Two-Dimensional Material

Two-dimensional materials are a newly emerging area, which have chemical func-
tionality and ultrathin structure with a great degree of anisotropy.

From: Biomedical Applications of Graphene and 2D Nanomaterials, 2019

Related terms:

Graphene, Nanostructure, Thermal Conductivity, Heterojunction, Graphite, Transi-

tion Metal Dichalcogenides, Nanostructured Material

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The Development of High-Tem-

perature Superconductors and 2D
Iron-Based Superconductors
Xun Geng, Jiabao Yi, in Nano-Sized Multifunctional Materials, 2019

Abstract
2D materials have attracted extensive interest due to its excellent properties such
as high mobility, high conductivity and high mechanical strength and long spin
diffusion length for spintronics devices. Many researches have focused on the 2D
materials with pure form. However, doping in 2D materials have been paid more
and more attention because novel properties can be achieved by doping, such as
possessing both semiconductor and spin behavior, achieving high sensitivity as well
as high power harvest efficiency. In this chapter, we will discuss the preparation
method for 2D materials doping, theoretical modeling, the properties achieved by
doping and their applications.

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Optical Biochemical Sensors Based on

2D Materials
B.N. Shivananju, ... Qiaoliang Bao, in Fundamentals and Sensing Applications of 2D
Materials, 2019

10.2 Biochemical Optical Sensing Properties of 2D Materials

2D materials have exceptional biochemical optical sensing properties. First, due to
the atomic-thin layer structure and large surface area, they are excellent substrates
for adsorption of biomolecules via π–π stacking. Second, the large surface-to-volume
ratio allows high-energy transfer efficiency and fast response time due to ultrafast
carrier mobility. Moreover, the 2D materials of interest possess excellent biocompat-
ibility, exceptional fluorescence-quenching ability, broadband light absorption, high
chemical stability, outstanding robustness and flexibility [1,48]. Therefore, 2D mate-
rials have become widespread in biochemical sensing, diagnostics, and health-care
applications [1,48]. The most striking features of optical biochemical sensors based
on 2D materials are ultra-sensitivity and ultrafast response, thereby posing the
potential to replace some of the current electrical sensors used for biochemical
sensing applications [1,46].

Fig. 10.1 shows the basic mechanism of biochemical sensing based on 2D mater-
ial-coated optical sensor. When biochemical molecules come into contact with the
2D material, the Fermi level of the 2D material will shift either to p-type or n-type,
changing its optoelectronic properties [1]. Thus the conductivity of the 2D material
can be easily varied by biochemical doping, which is a very important attribute for
any biochemical sensing using optoelectronic and photonic devices. The interaction
between the biochemical molecules and the surface of the 2D material results in a
change in the electron-hole carrier density of the 2D material, which in turn changes
the local refractive index of 2D materials as shown in Eq. (10.1) [1]:

Figure 10.1. Biochemical sensing principle of 2D materials coated optical sensors.

(10.1)

where g,r and g,i are the real and imaginary parts of the conductivity of a 2D
material, is the frequency of light, and Δ is the thickness of 2D material. The
optical output (wavelength, intensity) of 2D material-coated optical device (neff) is
determined by the refractive index of 2D material (n2DM), which in turn depends on
the interaction of biochemical molecules on the surface of the 2D material [1].

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Introduction
Hywel Morgan, ... Dattatray J. Late, in Fundamentals and Sensing Applications of 2D
Materials, 2019

2D materials gained a huge interest among the research community after the first
report of the preparation of graphene by a simple micromechanical exfoliation of
highly oriented pyrolytic graphite in 2004 [1]. Understanding the different unusual
physical properties and applications of graphene provided researchers with the path
to explore the vibrant area of 2D layered materials over the past decade [2]. The zero
bandgap of graphene has limited its application, which led to a search for alternate
materials. Transition metal dichalcogenides are among the heavily studied 2D ma-
terials that differ from the semimetallic characteristic of graphene. They show novel,
diverse, and tunable layer-dependent properties that can be controlled by their
crystalline structure, number of stacking layers, and defect concentration [3]. Several
hundred different 2D materials with extraordinary physical and chemical properties
have been identified, including silicone [4], germanene [5], h-BN [6], graphene [7],
black phosphorous [8], MXenes [9], etc. The 2D materials can be semiconductor [10],
metal [11], semimetal [12], or superconductors [13]. Also, the indirect bandgap to
the direct bandgap transition of the 2D material is possible by tuning the number
of layers. By controlling the direct bandgap of the material it is possible to achieve
enhanced photoluminescence, optoelectronic properties, and controllable electrical
properties suitable for fabrication of high-performance transistors [14]. Similarly,
hybridization with different 2D materials provides a very effective and powerful way
not only to control the physiochemical properties of hybridized species but also
to explore nanocomposites with novel functionalization [15]. Therefore these 2D
materials show promise for a range of novel applications that are not possible with
bulk materials. To exploit the potential of 2D materials, researchers need to advance
the synthesis, properties, characterization, and applications of the material. Early
experiments on 2D materials were carried out on single layers, which were exfoliated
from bulk crystals using adhesive tape, which limits the size of the devices to be
in the range of tens of micrometer [10,16]. Recent advances in 2D materials have
now enabled the industrial requirement of wafer-scale growth for many different
materials, opening new ways to direct industrial applications in various devices such
as sensors, solar cells, catalyst, and others [16]. Along with these improved materials
comes the need for synthesis/growth, characterization, and sensing application that
can directly probe their electronic and optical properties over a wide range of energy
and spatial scales.

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2D Nanomaterials for Gene Delivery

Mohammad Nazmul Hasan, ... Yong-Kyu Lee, in Biomedical Applications of
Graphene and 2D Nanomaterials, 2019

Abstract
Two-dimensional materials have attracted much interest in recent years owing
to their chemical and optical properties. The potential of 2D materials such as
carbon-based nanomaterials and graphene analogues such as transition metal
dichalcogenides (TMDCs) in gene delivery have opened a new door of opportunity as
cancer theragnostic. In this chapter, we will elaborate the idea of various types of 2D
materials, including graphene quantum dot, transition metal oxides (TMOs), hexag-
onal boron nitride (hBN), graphitic C3N4 and 2D clay materials, and newly added
ultrathin black phosphorus (BP) monolayers, and their synthesis, subclassifications,
and gene delivery applications. Moreover, there are functionalized 2D nanomaterials
consisting of different types of polymers that can be very useful for modern-day gene
delivery applications.

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Fundamentals and Properties of 2D Ma-

terials in General and Sensing Applica-
tions
Dattatray J. Late, ... Chandra Sekhar Rout, in Fundamentals and Sensing Applications
of 2D Materials, 2019

2.7 Conclusion
2D materials have distinct chemical and physical properties including layered struc-
ture, high-surface area, layer-dependent optical bandgap, and variation of chemical
compositions. This makes them potential substitutes for various conventional ma-
terials in sensing. They have improved properties and detection limits which are very
important when sensitivity and measuring quanta are involved. The sensor platforms
range from field-effect transistors, electrochemical sensors to physical sensors. 2D
materials are compatible with any sensor assembly, and many more new members
with distinctive properties are being added to this family. In the near future these
materials will be found in markets such as wearable electronics, optolectronics, and
semiconductor technology.

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Synthesis, Characterization, and Prop-

erties of Graphene Analogs of 2D Mate-
rial
Pratik V. Shinde, Manoj Kumar Singh, in Fundamentals and Sensing Applications of
2D Materials, 2019

4.1 Introduction
2D materials open a new frontier in material science due to their excellent electronic,
mechanical, and optical properties, which originate from their ultrathin thickness
and 2D morphological features. In the early part of the 20th century, based on
concepts from classical physics, researchers said that 2D materials were thermo-
dynamically unstable materials at any finite temperature due to thermal lattice
fluctuations. Material science had a significant scientific breakthrough in 2004,
after the isolation of monolayer graphene by mechanical exfoliation. The invention
of single-layer graphene has shown not only that it is possible to create stable
single atom-thin layers but also these atomic layers can have fundamentally different
electronic structures and properties from the parent material. Following on from the
discovery of graphene, research into 2D material was stimulated in various fields
such as supercapacitors, sensors, photonics, optoelectronics, transistors, biomedical
applications, and so on [1–6].

2D materials are atomically thin crystalline solids having intralayer covalent bonding
and interlayer van der Waals (vdWs) bonding. These materials are unique due to
unprecedented properties that are unparalleled when compared to their bulky coun-
terparts. Due to having a limited number of atomic layers and its high mobility, 2D
crystal shows different electrical properties such as high surface area, a surface state
free nature, as well as a dangling bond-free surface [7]. Properties such as strong
light matter interaction, high mechanical strength, high optical nonlinearity, and a
strong quantum Hall effect (QHE) make 2D material optimal for many emerging
applications [8].
Graphene is an atomically thin sp2 carbon-layered material with a honeycomb
lattice structure [9]. Many remarkable properties such as a large surface area,
high charge-carrier mobility, high thermal conductivity, high optical activity, high
mechanical strength, and low Young’s modulus make graphene the most studied
material in the 2D family over the last decade [10,11]. However, the lack of bandgap
and low current on/off ratio made graphene unsuitable for commercial applications,
so researchers have placed more attention on other 2D materials such as hexago-
nal-boron nitride (h-BN), TMDCs, metal oxides, metals halides, MXenes, and Xenes
[12].

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Two-Dimensional Nanomaterials in
Cancer Theranostics
Jiuhai Wang, Mo Yang, in Theranostic Bionanomaterials, 2019

11.4 Summary and Future Perspectives

2D material, without a doubt, has won great research interests and achieved signif-
icant progress in both fundamental studies and further biological applications over
the past decade. Particularly, theranostic 2D nanomaterials with three functions,
that is, imaging agent, therapeutic agent, and targeting moiety, have been under
extensive investigation aimed at achieving early diagnosis as well as effective therapy
of tumors with targeting ability.

Medical imaging is considered as the most effective way to monitor tumor growth
in clinical settings. Among all the imaging modalities, optical imaging, MRI, PA,
CT, and PET are the commonly used techniques for tumor diagnosis. The develop-
ment of 2D nanomaterials provides opportunities for the combination of multiple
imaging modalities in a single nanoplatform to achieve multimodal imaging. Such
nanoplatforms include iron-, gadolinium-, and manganese-based nanomaterials in
combination with TMDs or AuNRs such as MIL-100, Mn(BDC)(H2O)2, Gd(BDC)-
1.5(H2O)2, ION-MoS2/WS2, MOF-AuNR, MnO2-AuNR, etc. With the functionaliza-

tion of targeting molecules, these nanoprobes present a unique capability to be

selectively localized at tumor site. 2D imaging nanoprobes with drug carrier ability,
such as MnO2 nanosheets loaded with DOX in a high loading capacity, are suitable
for imaging-guided chemotherapy of cancer. Some nanomaterials have an intrinsic
therapeutic effect under certain conditions such as NIR light irradiation.
Nanomaterials have long been utilized for disease therapeutics both in the laboratory
and clinic. 2D nanomaterials, due to their extremely large surface area, are superior
carriers for drug delivery compared with materials in other dimensions. There
have been various 2D nanocarriers that have been developed to deliver anticancer
drugs, such as MTX, DOX, and 5-FU, to cancer cells for tumor chemotherapy. A
number of novel 2D nanomaterials with intrinsic photothermal and photodynamic
properties are suitable for localized phototherapy of cancer. The combination of
chemotherapeutic drugs and PTT/PDT agents lead to a photothermal release of
drugs and unprecedented synergistic therapeutic efficacy. Recent attempts to apply
the 2D nanomaterial in the synergistic therapy of Alzheimer’s disease seem to have
a promising future.

Despite the fact that great progress has been made in the development of theranostic
2D nanomaterials in the past decade, these agents are far from being applied
clinically. Future efforts need to be made on the clinical translation of nanother-
anostic agents, which means that these theranostic nanomaterials should be tested
in animal models in order to fully understand the potential toxicity. Furthermore,
theranostic nanocarriers for chemotherapeutic drug delivery need to have better
targeting efficiency so as to avoid any harmfulness to the normal tissues. In order
to meet the need of potent cancer therapies, newly designed 2D nanomaterials
are expected to concentrate on addressing each specific case of cancer, achieving
a personalized cancer treatment. By understanding the fundamentals of cancer
development and the mechanism of the interactions between nanomaterials and
cancer cells, chemists and material scientists would be able to accelerate the progress
of applying 2D nanomaterials in the clinic.

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Two-Dimensional Nanomaterials:
Crystal Structure and Synthesis
Khaled Parvez, in Biomedical Applications of Graphene and 2D Nanomaterials, 2019

3.2 Liquid-Phase Exfoliation

Two-dimensional materials can be exfoliated in liquid environments exploiting ul-
trasounds to extract individual layers. The liquid-phase exfoliation generally involves
three steps: (i) dispersion in a solvent, (ii) exfoliation, and (iii) purification. The third
step is necessary to separate exfoliated from unexfoliated flakes and usually requires
ultracentrifugation. Exfoliation can be done via chemical wet dispersion followed
by ultrasonication both in aqueous and nonaqueous solvents. The basic idea is that
 sonication can induce liquid cavitation, which in turn induces bubbles in the solu-
tion. Microjets and shockwaves passed through the layered bulk crystals dispersed in
solution when these bubbles collapse. In this case, an intensive tensile stress will be
generated on the layered bulk crystals, thus leading to the exfoliation of layered bulk
crystals into thin layers of sheets. The key factor for achieving efficient exfoliation
of layered bulk crystals is matching the surface energy between the layered bulk
crystal and the solvent system. Graphene was first exfoliated in liquid phase by
Coleman’s group in 2008 by ultrasonicating the graphite in N-methylpyrrolidone
(NMP) (11). The obtained graphene sheets are considered to be pristine because no
chemical functionalization is involved. After centrifugation to remove unexfoliated
bulk crystals, the remaining dispersion consists of 28% single-layer graphene.
Unfortunately, the yield of single-layer graphene was very low, approximately 1 wt%
with a concentration of 0.01 mg/mL that is relatively low for further application.
Further optimization of solvents led to some improvements in the dispersability of
graphene. For instance, concentrations as high as 0.03 mg/mL, 0.1 mg/mL, and 0.5-
 mg/mL using ortho-dichlorobenzene (ODCB) (55), perfluorinated aromatic solvents
such as pentafluorobenzonitrile (56) and benzylamine (57). However, due to the long
ultrasonication process, the lateral dimension of the LPE graphene is relatively small
(< 3 μm). Despite the significant progress achieved in the exfoliation of graphite, the
aforementioned solvents have a high-boiling point and are relatively toxic. Therefore,
efforts have been devoted to the exploration of low-boiling-point solvent for the
sonication-assisted liquid exfoliation. For example, Coleman and coworkers have
demonstrated the sonication of graphite in some low-boiling solvents, including
isopropanol and chloroform to obtain a relatively high concentration of graphene
suspensions (58). Some other low-boiling solvents such as propanol and acetonitrile
were also used for LPE of graphite (59,60).

Besides graphene, Coleman’s group further extended LPE method for the exfoliation
of other layered bulk crystals into 2-D nanosheets including MoS2, MoSe2, WS2,
h-BN, NbSe2, TaSe2, NiTe2, MoTe2, and Bi2Te3 (12). Both the experimental and
theoretical results suggested that the good matching of surface tension between
the layered crystals and the solvents is a key factor for the efficient exfoliation (12).
The solvent is also important in stabilizing the exfoliated nanosheets and prohibiting
their restacking and/or aggregation. Zhou et al. also demonstrated that the mixer of
water and ethanol is effective for exfoliating and dispersing TMDC nanosheets (61).

Water is a natural solvent choice because of its nontoxicity, which can provide
possibilities for manipulation, in particular thin film fabrication. However, pure
water is inefficient to exfoliate 2-D crystals due to large surface energy. However,
a recent study has demonstrated that pure water can be a promising solvent in
the sonication-assisted exfoliation method by simply heating the water at elevated
temperature (e.g., 60°C) (62). At this point, water becomes both effective for the
exfoliation of layered bulk crystals of graphite, h-BN, MoS2, WS2, and MoSe2 into
2-D nanosheets in the sonication process and the stabilization of the exfoliated
nanosheets after exfoliation because of the presence of the platelet surface charges
induced by edge functionalization or intrinsic polarity. The successful exfoliation of
layered bulk crystals in pure water makes this method promising for the preparation
of thin 2-D nanomaterials for practical applications.

In the LPE method, the effective exfoliation can only be achieved in solvents with
matching surface energy to the layered bulk crystals, thereby making it difficult
to find a suitable solvent for each system for each layered bulk crystal. Alternatively,
sonication of layered bulk crystals in aqueous solution with additional polymers or
surfactants is another promising way for exfoliating them into thin 2-D nanosheets
(Fig. 6) (63). The surface tension of the aqueous solution can be easily tuned by
addition of polymers or surfactants, thus matching it to the surface energy of the
layered bulk crystals and achieving efficient exfoliation of layered materials (64). In
a rigorous investigation on surfactant-assisted graphite exfoliation in water, a variety
of ionic and nonionic surfactants were explored. For example, anionic surfactants
such as 4-dodecylbenzenesulfonic acid (SDBS) and sodium cholate (SC) have been
reported to successfully exfoliate graphene from graphite with a concentration of
0.1 mg/mL and 0.3 mg/mL in water, respectively (65,66). Some other ionic sur-
factants, such as sodium deoxycholate (SDC), cetyltrimethylammonium bromide
(CTAB), and acetic acid, have also been used to assist the exfoliation of graphite
by sonication (67,68). Several nonionic surfactants for exfoliating 2-D nanosheets
in aqueous solutions have been employed such as Pluronic P-123, polyoxyethylene
sorbitan monooleate (Tween 80), polyoxyethylene sorbitan trioleate (Tween 85), poly-
oxyethylene(4)dodecyl ether (Brij 30), and polyoxyethylene octyl phenyl ether (Triton
X-100) (69). In addition to these, several polymers such as polystyrene (PS), polyvinyl
chloride (PVC), polymethyl methacrylate (PMMA), poly[styrene-b-(2-vinylpyridine)]
(PS-b-P2VP), and poly(isoprene-b-acrylic acid) (PI-b-PAA) have also been investigated
for sonication-assisted exfoliation of bulk crystals (69–71).
Fig. 6. Schematic illustration of sonication-assisted liquid exfoliation of graphite into
graphene.Reproduced with permission from Ciesielski, A.; Samori, P. Chem. Soc.
Rev. 2014, 43, 381,Copyright © 2014 the Royal Society of Chemistry.

So far, the sonication-assisted liquid exfoliation method has been widely utilized
for exfoliation of numerous layered compounds into thin 2-D nanomaterials,
such as graphene (63), TMDCs (e.g., MoS2, WS2, MoSe2, WSe2, MoTe2, and TaSe2)
(12,72–74), h-BN (12,72), topological insulators (e.g., Bi2Te3, Bi2Se3, and Sb2Te3)
(75,76), black phosphorous (BP) (77,78), and g-C3N4 (79). In addition to thickness, the
concentration and lateral size of the obtained nanosheets can be roughly tuned by
controlling the solvent system, sonication time, ultrasonic power, temperature, sur-
factants, and/or additives. Currently, the sonication-assisted liquid-phase exfoliation
might be the most widely used approach for the preparation of solution-dispersed
2-D nanomaterials. However, there are several disadvantages for the sonication-as-
sisted LPE method. Among them, the yield of the single-layer nanosheets is low.
As known, some of the extraordinary properties of 2-D nanomaterials only can be
observed in its single-layer form. Also, the lateral size of the produced nanosheets
is relatively small because the sonication force breaks down the big nanosheets into
small fragments. Moreover, for the sonication in aqueous polymer and/or surfac-
tant solution, the residual surfactants adsorbed on the exfoliated nanosheets are
undesirable for their applications in electronics, optoelectronics, and energy storage
devices. The sonication process also may induce some defects on the exfoliated 2-D
nanosheets, which will affect their properties.

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The Graphenes Cousins From Dream

to Reality
Paolo Bondavalli, in Graphene and Related Nanomaterials, 2018

Germanane
This 2D material is the germane-based version of graphane [32]. In this case we
have 2D germanium bonded with H atoms. This 2D material has characteristics that
could also be more interesting compared to germanene. Firstly, this material can be
obtained by exfoliation as demonstrated by Bianco et al. in 2013 [33]. They reported
a unique method for generation of stable, single-layered germanane, converting
-CaGe2, a Zintl phase material, into a layered GeH by placing a large synthesized
crystal into aqueous HCl at −40°C. This process is called topotactic deintercalation
(Fig. 4.3).

Figure 4.3. (A) Top view of GeH, (B) side view of GeH.Reproduced from W. Amamou,
P.M. Odenthal, E.J. Bushong, D.J. O'Hara1, Y. K. Luo, J. van Baren, I. Pinchuk, Y. Wu,
A. S. Ahmed, J. Katoch, M.W. Bockrath, H.W.K. Tom, J.E. Goldberger, R.K. Kawakami,
Large area epitaxial germanane for electronic devices, 2D Mater. 2 (2015) 035012,
https://doi.org/10.1088/2053-1583/2/3/035012.
Zintl phase materials consist of an alkali or alkaline metal (groups 1, 2) and a
metal or metalloid (groups 13, 14, 15, 16). In the CaGe2 Zintl phase materials,
the crystal structure resembles that of an intercalation layered compound. -CaGe2
has alternating planes of covalently bonded germanium atom layers separated by
ionically bonded interstitial calcium. Germanane is silver-black and unlike silicene,
it does not require a substrate to be stable. GeH shows a van der Waals gap of
5.9 Å, much larger than similar layered structures and large enough to serve as a
host for the possible intercalation of many different species. The atomic structure
of germanane is not flat like graphane or graphene and theoretical calculations
do not show the existence of a Dirac cone. However, germanane has a theoretical
surprising high mobility, much higher than that of its bulk material, as pointed out
by Bianco et al., 18,200 cm2 V−1 s−1, which is almost a 5-fold increase over that of
bulk Ge (3900 cm2 V−1 s−1) and 10-fold compared to silicon. We can also mention
the recent pioneering work of Amamou et al. in 2015 [34], where scientists reported
the synthesis and transfer of epitaxial germanane (GeH) onto arbitrary substrates by
electrochemical delamination and investigated its optoelectronic properties.

In this work, for the first time GeH films with thickness ranging from 1 to 600 nm
(2–1000 layers) and areas up to 1 cm2 were reliably transferred, as shown in Fig. 4.4,
and characterized by photoluminescence, X-ray diffraction, and energy-dispersive
X-ray spectroscopy. Scientists highlighted a wavelength-dependent photoconduc-
tivity measurements on few-layer GeH exhibit an absorption edge and provide
a sensitive characterization tool for ultrathin germanane materials. The transfer
process also enables the possibility of integrating germanane into vertically stacked
heterostructures opening the route for their implementation in new generation of
opto-electronics devices, even the research is only at the beginning and maybe it
has been delayed by the interest captured by graphene.

Figure 4.4. (A) Schematic of the transfer process, (B) optical image of

PMMA/GeH/Ge(111), (C) optical image of the electrochemical cell, (D) optical im-
age of the floating PMMA/GeH film, and (E) optical image of GeH transferred to
SiO2.Reproduced from W. Amamou, P.M. Odenthal, E.J. Bushong, D.J. O'Hara1, Y.K.
Luo, J. van Baren, I. Pinchuk, Y. Wu, A.S. Ahmed, J. Katoch, M.W. Bockrath, H.W.K.
Tom, J.E. Goldberger, R.K. Kawakami, Large area epitaxial germanane for electronic
devices, 2D Mater. 2 (2015) 035012, https://doi.org/10.1088/2053-1583/2/3/035012.

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Challenges and Opportunities in Mole-

cular Beam Epitaxy Growth of 2D Crys-
tals
Suresh Vishwanath, ... Huili G. Xing, in Molecular Beam Epitaxy (Second Edition),
2018

20.3.3 On Quasi-2D Substrates

Although 2D materials are ideal substrates free of dangling bonds, they are not
usually epi-ready substrates. They are not epi-ready because of the lack of availability
of single crystal, atomically smooth substrates. Substrates such as GaAs (Ueno et
al., 1990) and GaP (Hammond 1995) were the early epi-ready substrates on which
MBE MoSe2 growth was attempted. For growth on GaP, a GaSe buffer layer was
grown on sulfur-terminated GaP and then MoSe2 was grown on it. For the growth
of MoSe2 directly on Se annealed GaAs(111) at 620°C, growth of 2Hb polytype of
MoSe2 was observed. This was seen by tracking the RHEED intensity of the specular
point and nonspecular point (1,0,11.5). The observed period from the (1,0,11.5)
beam is exactly twice that from the specular beam, indicating a BL growth mode
(Ohuchi et al., 1991) (see Fig. 20.17). Growth on GaAs was also investigated both
on Ga face and As face of GaAs after sulfur passivation using (NH4)2Sx treatment.
On S-GaAs, increasing growth temperature above 500°C causes S desorption, but
growth at 400°C causes broadening of the MoSe2 RHEED pattern with growth
duration. Hence, the first layer was grown at 400°C, and the remainder of the
layers were grown at 650°C. Furthermore, it was observed that MoSe2 films on
both Ga-terminated GaAs surfaces (GaAs(111)A) and As-terminated GaAs surfaces
(GaAs(111)B) had similar quality in terms of the crystallinity (Ueno et al., 1990). This
was also true for NbSe2 growth using MBE, which shows the transferability of this
technique across TMDs. Due to the infancy of the TEM technique in early 90s, the
abruptness of the MoSe2/GaAs junction was determined in-situ using EELS spectra
collected at different energies (Ueno et al., 1990). With advances in TEM, in-situ EELS
currently is not a very popular technique among MBE growers, but observations in
these early works show us that this technique could be quite useful in the case of
growth of ultra-thin heterostructures of 2D materials.

Figure 20.17. RHEED is a powerful tool in MBE growth of materials. Here, it has
been used to show that based on frequency of oscillations at two appropriately
chosen diffraction spots, we can ascertain the rotational order of the MBE-grown
MoSe2 to be 2H. RHEED intensity variation with time during the growth of MoSe2
thin film on GaAs(111) is shown in the figure.Source: Reproduced from Ohuchi,
F.S., Shimada, T., Parkinson, B.A., Ueno, K., Koma, A. Growth of MoSe2 thin
films with Van der Waals epitaxy. J. Cryst Growth 111 (1–4) (1991) 1033–1037.
doi:10.1016/0022-0248(91)91127-V.

Based on this initial observation, a careful study of MBE MoSe2 on GaAs (111)B
was done by Onomitsu et al. (2016). They grew an in-situ GaAs buffer layer using
metal-enhanced epitaxy and terminated their surface using a Se anneal of the
substrate slightly above the growth temperature. They report that the key to their
high-quality growth of MoSe2 at 600°C is the control of Mo flux at an extremely low
rate of ±20%, which corresponds to a growth rate of ~3300 s/layer of MoSe2. This
was controlled using electron impact emission spectroscopy (EIES). They observe
growth of large, triangular grains that are hundreds of nanometers in size. The
quality of the MoSe2 is investigated using XRD, Raman, and TEM. Using TEM, they
observe that the MoSe2 thin films can climb over the ML-high steps of GaAs (see Fig.
20.18), and the uniformity of Raman signal over several millimeters shows 1–2 MLs
of uniform growth. This is the first reported use of EIES for 2D material growth, and
it is likely to be a key technique for ultra-low flux control from e-beam systems, which
is critical for high-quality growth. This study shows that large area, high quality,
highly uniform MoSe2 can be grown on GaAs using MBE, but GaAs is not the ideal
substrate for device fabrication due to its bandgap comparable with the as-grown
film. Hence, MoSe2 grown on GaAs was recently released using KOH (aq.) at 90°C
and transferred to SiO2/Si substrate. On this transferred MoSe2, ambipolar transport
has been demonstrated using ionic gating (Chen et al., 2017). The low current and
temperature-dependent transport points to variable range hopping (VRH) transport
that is also observed in MBE-grown materials on 3D substrates (Roy et al., 2016; Dau
et al., 2017). VRH transport essentially means highly defective material. This shows
that despite claims of optically and structurally ‘high quality’ MBE-grown MoSe2 on
GaAs, extensive optimization of growth needs to be done to obtain electrically high
quality material and to understand if and to what extent the defects that cause VRH
transport are intrinsic to the material at the UHV growth conditions.

Figure 20.18. STEM images of the MoS2 on Se-terminated GaAs. It shows the
quasi-2D nature of Se terminated GaAs(111), high crystalline quality, and confor-
mality of MBE-grown MoSe2. The thicknesses of the MoSe2 thin films are (A) 1,
(C) 2, (D) 3, and (E) 4 MLs. In (B), the thickness is between 1 and 2 MLs, and
the second layer is partially formed. A magnified image of (A) is shown in (F),
in which atomic arrangements of MoSe2 and GaAs are schematically drawn. The
quasi-vdW gap structure is clearly observed. In (G), the incident electron beam is
parallel to the direction; it is perpendicular to the direction for all other images.
From the direction, the dog-leg structure of MoSe2 is not observed, indicating
excellent in-plane alignment. In (H), a 2-ML-thick MoSe2 film grows in the lateral
direction and is even climbing up a molecular step of GaAs.Source: Reproduced from
Onomitsu, K., Krajewska, A., Neufeld, R.A.E., Maeda, F., Kumakura, K., Yamamoto,
H. Epitaxial growth of monolayer MoSe2 on GaAs. Appl. Phys. Exp. 9 (11) (2016)
115501.
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