [11]. A normal force FN ≈ 2 μN was required to
explained for instance in Ref. [14]. initiate damage, independently of the scan velocity. The MoS2
The scanning electron microscopy images were obtained is peeled off during the scratch test in the form of flakes which
by a Zeiss Sigma VP at a beam energy of 15 kV using the are multiply folded (as discussed below) but not completely
in-lens detector of the system. detached from the substrate. The bare SiO2 regions remaining
Scratch tests were performed with a NanoWizard 4 AFM after peeling [Fig. 1(b)] have a triangular shape with cutoff
(JPK Instruments) by using AIST-NT D300 AFM cantilevers line initially following the zigzag direction of MoS2 (as seen
with single crystal diamond tips (spring constant k = 35 N/m, also from comparison with the orientation of the island) but
nominal tip radius r ≈ 20 nm) glued on them [Ref. [10] (Fig. suddenly turning by 90o along the armchair direction and
S2)]. Normal force calibration of the cantilevers was done by ending back up in the scratch line. The lateral force (friction)
the thermal noise deflection method, as described in Ref. [15]. profile acquired while scratching is rather irregular [as seen
Lateral force calibration of the cantilevers were done by the in the example given in Ref. [10] (Fig. S4)] as compared to
wedge calibration method, as described in Ref. [16]. Tip the profiles on the bulk material surface presented in the next
velocity and normal force were set constant during scratching. section. The fluctuations of the friction force are in the order
Both samples were scratched with different tip velocities and of 500 nN and bear no clear resemblance with the morphology
normal forces sufficient for scratching MoS2 , in the range of of the scratched surface.
1–3 μN. Lateral deflection of the cantilever and tip height As seen in Fig. 1(b) the material displaced by the diamond
were recorded while scratching in real time. Samples were tip is arranged asymmetrically with respect to the scratch line,
scanned before and after scratching in tapping mode with which is possibly due to the chosen direction of motion (far
the same tip. Scratches were made parallel to the step edges from the zigzag and armchair crystallographic orientations)
on MoS2 triangles (zigzag direction) [11], and in arbitrary and/or to the structure of the very end of the tip. More details
directions on the bulk sample. To minimize the effect of on the morphology of the displaced material are given in the
build-up on the tip, scratches in each set were made in an inset. On the lower side of the scratch the peeled layers show
irregular order. evidence of wrinkling (yellow arrows) and multiple folding
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FIG. 4. AFM topography image of the bulk MoS2 surface after scratching. The set points are 1, 1.5, 2, 2.5 and 3 μN from left to right. Tip
velocities during scratch are 100 nm/s, 320 nm/s, 1 μm/s, 3.2 μm/s, and 10 μm/s from bottom to top. The arrow corresponds to the scratch
direction.
conditions as the monolayer. In this case, we performed section. Every time the friction force reaches a critical value
25 scratch tests with five different scan velocities and five corresponding to the peaks in Fig. 5(b), the chip detachment
different values of the normal force FN . The minimum force advances (with possible sliding of inner layers past each other
required to damage the surface and build up MoS2 structures [28]) until the process ends and a new chip starts to be formed
is 2 μN, i.e., in the same range observed for the MoS2 at a moment not clearly defined in the friction profiles.
monolayer on SiO2 . Above this threshold, a series of chips The average slope k of the lateral force curves in the
with variable length and height (up to 150 nm and ∼75 nm, stick phase, which corresponds to the lateral stiffness of the
respectively) are formed for all values of the scan velocities. tip-substrate contact [29], has been estimated for all values
At the threshold value of FN = 2 μN the series is present only
along limited sections of the scratched line (if v < 10 μm/s).
Note that we use the term “chips” to identify these structures
since the comparison between their height and the depth of
the scratch groove (two to five monolayers) implies that the
structures must contain voids. Due to the high curvature (R ∼
5−20 nm) the chips could not be resolved in details as the
flakes in Sec. III A. On the other hand, important information
could be inferred from the friction force variations recorded
while scratching.
In Fig. 5, the friction variations are overlapped to cor-
responding cross-sections of the chips, as recorded by the
same tip after scratching. The friction fluctuates irregularly
(with rms of up to 2.2 μN) on the undamaged part of the
MoS2 surface, whereas a clear saw-tooth profile is observed
when the chips are built up. These profiles are reminiscent
of the stick-slip motion accompanying the rippling of brittle
[24] or compliant surfaces [25] scratched by a silicon tip.
Differently from those cases, where the stick-slip repetition
d corresponds to the distance between two ripples, d is less
than the linear size of the chips, although still in the tens of
nm range (see below). It is also noticeable that the baseline
of the friction force follows the topography of the scratch
by increasing in the areas of build-up, whereas the stick-slip
motion does not show any noticeable correlation with it. The
stick slip is thus indicating discontinuous advancement of the
tip accompanied by detachment and bending but no folding
of a chip as schematically shown in Fig. 2(b). It is indeed
well-known that the bending stiffness D of MoS2 layers grows
rapidly with their thicknesses and the strain energy even more.
For instance, the bending stiffness of a MoS2 flake formed by
three monolayers is one order of magnitude larger than the
value of D = 9.6 eV corresponding to one monolayer only
[26]. At the same time the strain energy becomes two orders of FIG. 5. (a) Topography profiles after scratching (thin curves) and
magnitude higher than the interlayer binding energy between overlaid lateral deflection signals during scratches (thick curves) cor-
monolayers, 0.32 J/m2 [27]. As a result, the chips simply responding to the scratch lines marked with asterisks in Fig. 4. (b) In-
bend with radii of curvature of few tens of nm but do not sets corresponding to the rectangle in (a). Vertical bars correspond to
fold on the substrate as the monolayers in the previous sub- 2 nm (continuous lines) and 1 μN (dashed lines), respectively.
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