Piezoelectricity in single-molecular-layer transition metal dichalcogenide
Hanyu Zhu1, Yuan Wang1, Jun Xiao1, Ang-Yu Lu2, Lain-Jong Li2 and Xiang Zhang1
Background
Piezoelectricity: definition
Piezoelectricity allows precise and
robust conversion between electricity
and mechanical force, and arises
from the broken inversion symmetry
in the atomic structure. It has found a
wide range of applications in nano-
electro-mechanical systems (NEMS).
Material challenge
Rough surface
and dangling bonds
What is the ultimate scale limit of piezoelectric devices? For traditional
materials it is challenging to get high-quality surface for freestanding
structures. In addition, when the thickness approaches a single molec-
ular layer, the large surface energy can cause piezoelectric structures
to be thermodynamically unstable. Prior to this study, there was no ex-
perimental measurement of the intrinsic piezoelectric properties of
sub-nanometer crystals.
Opportunity: layered materials
Chhowalla et al, 2013
S 0.3
Mo
Transition-metal dichalcogenides, such
as MoS2 can retain their structural asym-
metry down to the single-layer limit with-
out lattice reconstruction under ambient
condition, that enables two dimensional
piezoelectricity. The membrane has a
total thickness of 0.6 nm and is biocom-
patible for device applications.
1
NSF Nano-scale Science and Engineering Center (NSEC), University of California, Berkeley, CA, USA
2
Physical Science & Engineering Division, King Abdullah University of Science and Technology, Thuwal, Saudi Arabia
Measure in-plane piezoelectricity Angular & layer dependence Acknowledgement & References
Supported by the US DOE Energy Frontier Research Center under
Application: Due to its 3-fold symmetry the piezoelectric cou-
We combined a laterally applied E award DOE DE-AC02-05CH11231 and NSF EFRI 2-DARE 1542741
Resonator & Motor pling of the MoS2 monolayer is:
electric field and nano-indentation
(electricity to strain) θ
in an atomic force microscope [1] Hanyu Zhu, et al., Observation of piezoelectricity in free-standing
(AFM) to measure the in-plane monolayer MoS2, Nature Nanotechnology 10, 151–155 (2015).
piezoelectrically generated mem- The change of sign from the upper devices to the [2] Ang-Yu Lu, et al., Janus atomic monolayers of transition metal di-
brane stress. Suspending MoS2 lower ones allowed us to assign the atomic orien- chalcogenides, Nature Nanotechnology, AOP 100 (2017).
minimized substrate effects such as Optical lever tation, i.e. differentiating the crystal with its mirror
doping and parasitic charges. The image. We also measured the thickness depen-
dence of the piezoelectric coefficient from natural
Sensor & Generator
two electrodes were oppositely
biased relative to substrate to Cantilever 2H-MoS2 crystals. For even-layer membranes, Other IoT Related Works
(strain to electricity) reduce electrostatic force. The ac- the contributions to piezoelectricity from alternat-
-
tuation frequency was kept much ing orientations of adjacent layers cancelled.
Au electrode
That’s why bulk 2H-MoS2 is not piezoelectric.
lower than the mechanical reso-
nance and quasi-static analysis is + 350
coupling (pC/m)
applicable. SiO2 300 300
Piezoelectric
200
Si substrate
100
250
0 200
-100 150
-200 100
Device fabrication -300
-10 0 10 20 30 40 50 60 70
50
0
1 2 3
Angle (deg) Layer number
MoS2 monolayer was produced by
mechanical exfoliation on
Size effect in
poly-methyl-methacrylate (PMMA).
The electrodes were designed to
Out-of-plane piezoelectricity
ferroelectric materials
be parallel to or at 60° with respect Light emitting diode integrated on silicon:
to the sharply cleaved edges. Sus- H2 plasma Efficient carrier injection and light emission was achieved in
pension, mechanical clamping and stripping heterojunctions of monolayer MoS2 (n-type) and heavily doped
electrical contact were simultane- (p-type) silicon. (Ye et al., Exciton-dominant electroluminescence from
ously achieved by one-step elec- Thermal a diode of monolayer MoS2, Appl. Phys. Lett. 104, 193508 (2014).)
5 µm tron-beam lithography (EBL). The selenization
MoS2 flake was released by critical
point drying. Many piezoelectric NEMS designs rely on out-of-plane electromechan-
Peng et al, 2000 ical coupling. However MoS2 has out-of-plane mirror symmetry and no
Junquera et al, 2003
piezoelectricity along z-axis. We engineered a physical-chemical pro-
cess to selectively replace the sulfur atoms on one side with selenium
and created structural asymmetry.
Electric field
2 µm
Results
Monolayer laser on silicon: Using a whispering gallery cavity with a
15 Scanning piezoresponse high quality factor and optical confinement, we observe bright excitonic
40 lasing from a monolayer WS2 at visible wavelengths under optical
pumping, a major step towards two-dimensional on-chip optoelectron-
Piezoelectric
30 10
load (pN)
Load (nN)
ics for optical communication and sensing. (Ye et al., Monolayer exci-
20
5 tonic laser, Nat. Photon. 9, 733–737 (2015).)
10
0 0
0 20 40 60 80 0 20 40 60 80 500 nm
Depth (nm) Depth (nm)
The experimental load of on a 0.4
monolayer MoS2 device (black
stress (mN/m)
Piezoelectric
y
scatter) was fit with Y2D = (1.2 ±
0.1) × 102 N m−1 and σ2D = 45 ± 0.2
The MoSSe flakes were directly synthesized
x 5 mN m−1 (red curve). For this 0.1 on atomically flat conductive substrates. We
device, piezoelectric stress of Δσ used piezoresponse force microscopy (PFM)
0.0 500 nm
Electric field = 0.12 ± 0.02 mN m −1
was with resonance enhancement. DC bias was
p
0 1 2 3 Large-scale chemical assembly of atomically thin circuits:
deduced. A positive sign was applied to balance the potential of the tip and
Driving Voltage (V) Spatially controlled synthesis of heterostructures made of monolayer
assigned because the signal and the substrate and minimized the electrostatic effect. There is clear piezo-
MoS2 and graphene enables high-performance flexible circuits. Zhao
the driving voltage were in phase. The piezoelectric stress increased electric contrast between the a MoSSe monolayer and the substrate, but
et al., Large-scale chemical assembly of atomically thin transistors and
with ramping driving voltage (black scatter). A linear fit (red curve) no contrast for random alloy or folded bilayer. The estimated piezoelectric
circuits, Nat. Nano. 11, 954–959 (2016).
gives e11 = (2.9 ± 0.5) × 10−10 C/m (or d = (2.9 ± 0.5) pm/V, The values coefficient d33 is around 0.1 pm/V, and can potentially be improved by in-
agree well with previous ab initio calculations and experiments. creasing the dipolar contrast.