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2D FERROELECTRICITY AND
PIEZOELECTRICITY FOR ELECTRONIC
DEVICES
YUAN Shuoguo
PhD
The Hong Kong Polytechnic University
2020
The Hong Kong Polytechnic University
Department of Applied Physics
2D ferroelectricity and piezoelectricity for electronic devices
YUAN Shuoguo
A thesis submitted in partial fulfillment of the requirements for the degree
of Doctor of Philosophy
August 2019
CERTIFICATE OF ORIGINALITY
I hereby declare that this thesis is my own work and that, to the best of my knowledge
and belief, it reproduces no material previously published or written, nor material that
has been accepted for the award of any other degree or diploma, except where due
acknowledgement has been made in the text.
(Signed)
YUAN Shuoguo (Name of student)
fffI YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
Abstract
Abstract
Two-dimensional (2D) layered materials have attracted enormous interests in
fundamental research and industrial applications due to their excellent physical
properties, such as electronic, optoelectric, thermal, optical, mechanical and magnetic
properties. Recently, ferroelectricity and piezoelectricity in 2D layered material
family were addressed, which leads to great potential applications for atomic-scale
smart electronic devices. The emerging 2D ferroelectricity and piezoelectricity can
yield fascinating behaviors with various functional devices.
In this thesis, firstly, the MoTe2 samples were prepared using mechanical
exfoliation and laser process. By combining first-principle calculations and
experimental studies, the robust room-temperature out-of-plane ferroelectricity is
realized in the monolayer MoTe2 with unexploited distorted 1T (d1T) phase. The
ferroelectricity origin in d1T-MoTe2 results from the spontaneous symmetry breaking
due to the relative atomic displacements of Mo atoms and Te atoms. A large ON/OFF
resistance ratio is achieved in ferroelectric devices composed of MoTe2 based van der
Waals (vdW) heterostructure. Secondly, piezoelectricity in 2D material family has
largely been predicted by theoretical calculations, but still few experimental
observations from them. The out-of-plane piezoelectric response can be achieved in
2D layered material In2Se3. In addition, a high-precision actuator device based on the
fffII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
Abstract
piezoelectricity in 2D atomic scale is demonstrated. Moreover, the vertical
ferroelectric polarization characteristic of In2Se3 is investigated by piezoresponse
force microscopy, which can retain the ferroelectric behaviour down to 6 nm. Thirdly,
the vertical piezoelectric response of several 2D layered materials is theoretically
absent via electric field or strain applied perpendicular to their surface due to the
inversion symmetry. Recently, vertical piezoelectric properties of In2Se3 were
reported, which exhibits low piezoelectric response. A remarkably enhanced
out-of-plane piezoelectric performance in 2D layered vdW heterostructure is reported.
In particular, the vdW heterostructure based piezoelectricity is not restricted by
layer-dependence and edge-effect. The enhanced piezoelectric properties result from
the band offset. In addition, the vdW heterostructure can be extended to other 2D
materials like WS2. The heterostructure is fabricated onto silicon substrate which is
compatible with state-of-the-art microfabrication technology.
The 2D ferroelectricity and piezoelectricity have been studied. The ferroelectric,
piezoelectric properties and related device applications of 2D materials have been
investigated. These studies provide a platform for designing new functionalities and
achieving unexpected applications in atomic-scale smart electronic devices and
electromechanical systems.
fffIII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Publications
List of Publications
Journal Papers
1. Shuoguo Yuan, Xin Luo, Hung Lit Chan, Chengcheng Xiao, Yawei Dai, Maohai
Xie, and Jianhua Hao*. Room-temperature ferroelectricity in MoTe2 down to the
atomic monolayer limit, Nature Communications 10, 1775 (2019).
2. Shuoguo Yuan, Weng Fu Io, Jianfeng Mao, Yancong Chen, Xin Luo, and Jianhua
Hao*. Large out-of-plane piezoelectricity in two-dimensional layered material
indium selenide, 2020, to be submitted.
3. Shuoguo Yuan, Sin-Yi Pang, and Jianhua Hao*. 2D transition metal
dichalcogenides, carbides, nitrides and their applications in supercapacitors and
electrocatalytic hydrogen evolution reaction, Applied Physics Reviews 7, 021304
(2020).
4. Shuoguo Yuan, Zhibin Yang, Chao Xie, Feng Yan, Jiyan Dai, Shu Ping Lau,
Helen L.W. Chan, and Jianhua Hao*. Ferroelectric-driven performance
enhancement of graphene field-effect transistor based on vertical tunnelling
heterostructures, Advanced Materials 28, 10048 (2016).
5. Weng-Fu Io, Shuoguo Yuan, Lok-Wing Wong, Sin-Yi Pang, and Jianhua Hao*.
Temperature-and thickness-dependence of robust out-of-plane ferroelectricity in
fffIV YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Publications
CVD grown ultrathin van der Waals α-In2Se3 layers, Nano Research
https://doi.org/10.1007/s12274-020-2640-0 (2020).
6. MeilinTu, Haipeng Lu, Songwen Luo, Hao Peng, Shangdong Li, Zhengdong Ke,
Shuoguo Yuan, Wen Huang, Wenjing Jie*, and Jianhua Hao*. Reversible
transition between bipolar memory switching and bidirectional threshold switching
in 2D layered K-birnessite nanosheets, ACS Applied Materials & Interfaces
https://doi.org/10.1021/acsami.0c04872 (2020).
7. Ran Ding, Chun-Ki Liu, Zehan Wu, Feng Guo, Sin-Yi Pang, Lok Wing Wong,
Weng Fu Io, Shuoguo Yuan, Man-Chung Wong, Michal Bartlomiej Jedrzejczyk,
Jiong Zhao, Feng Yan, and Jianhua Hao. A general wet transferring approach for
diffusion-facilitated space-confined grown perovskite single-crystalline
optoelectronic thin films, Nano Letters 20, 2747 (2020).
8. Sin-Yi Pang, Yuen-Ting Wong, Shuoguo Yuan, Yan Liu, Ming-Kiu Tsang, Zhibin
Yang, Haitao Huang, Wing-Tak Wong, and Jianhua Hao*. Universal strategy for
HF-free facile and rapid synthesis of two-dimensional MXenes as multifunctional
energy materials, Journal of the American Chemical Society 141, 9610 (2019).
9. Gongxun Bai, Shuoguo Yuan, Zhibin Yang, Yuda Zhao, Sin Yuk Choi, Yang Chai,
Siu Fung Yu, Shu Ping Lau, and Jianhua Hao*. 2D layered laterials of rare-earth
fffV YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Publications
Er-doped MoS2 with NIR-to-NIR down- and up-conversion photoluminescence,
Advanced Materials 28, 7472 (2016).
10. Hung-Lit Chan, Shuoguo Yuan, and Jianhua Hao*. Vertical graphene tunneling
heterostructure with ultrathin ferroelectric BaTiO3 film as a tunnel barrier, Physica
Status Solidi RRL 12, 1800205 (2018).
11. Huiying Du, Meilin Tu, Songwen Luo, Shangdong Li, Shuoguo Yuan, Tianxun
Gong, Wen Huang, Wenjing Jie*, and Jianhua Hao*. Transition from nonvolatile
bipolar memory switching to bidirectional threshold switching in layered MoO3
nanobelt, Journal of Materials Chemistry C 7, 12160 (2019).
fffVI YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Publications
Presentations in International Conferences
1. Shuoguo Yuan, Hung-Lit Chan, Jianhua Hao*. Piezoelectricity and
ferroelectricity in 2D layered materials for electronic devices, poster presentation,
2019 MRS Spring Meeting and Exhibit (April 22-26, 2019), Phoenix, Arizona.
(The Best Poster Award in the MRS Symposium)
2. Shuoguo Yuan, Zhibin Yang, Jianhua Hao*. Ferroelectric control of vertical
graphene field-effect transistor based on tunnelling heterostructures, poster
presentation, The 20th Physical Society of Hong Kong Conference (June 16-17,
2017), The Hong Kong University of Science and Technology, Hong Kong.
fffVII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
Acknowledgements
Acknowledgements
First and foremost, I would like to express my highest respect and sincere
appreciation to my supervisor, Prof. Jianhua Hao for his valuable suggestion, patient
guidance and continuous encouragement throughout the whole period of my
postgraduate study. His profound scientific insight and enthusiastic attitude towards
science and research has deeply inspired me to accomplish my PhD study.
I would like to express my great gratitude to Prof. Xin Luo, Prof. Maohai Xie,
Prof. Jiyan Dai, Prof. Feng Yan, Dr. Yang Chai for their generous assistance on my
experimental research or course study. I want to thank Dr. Vincent Chan and Dr.
Hardy Lui for their help in facility utilization in our department and materials research
centre in UMF.
I gratefully also appreciate our groupmates Dr. Wenjing Jie, Dr. Zhibin Yang, Dr.
Gongxun Bai, Dr. Wei Xu, Dr. Li Chen, Dr. Ming-Kiu Tsang, Dr. Ran Ding, Dr.
Beining Zheng, Mr. Man-Chung Wong, Mr. Hung-Lit Chan, Ms. Weng Fu Io, Ms.
Yongxin Lyu, Ms. Sin-Yi Pang, Mr. Feng Guo, Mr. Menglin Song, Mr. Jianfeng Mao,
Mr. Zehan Wu, Ms. Yuen-Ting Wong, Ms. Yuqian Zhao for their kind support to my
experiments. Besides, I would like to give my thanks to my friends and classmates for
their kind help and friendship.
fffVIII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
Acknowledgements
Lastly, I would like to thank my family for their endless love, support and
encouragement throughout my study and life.
fffIX YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
Table of Content
Table of Content
Abstract .......................................................................................................................... I
List of Publications ...................................................................................................... III
Acknowledgements .................................................................................................... VII
Table of Content ........................................................................................................... IX
List of Figures ........................................................................................................... XIII
List of Tables ........................................................................................................... XXII
List of Acronyms.................................................................................................... XXIII
Chapter 1 Introduction ................................................................................................... 1
1.1 Background of two-dimensional materials ...................................................... 1
1.1.1 Graphene ................................................................................................... 1
1.1.2 Transition metal dichalcogenides .............................................................. 4
1.1.3 Group III-VI compounds .......................................................................... 5
1.1.4 Graphene analogous .................................................................................. 7
1.2 Ferroelectric and piezoelectric properties of nanoscale films .......................... 9
1.2.1 Typical ferroelectric materials ................................................................... 9
1.2.2 Typical piezoelectric materials ................................................................ 16
1.3 Significance of research ................................................................................. 19
fffX YUAN Shuoguo
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Table of Content
1.4 Structure of thesis .......................................................................................... 22
Chapter 2 Experimental Methods ................................................................................ 24
2.1 Fabrication methods of 2D materials ............................................................. 25
2.1.1 Exfoliation ............................................................................................... 25
2.1.2 Physical vapor deposition ....................................................................... 28
2.1.3 Chemical vapor deposition ...................................................................... 30
2.2 Measurement methods ................................................................................. 32
2.2.1 Optical characterization .......................................................................... 32
2.2.2 Structural characterization ...................................................................... 33
2.2.3 Piezoresponse force microscopy characterization .................................. 38
2.2.4 Transport characteristic measurement ..................................................... 40
Chapter 3 Ferroelectricity in distorted 1T phase MoTe2 .............................................. 42
3.1 Introduction .................................................................................................... 42
3.2 Experiment ..................................................................................................... 51
3.2.1 Fabrication of d1T-MoTe2 samples ......................................................... 51
3.2.2 Thickness characterization of d1T-MoTe2 .............................................. 51
3.2.3 Raman characterization of d1T-MoTe2 ................................................... 53
3.2.4 Structural characterization of d1T-MoTe2 ............................................... 56
3.3 Ferroelectric characterization of d1T-MoTe2 ................................................. 59
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3.4 Ferroelectric mechanism of d1T-MoTe2 ........................................................ 65
3.5 Ferroelectric tunnel junction devices ............................................................. 69
3.6 Summary ........................................................................................................ 75
Chapter 4 Out-of-plane Piezoelectricity in the Exfoliated In2Se3 ................................ 77
4.1 Introduction .................................................................................................... 77
4.2 Experiment ..................................................................................................... 83
4.2.1 Preparation and measurement of In2Se3 samples .................................... 83
4.2.2 Phase characterization of In2Se3 samples ................................................ 84
4.3 Out-of-plane piezoelectric properties of In2Se3 ............................................. 87
4.4 Out-of-plane ferroelectric properties of In2Se3 .............................................. 93
4.5 Simulated piezoelectric actuator devices ....................................................... 96
4.6 Summary ........................................................................................................ 98
Chapter 5 Out-of-plane Piezoelectricity in Van der Waals Heterostructure .............. 100
5.1 Introduction .................................................................................................. 100
5.2 Experiment ................................................................................................... 101
5.2.1 Fabrication of In2Se3, MoS2 and WS2 samples ..................................... 101
5.2.2 Raman and PL characterizations of In2Se3/MoS2 heterostructure ......... 103
5.2.3 Raman and PL characterizations of In2Se3/WS2 heterostructure........... 104
5.2.4 Strcutural characterization of In2Se3 ..................................................... 105
fffXII YUAN Shuoguo
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Table of Content
5.3 Vertical piezoelectric properties of vdW heterostructure ............................. 107
5.3.1 Piezoelectricity in In2Se3 ....................................................................... 107
5.3.2 Piezoelectricity in monolayer MoS2 ..................................................... 109
5.3.3 Piezoelectricity in In2Se3/MoS2 vdW heterostructure ........................... 111
5.3.4 Piezoelectricity in In2Se3/WS2 vdW heterostructure ............................. 113
5.4 Physical mechanism of piezoelectric properties of vdW heterostructure .... 115
5.5 Summary ...................................................................................................... 121
Chapter 6 Conclusion and Future Prospect ................................................................ 122
6.1 Conclusion ................................................................................................... 122
6.2 Future prospect............................................................................................. 124
References .................................................................................................................. 127
fffXIII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
List of Figures
Figure 1.1 a) Schematic of monolayer graphene lattice.7 b) The electronic band
structure of graphene8. ................................................................................................... 4
Figure 1.2 Crystal structures of MoS2 with different polymorphisms9.......................... 5
Figure 1.3 Crystal structure of monolayer a) and bilayer b) α-In2Se3. .......................... 7
Figure 1.4 The hysteresis loop of typical ferroelectric materials. ................................ 10
Figure 1.5 The relationship between dielectrics, piezoelectrics, pyroelectrics and
ferroelectrics. ............................................................................................................... 11
Figure 1.6 The energy barrier diagram of the FTJ for two different polarization
directions, M1 stands for the metal 1, FE stands for ferroelectric barrier and M2
respresents the metal 249
. ............................................................................................. 14
Figure 1.7 Schematic of typical piezoelectric effect. ................................................... 17
Figure 2.1 A typical method to fabricate the 2D flakes by mechanical exfoliation75
. . 26
Figure 2.2 Liquid exfoliation based on sonication. The bulk crystal is sonicated in a
solvent system, which leads to exfoliate into the 2D nanosheets76
.............................. 28
Figure 2.3 Schematic of the PLD equipment78
............................................................ 29
Figure 2.4 Schematic of CVD growth ......................................................................... 32
Figure 2.5 Basic principle of Raman scattering ........................................................... 34
fffXIV YUAN Shuoguo
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List of Figures
Figure 2.6 Schematic of the second harmonic generation in non-centrosymmetric
materials, in which the excitation frequency is half of the generated light86
............... 35
Figure 2.7 Schematic of working principle of PFM .................................................... 40
Figure 2.8 Schematic of the experimental setup of CAFM95
....................................... 41
Figure 3.1 a) OM image of d1T-MoTe2, scale-bar, 3 μm. b) AFM image and
corresponding height profile of monolayer d1T-MoTe2, scale-bar, 0.5 μm. c) AFM
image of d1T-MoTe2 nanosheets onto Pt substrate, scale bar, 2 μm. d) Cross-sectional
TEM image of d1T-MoTe2, scale bar, 6 nm ................................................................. 52
Figure 3.2 Experimental and calculated Raman spectra of 2H and d1T-MoTe2 .......... 54
Figure 3.3 a) XPS spectra of d1T-MoTe2. b,c) HRTEM images of 2H and d1T-MoTe2,
arrows denote Te defects, scale-bar, 2 nm. d,e) EDS curves of 2H-MoTe2 and
d1T-MoTe2. .................................................................................................................. 57
Figure 3.4 a) OM image of MoTe2 nanosheets onto monolayer graphene. b) AFM
image and height curve of 5 layers d1T-MoTe2 nanosheets onto monolayer graphene.
c) Cross-sectional TEM image of 5 layers d1T-MoTe2 on monolayer graphene. d)
Raman spectrum of monolayer graphene layer used. e,f) Raman spectra of 5 layers
2H-MoTe2 and d1T-MoTe2 nanosheets onto monolayer graphene. ............................. 58
Figure 3.5 a) PFM phase hysteretic and butterfly loops of monolayer d1T-MoTe2. b,c)
PFM phase hysteretic and butterfly loops of d1T-MoTe2 before and after 30 days. d)
fffXV YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
PFM phase image of monolayer d1T-MoTe2, where the electrical poling was applied
by writing two square patterns with ± 8 V, scale bar, 1 μm ......................................... 61
Figure 3.6 a) Phase signals of d1T-MoTe2 nanosheets with different layer number onto
Pt substrate (layer number n=2, 3, 4, 9). b) The PFM phase hysteretic loop of 5 layers
d1T-MoTe2 nanosheets onto monolayer graphene. c,d) PFM phase hysteretic loops of
2H and d1T-MoTe2 taken at random locations, the inset shows the randomly selected
locations. e,f) In-plane PFM amplitude (top) and phase images (bottom) of
d1T-MoTe2 with 5 layers. ............................................................................................. 62
Figure 3.7 a) Raman spectra of d1T-MoTe2 film by MBE. b) Surface topography of
MoTe2 film by MBE. c) STM image of monolayer MoTe2 films by MBE. d,e) PFM
phase loops of monolayer MoTe2 films deposited onto HOPG and SiC substrate. f,g)
PFM amplitude loops of monolayer MoTe2 films deposited onto HOPG and SiC
substrate. h) Second harmonic generation spectrum from monolayer d1T-MoTe2 ..... 64
Figure 3.8 a) Top-view HRTEM image and intensity profile, the atomic structure of
d1T-MoTe2 is placed on top, scale-bar, 0.5 nm. b) Atomic structure image of
monolayer d1T-MoTe2 and the inset shows atomic structure model (cyan and orange
colors represent Mo and Te atoms, respectively), scale-bar, 0.2 nm. .......................... 66
Figure 3.9 a) Phonon dispersion of d1T-MoTe2. b) Phonon dispersion of the 1T-MoTe2,
with the structure of 1T shown in the middle. The unstable modes in M and K points
fffXVI YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
lead to the 1T′ and d1T-MoTe2, respectively. c) Energy barrier between d1T and
1T-MoTe2 (lable the 1T below the image at the lower middle, and the d1T at the upper
image). d) The top view of the trimerized/d1T-MoTe2, the structures show no
difference in trimerized and d1T-MoTe2 in the top view. The side view shows the
difference between the e) trimerized and f) d1T structure. g) The change of the dipole
moment in the d1T phase and the trimerized structure. h,i) Top-view and side-view of
charge density difference between ferroelectric d1T and paraelectric 1T phases (green,
purple, cyan, orange and pink colors denote negative charge, positive charge, Mo
atom, Te atom and polarization, respectively) ............................................................. 68
Figure 3.10 Layer-dependent Tc of d1T-MoTe2. .......................................................... 71
Figure 3.11 a) Temperature dependence of PFM phase loops of 5 layers d1T-MoTe2. b)
PFM phase loops of 16 layers d1T-MoTe2 at room temperature. c,d) AFM image and
height profile of MoTe2 with 16 layers ........................................................................ 71
Figure 3.12 Energy difference of the d1T phase and 1T phase with increasing layer
thicknesses. .................................................................................................................. 72
Figure 3.13 I-V characteristic of monolayer d1T-MoTe2 on Pt and inset shows the
energy diagram of FTJ devices .................................................................................... 73
Figure 3.14 I-V characteristic of few-layer d1T-MoTe2 on graphene and inset shows
the schematic of device structure ................................................................................. 74
fffXVII YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
Figure 3.15 a) Structure illustration of the d1T-MoTe2 and graphene heterostructure,
as well as the bandstructure of the heterostructures. b) The characteristic band of the
graphene is highlighted with the red ball, with the size proportional to the weights of
the electronic states on to the C atom .......................................................................... 75
Figure 4.1 Raman characterizations of α-In2Se3 nanosheets. a) OM image of In2Se3
nanosheets, scale bar, 4 μm. b) AFM images in the red square of OM image and
corrsponding height profile of 3 nm In2Se3 nanosheets, scale bar, 0.3 μm. c) Thickness
dependent Raman spectra of In2Se3 nanosheets. d) Raman spectrum of In2Se3
nanosheets .................................................................................................................... 85
Figure 4.2 a,b) XPS spectra of In2Se3 nanosheets. c,d) Elemental mapping of In and
Se. e,f) high-resolution TEM image of In2Se3 (scale bar, 3 nm) and the inset shows
SAED pattern of In2Se3 nanosheets ............................................................................. 86
Figure 4.3 EDS of In2Se3 nanosheets. .......................................................................... 87
Figure 4.4 Piezoelectrcity in α-In2Se3 nanosheets onto Pt substrate. Amplitude images
of 20 layers In2Se3 with different drive voltages (a: 1 V; b: 2 V; c: 3 V; d: 4 V; scale
bar, 0.3 μm) ................................................................................................................ 88
Figure 4.5 SHG spectrum of In2Se3. SH spectral intensity at 399 nm generated in
reflection of In2Se3 ....................................................................................................... 89
Figure 4.6 Amplitude images of In2Se3 onto SiO2/Si substrate with different drive
fffXVII
I YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
voltages (a: 1 V; b: 2 V; c: 3 V; d: 4 V; scale bar, 2.5 μm) ........................................... 90
Figure 4.7 Surface topography a) and PFM amplitude image b) of 20 nm In2Se3 onto
SiO2/Si substrate, scale bar, 2 μm). Surface topography c) and PFM amplitude image
d) of 20 nm In2Se3 onto SiO2/Si substrate, scale bar, 15 μm. ...................................... 91
Figure 4.8 Piezoelectric properties d33 of In2Se3 onto SiO2/Si substrate with number of
layers. ........................................................................................................................... 91
Figure 4.9 Fifty phase hysteresis a) and amplitude loops b) of In2Se3 nanosheets ...... 95
Figure 4.10 Surface topography a) and PFM phase image b) of 20 layers In2Se3
nanosheet...................................................................................................................... 95
Figure 4.11 Surface topography a) and PFM phase image b) of 6 layers In2Se3
nanosheet...................................................................................................................... 96
Figure 4.12 Simulation of the atomical deformation actuator based on out-of-plane
piezoelectricity. a) The thickness dependent amplitude loops of In2Se3. b) The
thickness dependence of out-of-plane piezoelectric response of In2Se3 nanosheets. c)
Deformation of 11 nm In2Se3 with an applied voltage of −8 V. d) Deformation of
upper surface of In2Se3 at different applied voltage. e) Surface deformation of In2Se3
at different voltages. f) The thickness dependence of surface deformation for the
In2Se3............................................................................................................................ 98
Figure 5.1 a) Raman spectrum of MoS2. b) Raman spectrum of In2Se3. c) PL spectrum
fffXIX YUAN Shuoguo
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List of Figures
of In2Se3 ..................................................................................................................... 103
Figure 5.2 a) Raman spectrum of In2Se3. b) Raman spectrum of WS2. c) PL spectrum
of WS2 ........................................................................................................................ 105
Figure 5.3 Structural characterizations of α-In2Se3. a) Atomic structure of In2Se3. b)
Thickness dependent Raman spectra of In2Se3. c) XPS spectra of In2Se3. d,e)
Elemental mapping of In and Se. f) high-resolution TEM image of In2Se3 (scale bar, 3
nm) and the inset shows SAED pattern of In2Se3 ...................................................... 107
Figure 5.4 Amplitude images of In2Se3 onto SiO2/Si substrate with different drive
voltages. a) The surface topography and height profile of In2Se3 exfoliated onto
SiO2/Si substrate, scale bar, 2.5 μm. b) 1 V; c) 2 V; d) 3 V; e) 4 V; f) Amplitude versus
drive voltage loop. The linearly fitted result exhibits that the out-of-plane
piezoelectric coefficient d33 is ~7.6 pm/V ................................................................. 109
Figure 5.5 Piezoelectricity in monolayer MoS2. a) Optical microscope image and b)
PL mapping of monolayer CVD grown MoS2 onto SiO2/Si substrate (scale bar, 10
μm). c) Raman spectrum of monolayer CVD grown MoS2 onto SiO2/Si substrate. d)
AFM image and e) PFM amplitude image of monolayer CVD grown MoS2. f) Optical
microscope image and g) Raman spectrum of monolayer exfoliated MoS2 onto
SiO2/Si substrate (scale bar, 2.5 μm). h) Surface topography and i) PFM amplitude
images of monolayer exfoliated MoS2 onto SiO2/Si substrate .................................. 110
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List of Figures
Figure 5.6 Piezoelectricity in In2Se3/MoS2 heterostructure. a) Surface topography and
the inset shows the height profile of 40 nm In2Se3 fabricated onto monolayer MoS2
(scale bar, 1.5 μm). The enlarged PFM amplitude images of In2Se3/MoS2, b) 1 V; c) 2
V; d) 3 V. The larger scale PFM amplitude images of In2Se3/MoS2, e) 1 V; f) 2V; g) 3V,
exhibiting remarkable piezoelectricity. h) Amplitude vs drive voltage loop of
In2Se3/MoS2 heterostructure ...................................................................................... 112
Figure 5.7 a-c) The quantitative piezoresponse profiles of the extracted out-of-plane
PFM amplitude of In2Se3/MoS2 with different drive voltages. d) Thickness
dependence of the piezoelectric coefficient d33 of In2Se3/MoS2 ................................ 113
Figure 5.8 a) OM image of monolayer CVD grown WS2 onto SiO2/Si substrate, scale
bar, 5 μm. b) PL mapping of monolayer WS2 onto SiO2/Si substrate. c) AFM image
and d) PFM amplitude image of monolayer WS2 ...................................................... 114
Figure 5.9 The PFM amplitude images of In2Se3/WS2 vdW heterostructure (scale bar,
4 μm). a) 1 V; b) 2 V; c) 3 V. d-f) The quantitative piezoresponse profiles of the
extracted PFM amplitude of In2Se3/WS2 with different drive voltages ..................... 115
Figure 5.10 a) Atomic structure of In2Se3/WS2. b) Schematic band structure of
In2Se3/MoS2. c,d) UPS spectra of In2Se3. e,f) UPS spectra of MoS2 ......................... 117
Figure 5.11 a) Atomic structure of In2Se3/WS2. b) Schematic band structure of
In2Se3/WS2. c,d) UPS spectra of WS2 ........................................................................ 118
fffXXI YUAN Shuoguo
THE HONG KONG POLYTECHNIC UNIVERSITY
List of Figures
Figure 5.12 a) Atomic structure and band structure of the In2Se3/MoS2 heterostructure
when the polarization of In2Se3 is pointing downward. b) The atomic structure and
band structure of the In2Se3/MoS2 heterostrucutre with polarization pointing upward.
The charge density difference between the heterostructure and its components is
plotted overlap above the atomic structure, Δn=nIn2Se3/MoS2-nIn2Se3-nMoS2, the red and
the blue colours denote the charge accumulation and deplection, respetviely. c) and d)
is the plane-averaged differential charge density of a) and b), respetively ................ 120
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List of Tables
List of Tables
Table 3.1 LDA calculated Gamma point Phonon frequency (cm−1
) and the relative
irreducible representation for the d1T, 2H and 1T phase MoTe2, the Raman (R) and
Infrared (I) activity are also indicated. Due to the absentence of the inversion center,
all the modes in d1T-MoTe2 are both Raman and infrared active. ………………… 55
Table 3.2 Comparison of the critical or thinnest thickness and Curie temperature (Tc)
with the previously reported common ferroelectric materials possessing out-of-plane
ferroelectricity by experiments (RT represents room temperature)... .......................... 63
Table 4.1 The calculated elastic stiffness coefficients (Cml, unit: GPa) and the
piezoelectric coefficients of bulk In2Se3 under different compressive strains (eij, unit:
10-10
C/m; dij, unit: pm/V).. .......................................................................................... 93
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List of Acronyms
List of Acronyms
Acronyms Description
2D Two-dimensional
vdW Van der Waals
FTJ Ferroelectric tunnel junction
FeRAM Ferroelectric random access memory
TER Tunnel electroresistance
CVD Chemical vapor deposition
PLD Pulsed laser deposition
MBE Molecular beam epitaxy
PFM Piezoresponse force microscopy
AFM Atomic force microscopy
CAFM Conductive atomic force microscopy
STM Scanning tunnelling microscopy
XPS X-ray photoemission spectroscopy
HRTEM High-resolution transmission electron microscopy
STEM Scanning transmission electron microscopy
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EDS Energy dispersive spectroscopy
SHG Second-harmonic generation
OM Optical microscopy
UPS Ultraviolet photoelectron spectroscopy
VBM Valence band maximum
CBM Conduction band minimum
PL Photoluminescence
d1T Distorted 1T
DFT Density functional theory
TMDs Transition metal dichalcogenides
h-BN Hexagonal boron nitride
BP Black phosphorus
MXenes Transition metal carbides and/or nitride
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Chapter 1 Introduction
1.1 Background of two-dimensional materials
1.1.1 Graphene
The demand for more compact and powerful devices in electronic applications
has been growing since silicon has reached its limit. The most promising application
of graphene is to become a substitute for silicon, making ultrathin transistors for the
production of future supercomputers. Traditional semiconductors and conductors,
such as silicon and copper, have released some energy in the form of heat from
traditional semiconductors and conductors due to collision of electrons and atoms, and
the computer chips waste much electrical energy in this way. In the past decade, 2D
layered materials have drawn much more attention in fundamental research and
various applications.1-5
When the materials size approached atomic scale, 2D
materials exhibit attractive characteristics different from their bulk materials. In 2004,
graphene is the first 2D layered material discovered using mechanical exfoliation
method.6 Each carbon atom of graphene has an unbonded p-electron perpendicular to
the σ orbital of the plane of the carbon atom, forming a highly parabolic large π bond
on both sides of the lattice plane, which can be free and efficient in the crystal. The
speed of movement is up to 1/300 of the speed of light and the electron energy is not
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lost, giving graphene good conductivity. One of the most striking properties of
graphene is its extraordinary electronic properties, which offers great potential for its
essential properties and electronic devices applications. The large π bond electrons
that are highly crucible on both sides of the lattice plane have the light-absorbing and
nonlinear optical properties, Dirac carrier characteristics, and quantum Hall effect at
room temperature. Figure 1.1a shows the schematic strcuture of monolayer graphene.
There are two interpenetrating carbon atoms per unit cell in the lattice.7 The bond
length between two nearest neighboring carbon atoms is around 1.42 Å and the lattice
parameter is around 2.46 Å. Due to its unique two-dimensional structure and
electronic band structure, electrons in graphene can be compared to relativistic
particles, which means that these electrons can be regarded as massless Dirac-Ferimi,8
as shown in Figure 1.1b. This unique electronic property provides an ideal platform
for studying the relativistic effects. Another unique property is that when graphene is
thicker than three layers, electrons are allowed to pass a few microns without
scattering. This property ensures that graphene has an extremely high charge carrier
mobility and conductivity at room temperature. The graphene electron mobility at
room temperature exceeds 15000 cm2 /V·s, which is higher than that of carbon
nanotubes or silicon crystals and the resistivity is only about 10-6
Ω·cm, which is
lower than that of copper or silver. By replacing silicon with graphene, computer
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processors can run hundreds of times faster. These excellent properties make graphene
possess promising applications in high frequency devices, field effect transistors, solar
cells, touch screens, spin devices, field emission materials, sensitive sensors, high
performance batteries, supercapacitors, micro-nano electromechanical devices, and
composite materials. Graphene is also an important type of transparent conductive
materials. In the visible region, the transmittance of four layers graphene is
comparable to that of the conventional ITO film. On the other band, the transmittance
of monolayer graphene is higher than that of the ITO film. Graphene is almost
completely transparent and has a light transmittance of up to 97.7%. The thermal
conductivity of graphene is as high as 5300 W/m·K, which is higher than that of
carbon nanotubes and diamond. These features make it ideal for use as a raw material
for transparent electronic products such as transparent touch displays, illuminators
and solar panels. Based on the excellent physical properties of graphene, graphene has
extraordinary potential in a wide variety of applications.1-7
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Figure 1.1 a) Schematic of monolayer graphene lattice.7 b) The electronic band
structure of graphene.8
1.1.2 Transition metal dichalcogenides
The transition metal dichalcogenides (TMDs) are a chemically diverse class of
layered compounds with a general formula of MX2, where M represents a transition
metal element (e.g. Mo, Te etc) and X is a chalcogen (e.g. S, Se or Te). The
monolayer TMDs consist of a transition metal layer sandwiched by two chalcogen
layers and they are specially featured with the formation of different crystal
polytypes,9 as displayed in Figure 1.2. TMDs exist in different phases, including the
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semiconducting 2H phase, the metallic octahedral (1T) and distorted octahedral (1T′)
phases. The common semiconducting 2H phase MX2 is the most stable phase. The
2H-type MoS2 is dominant because it is thermodynamically stable in nature. The 2D
TMDs materials have wide applications in the fields ranging from electronic, optical,
optoelectronic and quantum devices to energy storage and catalysis.10-14
Figure 1.2 Crystal structures of MoS2 with different polymorphisms.9
1.1.3 Group III-VI compounds
Group III-VI compounds semiconductors M2X3 (M = Ga, In; X = S, Se, Te) are
an vital type of 2D layered materials because of the excellent electronic and
optoelectronic performance.15-18
Similar to 2D TMDs, M2X3 have the significant
advantages of atomic layer thickness, ultrahigh specific surface area and high
compatibility. Compared to TMDs, the M2X3 demonstrate other excellent
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characteristics, for example high carrier mobility, high charge density, etc.18
The most
common study with M2X3 stoichiometry is In2Se3. Typically, it has five known crystal
strcutures (α, β, γ, δ, and κ) at various temperatures. Among these phases, γ-In2Se3 has
a distorted wurtzite-like structure and δ-In2Se3 has a monoclinic structure. The
α-phase, β-phase and κ-phase In2Se3 are layered structures. It is generally believed
that the α-phase is thermodynamically stable. In each single-layer In2Se3, every
Se-In-Se-In-Se atomic layers form a stable 2D unit by covalent bonds, and the
different units are combined by a weak vdW interaction. The monolayer In2Se3
thickness is around 1 nm. The crystal structure of monolayer and bilayer α-In2Se3 is
displayed in Figure 1.3. The difference between the two common α-phase and β-phase
is the atomic arrangement and the atomic bond length, but their phases can be
transformed by means of temperature treatment.18
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Figure 1.3 Crystal structure of monolayer a) and bilayer b) α-In2Se3.
1.1.4 Graphene analogous
Besides the above 2D layered materials, there are some typical layered graphene
analogous materials, such as hexagonal boron nitride (h-BN), black phosphorus (BP),
Group III-VI layered semiconductors (MX), transition metal carbides and/or nitride
(MXenes), etc.
2D h-BN has honeycomb structure formed by hybridization of B and N atoms by
sp2 bonding, which is also called white graphene.
19,20 It consists of atomic-level planar
layers of alternating hexagonal B atoms and N atoms, which are joined together by
interlayer vdW interactions. The h-BN has excellent physical and chemical properties
such as wide band gap, high thermal conductivity, stability and oxidation resistance.
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Unlike the excellent conductivity of graphene, h-BN has extremely excellent
insulating properties, which makes it play an important role in various basic sciences
and technologies, such as charge fluctuation, contact resistance, gate dielectric,
passivation layer and atomic tunneling layer.
The bulk black phosphorus has a layered orthorhombic crystal structure. The
spacing between adjacent layers is 5.4 Å, and the layers are also connected by vdW
force. A single layer black phosphorus consists of a pleated honeycomb structure in
which the phosphorus atoms are connected to the other three atoms. Among four
phosphorus atoms, three of the atoms are in the same plane and the fourth atom is in
the adjacent parallel layer.21-23
Group III-VI layered semiconductors are a class of layered metal chalcogenides
having the general formula MX (M = Ga, In; X =S, Se, Te).24,25
GaSe is an example
of 2D layered materials from the Group III-VI family, which is connected by a
vertical stack of Se-Ga-Ga-Se layers by vdW forces. Each layer has a D3h
symmetrical hexagonal structure. The adjacent layer spacing is around 0.84 nm and
the lattice constant along the axis is around 0.40 nm.
MXenes, an emerging class of 2D layered transition metal carbides and/or nitride
materials, were discovered by Gogotsi group in 2011.26
MXenes were produced by
selective etching of the raw MAX phase materials, presented by a chemical formula
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of Mn+1AXn (n = 1, 2, or 3), where M2AX, M3AX2, or M4AX3, where M represents
the transition metal (Ti, V, Nb, etc), A stands for an element from group IIIA or IVA,
and X is carbon and/or nitrogen. Since M-A bonding (metallic bond) is weaker than
M-X (mixed metallic-ionic covalent bond), the A layer can be selectively etched from
the MAX phase by HF to become a Mn+1Xn (n = 1, 2 or 3) structure. The MXenes
have excellent physical and chemical properties, which have wide application
prospects in energy storage and catalysts.27-31
1.2 Ferroelectric and piezoelectric properties of nanoscale
films
1.2.1 Typical ferroelectric materials
Ferroelectrics are a class of dielectric crystals with spontaneous polarization
characteristics in which the spontaneous polarization orientation changes with the
applied electric field.32-35
When the external electric field is removed, its polarization
state can still be maintained. The most basic characteristic of ferroelectrics is
spontaneous polarization, which is mainly caused by the fact that the positive and
negative charges do not coincide in the ferroelectric unit cell to produce an electric
dipole moment. The property of ferroelectrics is called ferroelectricity and can be
macroscopically characterized by the hysteresis loop characteristics, as shown in
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Figure 1.4.
Figure 1.4 The hysteresis loop of typical ferroelectric materials.
With the rapid development of microelectronics technology, the miniaturization
and integration of electronic devices have become the current research trend.36
Integrated ferroelectrics thin films and semiconductor CMOS processes have broad
application prospects in many fields such as microelectronics, integrated optics,
optoelectronics, and microelectromechanics. In addition to excellent ferroelectric
properties, ferroelectric thin films also have piezoelectric properties, dielectric
properties, pyroelectric properties and other important features, as shown in Figure
1.5. All ferroelectric materials have piezoelectric properties. Piezoelectric materials
can provide polarized charges via applying external stress. Since the discovery in
1880, many materials have been reported to have the piezoelectric response, which
are widely used in actuators, transducers, sensors and energy applications. Moreover,
the inverse piezoelectric effect is also widely used in the generation of sound waves
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and scanning probe microscopy systems.37,38
Figure 1.5 The relationship between dielectrics, piezoelectrics, pyroelectrics and
ferroelectrics.
Typical perovskite structure ABO3 ferroelectrics are the most widely studied and
used ferroelectric materials. In the ABO3 structure, the A and B sites are occupied by
atoms with different valence states and radii. The B site is in the oxygen octahedron,
and different properties can be obtained by doping with different atoms.
BaTiO3-based materials are the first type of the discovered perovskite structure
ferroelectric materials. This type of material has the advantages of large residual
polarization, large dielectric constant and good fatigue performance, but the leakage
current density is high under high electric field condition, limiting the
functionalization of such materials for devices applications.39
The Pb(Zr,Ti)O3-based
ferroelectric material is another type of perovskite structure after the discovery of
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BaTiO3 series.40-42
The most common ferroelectric material is Pb(Zr,Ti)O3 thin film
which has been widely used due to its large residual polarization and low deposition
temperature. However, due to the presence of toxic lead, the environmental pollution
caused by the volatilization of lead has resulted in serious pollution to nature and
human living environment. BiFeO3 has a very large polarization, and its polarization
is as high as 100 μC/cm2. It has been widely studied as a typical single-phase
multiferroic material.43,44
Although the polarization of such material is very large, a
large leakage current is caused owing to the volatilization of Bi element and the
change of Fe element, which makes a gap with the practical application requirements
of the ferroelectric memory.
Since Bell Labs first proposed the concept of ferroelectric memory, it has
attracted great interest.45
Due to its advantages of non-volatility, fast read/write speed,
high storage capacity, low power consumption, fatigue and excellent radiation
performance, ferroelectric random access memory (FeRAM) is recognized as the
most promising next-generation memory, as it has a very large market application
prospect in the field of electronic information products in the future.46
Typical
FeRAM device is based on the capacitor structure, and its readout is destructive.
However, the ferroelectric tunnel junction (FTJ) is able to read using a change in the
quantum tunneling current through the ferroelectric ultrathin film, and thus its readout
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is non-destructive.47-49
A typical FTJ consists of two metal electrodes and an ultrathin
ferroelectric film, as shown in Figure 1.6. According to the basic principles of
quantum mechanics, if the barrier is thin enough, the charge carriers can pass through
the barrier, which means that the carrier has a probability to appear on another side of
the barrier. The charge carrier can tunnel through the ultrathin ferroelectric film,
depending on the barrier height and width. When the ultrathin ferroelectric film acts
as a barrier layer, the polarization of the ferroelectric film will cause a corresponding
polarization charge at the interface and the screening charge will be generated at the
interface. When the lengths of the Thomas-Fermi screening charge of the left and
right electrodes are different, the barrier height of the ferroelectric film will be
different when the polarization direction of the ferroelectric film is left or right, and
therefore the tunneling electro-resistance of the tunnel junction will also be different.
For FTJ, different ferroelectric polarization values are obtained for different
ferroelectric tunneling directions, and thus non-destructive reading of the memory can
be achieved. The tunnel electroresistance (TER) is an important indicator to evaluate
the performance of the FTJ. The tunnel transmission is exponentially related to the
square root of the average height of tunnel barrier. By applying a voltage to the tunnel
barrier, two spontaneous polarization directions result in two distinct resistance states.
The TER ratio is used to estimate the efficiency of ON state and OFF state resistance,
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and the equation of TER is expressed as follows, TER = (ROFF – RON)/RON, where RON
and ROFF stand for the resistances of ON state and OFF state, respectively.
Figure 1.6 The energy barrier diagram of the FTJ for two different polarization
directions, M1 stands for the metal 1, FE stands for ferroelectric barrier and M2
respresents the metal 2.49
Since the tunneling effect is not exhibited when the barrier layer is thick in the
FTJ, the thickness of the tunnel barrier layer is relatively thin. For ferroelectric
materials, the phenomenon of ferroelectric polarization is a collective effect, which is
a phenomenon exhibited by many dipoles, rather than a phenomenon exhibited by a
single dipole. Therefore, whether the ferroelectric material has a critical thickness,
that is, the ferroelectricity disappears when the thickness of the ferroelectric thin film
is less than a certain critical value.50-52
This problem is very important for the study of
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nanoscale ferroelectrics, which is also important for FTJ. Theoretical calculations and
experimental results have demonstrated that when the thickness of the ferroelectric
thin film is reduced to several unit cells, the ferroelectricity of the thin film can still
maintain.53-55
For a long time, it is generally believed that the critical thickness of
ferroelectricity is hundreds of nanometers, which hinders the application of
ferroelectric materials as a barrier layer in FTJ. Until 1999, Tybell et al. reported that
the epitaxially grown 4 nm Pb(Zr0.2Ti0.8)O3 film had a stable ferroelectric phase.56
In
2003, Ghosez et al. first used density functional theory (DFT) to verify that
ferroelectricity was still present in 2.4 nm BaTiO3 films.57
In the same year, Contreras
et al. reported the heterostructure of Pt/Pb(Zr0.52Ti0.48)O3/SrRuO3. The I-V curve was
studied and the change of electrical resistance was observed.58
In 2004, Fong et al.
found that the ferroelectricity of the 1.2 nm PbTiO3 film epitaxially grown on the
SrTiO3 substrate remained stable by experimental study.59
Until 2005, Tsymbal and
Kohlstedt et al. proposed the concept of FTJ, that is, the upper and lower electrodes
plus the ferroelectric barrier layer.60
In 2006, Tenne et al. confirmed that the 0.4 nm
BaTO3 film can still maintain its ferroelectricity.61
In 2009, Garcia et al. deposited
PbTiO3/La0.67Sr0.33MnO3 on a (001) NdGaO3 substrate with pulsed laser deposition,
and a 30 nm thick La0.67Sr0.33MnO3 film was used as a buffer layer and a bottom
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electrode. Under the condition of 1~3 nm thick BaTO3, when the direction of
ferroelectric polarization is reversed, a large change of electroresistance is observed.
By detecting the tunnel current passing through the thin layer, the polarization state of
the material can be read. In addition, these devices can achieve high storage densities
(about 16 Gb per square inch) for application in high-density storage.62
1.2.2 Typical piezoelectric materials
Unlike piezoelectric materials, ferroelectric materials have an electric
polarization under external electric filed and have residual polarization even after
removing the external electric field. Piezoelectric materials are a class of functional
materials that have a piezoelectric effect, as shown in Figure 1.7. The piezoelectric
effect refers to the effect of the material generating an electrical signal under external
force or the deformation of the material under applied electric field. Specifically,
when the material is deformed by external force, the relative displacement of positive
and negative ions in the unit cell makes the positive and negative charge centers no
longer coincide, resulting in macroscopic polarization of the material. The surface
charge density of the material is equal to the projection of the polarization in the
surface direction, a different electric charge will appear on both sides of the material
when the material is deformed by the external force. In contrast, when a piezoelectric
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material is polarized by applying an electric field, the material is deformed owing to
the displacement of the charge center. The piezoelectricity of a material is mainly
determined by the piezoelectric constant. Typically, all ferroelectric materials have
piezoelectric and inverse piezoelectric characteristics, making them widely used in
transducers, actuators, sensing, and energy applications.63,64
Since the piezoelectric
effect was discovered in 1880, the traditional piezoelectric materials mainly include
inorganic and organic piezoelectric materials.65-67
Figure 1.7 Schematic of typical piezoelectric effect.
The first type is inorganic piezoelectric material, which is divided into
piezoelectric crystal and piezoelectric ceramic.68
Piezoelectric crystal typically
corresponds to piezoelectric single crystals and piezoelectric ceramic generally refers
to piezoelectric polycrystals. Piezoelectric ceramic is typically synthesized by using
solid phase reaction. The piezoelectric ceramic has ferroelectric domains among the
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crystal grains of the ceramic, and the ferroelectric domains are composed of 180°
domains which are antiparallel in the spontaneous polarization direction and 90°
domains which are perpendicular to each other in the spontaneous polarization
direction. These domains are artificially polarized under the applied electric field, the
spontaneous polarization is sufficiently aligned according to the direction of the
external electric field and the remanent polarization is maintained after the external
electric field is cancelled, hence it has piezoelectricity. Such piezoelectric materials
mainly include BaTiO3, Pb(Zr,Ti)O3, PbTiO3, etc.69,70
The piezoelectric ceramics have
high piezoelectricity, high dielectric constant, low mechanical quality factor, large
electrical loss and poor stability, thus they are suitable for high-power transducers,
broadband filtering and piezoelectric sensors. Piezoelectric crystals generally
correspond to piezoelectric single crystals, which refer to crystals grown in a
long-range order according to the crystal lattice space. The piezoelectric crystal has
non-centrosymmetric structure and therefore is piezoelectric, such as quartz, LiNbO3,
TiNbO3, Pb(Mg1/3Nb2/3)O3, etc. The piezoelectric single crystals are used for standard
frequency-controlled oscillators and high selectivity filters.71
The second type is organic piezoelectric material, such as piezoelectric polymer
polyvinylidene fluoride (PVDF) and other related organic piezoelectric materials.72-74
These materials have the advantage of flexible, low-density and low-impedance,
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which are used for acoustic ultrasonic measurement, pressure sensing, etc. The
disadvantage is that the low piezoelectric strain constant, limiting the application as
an active emission transducer.
Currently, the demands for miniaturization and multifunction of electronic
devices are growing. 2D piezoelectric materials have drawn significant attention due
to the ultrathin scale, excellent electromechanical response and intergrating with other
materials. Therfore, these characteristics make 2D piezoelectric materials have the
potential applications for designing and development of nanomechanical system,
self-adaptive energy harvesting system, piezotronics, and smart electronic devices,
etc.
1.3 Significance of research
Ferroelectric materials have attracted intensive interest due to a wide range of
applications in smart sensors, capacitors, energy harvesting devices and non-volatile
memories. Ferroelectricity at the nanoscale has emerged as fertile ground for novel
physics and applications. However, maintaining the ferroelectricity in oxide-based
films below a critical thickness has been hampered by the intrinsic depolarization
effects, and the Curie temperature significantly decreases when a ferroelectric material
becomes thinner, which greatly limits their usefulness in modern high-density or
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nanoscale systems. Therefore, the critical thickness in the ferroelectric materials, such
as typical perovskite ABO3, is limited by the scale of a few unit cells. 2D layered
materials provide unprecedented possibilities to overcome the problems due to no
dangling bonds, no constraints of lattice mismatch, structure flexible characteristic and
compatibilities of other materials. It is noted that in-plane ferroelectricity is
experimentally reported in single-unit cell SnTe thin-films, whereas only thicker films
possess ferroelectric properties above room temperature. Ferroelectricity in single-unit
cell SnTe film is absent at room temperature and in-plane ferroelectricity is not suitable
for many promising applications. In addition, a few 2D materials are reported to
demonstrate few-layer ferroelectricity at room-temperature. Recently, several
monolayer 2D layered materials have been predicted to exhibit novel ferroelectric
phenomena by theoretical calculation, but still few experimental observations have
been reported from them so far. In this thesis, the experimental observation of
room-temperature ferroelectricty in an unexploited phase of MoTe2 down to the
monolayer limit was reported. The ferroelectricity mechanism is addressed by
combining structural characterizations and DFT calculations. Furthermore, an ultrathin
vdW heterostructure based FTJ device using the discovered 2D ferroelectrics is
constructed. The vdW heterostructure platform based on 2D ferroelectricity provides
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the way of developing ultrathin ferroelectric devices, which will facilitate the
miniaturization of next generation atomic-scale logical memory devices.
On the other hand, piezoelectricity in 2D vdW materials has attracted enormous
interest owing to promising unique applications in nanoscale electromechanical
systems, ultrasensitive sensors, high-precision actuators, piezotronics,
piezo-phototronics and energy conversion. In ultrathin atomic scale, in-plane
piezoelectricity has been experimentally reported in monolayer MoS2, WSe2, g-C3N4
and Se, which may not be suitable for wide applications in the vertical structural
nano-electromechnical systems. Currently, piezoelectricity in 2D material family has
been intensively predicted by theoretical calculations, but still few experimental
reports from them. Recent studies have reported that out-of-plane piezoelectricity
exists in MoSSe and α-In2Se3, which exhibits low piezoelectric response. Therefore,
enhancing the piezoelectric performance in 2D layered materials is still challenging.
Recent studies have demonstrated that the vdW heterostructure engineering can be
employed to generate the novel physical phenomena and performance, providing an
important approach to enhance various physical properties of 2D layered materials.
There is still no experimental study on the enhanced out-of-plane piezoelectric
performance via vdW heterostructure. The remarkable out-of-plane piezoelectric
response is achieved in 2D vdW heterostructure for the first time, which is different
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Chapter 1
from in-plane piezoelectricity in MoS2 restricted by edge-effect and odd-even layers.
In addition, high-precision actuator device based on the piezoelectricity in 2D atomic
scale is shown. Moreover, the vertical switching polarization characteristic of In2Se3
is also investigated, which can retain the ferroelectric behaviour down to 6 nm. The
heterostructure fabricated onto silicon substrate is compatible with state-of-the-art
microfabrication technology, which will result in the unexpected applications in
nanoelectronics and atomic-scale multifunctional coupling devices.
1.4 Structure of thesis
The chapters of this thesis are organized as follows:
Chapter 1: Introduction. In this chapter, the crystal structure and fascinating
properties of typical 2D layered materials are first introduced. Then, the perovskite
oxides-based nanoscale ferroelectric and piezoelectric materials are illustrated.
Following that, the motivations and objectives of this thesis are presented.
Chapter 2: Experimental methods. This chapter introduces the important
experimental methods used in this research, including fabrication methods of 2D
materials, structural characterization methods, ferroelectric and piezoelectric
properties measurement and transport characteristic measurement systems.
Chapter 3: Ferroelectricity in distorted 1T phase MoTe2. This chapter explores
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the fabrication of the samples, structure characterization, ferroelectric characterization
and physical mechanism in MoTe2. The devices based on ferroelectricity in MoTe2 are
demonstrated.
Chapter 4: Out-of-plane piezoelectricity in the exfoliated In2Se3. This chapter
demonstrates the preparation and structural characterization of In2Se3 samples, and
piezoelectric and ferroelectric properties of In2Se3 as well as its device applications.
Chapter 5: Out-of-plane piezoelectricity in van der Waals heterostructure. In
this chapter, the preparation and Raman characterization of vdW heterostructure are
shown. Piezoelectricity in various vdW heterostructures is presented. In addition, the
physical mechanism of piezoelectricity in vdW heterostructure is also discussed.
Chapter 6: Conclusion and future prospect. In this chapter, the results in this
thesis are summarized. In addition, future prospect of 2D ferroelectricity and
piezoelectricity and related applications is presented.
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Chapter 2
Chapter 2 Experimental Methods
This chapter will introduce the primary experimental methods which were used
in the thesis. 2D materials like MoTe2, In2Se3, MoS2, and WS2 were prepared by
mechanial exfoliation and chemical vapor deposition. The MoTe2 films were also
fabricated by molecular beam epitaxy (MBE). The Raman spectra of the samples were
measured by Raman spectroscopy. The chemical composition was measured using
X-ray photoelectron spectroscopy (XPS). A femtosecond laser was utilized to measure
the second-harmonic generation (SHG) signals of samples. The microstructures and
chemical compositions of samples were characterized by transmission electron
microscope (TEM) equipped with energy-dispersive X-ray spectroscopy (EDX). The
atomic structures of samples were measured by a scanning transmission electron
microscopy (STEM) aberration corrector operated. The surface topography of the
samples was characterized by using atomic force microscopy (AFM) and scanning
tunnelling microscopy (STM). The piezoresponse force microscopy (PFM)
measurements were performanced on a commercial atomic force microscope. The
PFM hysteresis loops, PFM phase and amplitude images were collected in the single
frequency or dual frequency resonance tracking mode. The vector PFM was also
performed by imaging the in-plane signal of samples. The I-V curves of the devices
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were measured by conductive atomic force microscopy (CAFM) at room temperature
to characterize the electrical transport characteristics.
2.1 Fabrication methods of 2D materials
2.1.1 Exfoliation
Mechanical exfoliation is a typical method to fabricate the 2D thin flakes.19,75
The method is to apply a force to debilitate the vdW interaction between the bulk
crystal layers with a tape, meanwhile, the in-plane covalent bonds of each layer are
not broken, which leads to peel off monolayer or few-layer 2D crystals. An adhesive
Scotch tape is pressed close to the 2D bulk crystal peeled into a thin flake via using
another adhesive surface. This process can be repeated several times to obtain an
appropriately thin flake, and then the tape with layered material crystals is pressed
against the target substrate surface. Finally, after peeling off the tape, monolayer or
few-layer thin flakes left on the substrate can be obtained, as shown in Figure 2.1. The
exfoliated samples via an optical microscope are to observe and identify the location
and possible thickness when a suitable substrate is employed.
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Figure 2.1 A typical method to fabricate the 2D flakesby mechanical exfoliation.75
Liquid exfoliation is also an important and simple approach of exfoliation to
fabricate the high yield 2D nanosheets.19,76,77
Currently, liquid exfoliation method has
been widely used to exfoliate a large number of the 2D bulk crystals (e.g., graphene,
TMDs, h-BN, BP, etc). Typically, sonication is the most common and simple method
to exfoliate the layered bulk crystals into 2D nanosheets (Figure 2.2). First, the 2D
bulk crystals were dispersed in a specific solvent and then treated with sonication for
a selective time. Then, the nanosheet suspension was purified through centrifugation
after sonication. The surface energy between the layered bulk crystal and liquid
solution plays an important role in performing efficient exfoliation of layered bulk
crystals. The thickness, size and concentration of the nanosheets can be generally
controlled by the sonication time, sonication temperature, solvent system, ultrasonic
power, etc. According to the experimental and theoretical results, the choice of the
liquid solution is a vital factor for the efficient exfoliation via minimizing the
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exfoliation energy. The liquid solution is to stabilize the exfoliated nanosheets and
prohibit their restacking and aggregating. The mixture of water and ethanol is usually
effective for exfoliating and dispersing TMD nanosheets.
It is worth noting that pure water or ethanol is not efficient in removing TMD
due to its large surface energy. The ultrasonic-based liquid exfoliation with effective
spalling can be realized in solvents where the surface energy matches the bulk crystals.
The surface energy of materials is different, which is difficult to find a suitable
solvent system for each bulk crystal. Meanwhile, the addition of a polymer or
surfactant to an aqueous solution for sonicating layered bulk crystals is another
powerful method for stripping them into ultrathin 2D nanosheets. By adding a
polymer or a surfactant to an aqueous solution, the surface tension of the aqueous
solution can be easily adjusted to match the surface energy of the bulk crystal, and
effective stripping of the layered material can be achieved.
Though the sonication-based liquid exfoliation method is the most widely used
for the preparation of 2D materials, there are several disadvantages for the sonication-
based liquid exfoliation. Firstly, the yield of the monolayer nanosheets is low because
some special properties of 2D materials can only be observed in the monolayer scale.
Secondly, for the ultrasonic treatment in aqueous polymer or surfactant solution, the
residual polymer or surfactant absorbed on the prepared nanosheets is not desirable
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for some device applications. Thirdly, the horiziontal size of the prepared nanosheets
is comparatively small because the ultrasound force decomposes the big flakes into
small fragments. Lastly, ultrasonic treatment may cause some defects on the prepared
nanosheets, which will change the properties of the nanosheets.
Figure 2.2 Liquid exfoliation based on sonication. The bulk crystal is sonicated in a
solvent system, which leads to exfoliate into the 2D nanosheets.76
2.1.2 Physical vapor deposition
Pulsed laser deposition (PLD) is an important technique to prepare the large area
high-quality thin film samples.78
PLD is a kind of physical vapor deposition method,
the typical PLD system includes three main sections: laser system, vacuum system
and deposition chamber, as shown in Figure 2.3. The fundamental working principle
of PLD includes the connection of the laser and the objective material in high vacuum
condition. During the thin film growth process, a pulsed laser is concentrated, and the
incident laser goes into the vacuum deposition chamber and hits on the surface of the
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target. Typically, a KrF excimer laser with a laser wavelength of 248 nm is utilized.
When the laser energy is sufficiently high, the material will make a plasma plume,
which incorporates atoms, particles, ions and cluster. The substrate is typically placed
in front of the objective material, and the plasma plume moves to the substrate in a
direction perpendicular to the surface of the target, and finally transports to the
substrate to agglomerate and nucleate to form a thin film. The thin film thickness can
be controlled precisely by the numbers of laser pulses or deposition time. To control
the pulsed laser into the chamber, laser path ought to be balanced accurately. The
sample quality of the PLD growth thin film is modulated by a series of experimental
parameters, for example, laser energy, substrate temperature, fabrication time, vacuum
pressure, and the distance between the target and substrate.
Figure 2.3 Schematic of the PLD equipment.78
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The MBE is another important type of physical vapor deposition method for the
preparation of high quality single-crystal films and nanostructures.79
The basic
principle is that in an ultra-high vacuum environment, molecules or atoms with
certain kinetic energy are deposited on the surface of a selective substrate by heating
the evaporation source, and then adsorption, migration or surface generation occurs.
Epitaxial growth of the material is achieved after the reaction. MBE is essentially a
non-equilibrium growth process, which is the process of vapor phase atomic
deposition onto the surface of the substrate to become a solid phase, as a result of
growth kinetics and thermodynamic interactions. The growth process of MBE is
carried out in an ultra-high vacuum environment to avoid interference of impurities.
The substrate is cleaned, and the epitaxial material is high in purity, and therefore
high-quality samples can be prepared. In addition, its evaporation rate is slow but
stable, and a single-crystal film with uniform composition and structure can be
obtained. The growth process has atomic scale controllability, and the film thickness
can be precisely controlled. A variety of 2D materials are currently available by this
method, such as graphene, silene, In2Se3, etc.
2.1.3 Chemical vapor deposition
The chemical vapor deposition (CVD) has been widely used for 2D layered
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materials growth.80-82
The CVD method is able to fabricate high quality and limited
defects with scalable dimensions and controllable thickness. During CVD growth
process, a pre-selected substrate is placed in the furnace chamber and one or more
gaseous precursors are circulated within the furnace chamber, and then the precursor
is reacted and/or deposited on the surface of the substrate, as shown in Figure 2.4.
Based on this method, ultrathin 2D nanosheets can be obtained under suitable
experimental conditions. It is worth noting that the electronic properties of 2D
materials such as graphene and TMDs are approaching the electronic properties of
mechanically exfoliated samples. Therefore, the ultrathin 2D materials grown by
CVD are also expected to be candidates for the fabrication of high performance
electronic and optoelectronic devices. Unlike the low yield and productivity of
mechanical exfoliation method, CVD can produce industrial-scale materials, which
shows broad application prospects in the electronic and optoelectronic devices. So far,
many ultrathin 2D TMDs nanosheets have been grown under different conditions
including MoS2, MoSe2, MoTe2, WS2, WSe2, WTe2, etc. Apart from pure TMDs
nanosheets, the alloyed TMDs nanosheets have been prepared, such as MoxW1-xS2,
MoS2xSe2(1−x), etc. In addition, lateral and vertical growth also can be controlled in the
2D TMDs heterostructure growth. Due to the different band gaps of TMDs nanosheets,
the lateral and vertical heterostructures can be considered as natural p-n junctions,
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making them ideal for building high performance electronic and optoelectric devices.
But the CVD strategy has a few shortcomings, for exmaple, the CVD-grown 2D
materials are constantly deposited on the selected substrates, which requires transfer
process to different substrates for further measurements. Typically, the CVD method
needs high temperature and inactive environment, which increases the fabrication
expense of samples.
Figure 2.4 Schematic of CVD growth.
2.2 Measurement methods
2.2.1 Optical characterization
The optical microscope provides a simple and rapid method to obtain
information about samples location, shape, and thickness.19,83
The working principle
of the optical microscope method is based on the interference of reflected light at
different substrate interfaces. When the sample introduces significant optical paths
and opacity perturbations, an optical contrast is produced between the bare substrate
and the 2D materials. Silicon coated with a silicon dioxide thin layer (SiO2/Si) is the
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most commonly used substrate to observe the 2D materials, especially, 285 nm thick
SiO2/Si. A part of the incident light is transmitted while another part is reflected to
each interface. The intensity of the collective reflected light with respect to
interference varies with locations depending on the sample thickness, absorption
coefficient, and difference in refractive index. The difference between the
experimental and calculated results may be attributed to the uncertainty of the optical
parameters of these ultrathin 2D materials. The contrast studies are very helpful to
investigate the physical properties of emerging 2D materials depending on their
layer-number. The approximate thickness based on the color contrast of 2D materials
can be identified. But for accurate thickness, further characterizations such as AFM,
STEM, Raman and photoluminescence (PL) spectroscopy are required.
2.2.2 Structural characterization
Raman spectroscopy is a fast, non-destructive means of giving material structure,
electronic information, and high spatial resolution.84,85
Beginning with the successful
characterization of graphene, Raman spectroscopy has been used to demonstrate the
layers number, crystal strcuture orientation, doping effect, phase, strain, and vdW
coupling of various ultrathin 2D layered materials. The basic mechanism of the
Raman spectroscopy is shown in Figure 2.5. When light illuminates on the objective
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material, both Rayleigh scattering and Raman scattering can be seen. Rayleigh
scattering is a sort of elastic scattering. Analysis of the frequency (wavelength) of the
scattered light reveals that