A Novel Temperature Dependent Method For Borophene Synthesis
A Novel Temperature Dependent Method For Borophene Synthesis
A Novel Temperature Dependent Method For Borophene Synthesis
A R T I C L E I N F O A B S T R A C T
Keywords: In energy, sensor, and biomedical applications, borophene is considered as an emerging and promising material.
Boron However, since bulk boron exhibits rather intricate spatial structures and multiple chemical properties, the
Borophene synthesis of borophene is yet to be considered as a challenging issue. A large amount of theoretical work has been
Novel method
conducted to characterize the properties of borophene incorporating the possible experimental methods. Un
Electrochemical exfoliation process
fortunately, synthesis of borophene and their properties in experimentation do not comply the theoretical ex
Cathode design
pectations within the desired level. There are some methods that have been used to synthesize borophene but
these techniques also have some limitations such as complexity and expensive. Due to this reason, the seeking of
new methods continues even now a day. In this research, a novel method has been proposed. This method is
nearly similar to the electrochemical exfoliation process of graphene production. Nevertheless, graphite is
conductive at ambient temperature, whereas boron is almost insulating at low temperature. Therefore, a new
design is explored with the boron attached heating coil so that it can act as a conductive material with increasing
temperature and confirmed the synthesis of borophene from boron by electrochemical exfoliation process. The
quality and crystallographic structure of anisotropic borophene with the change of temperature will also be
followed by this method. Apart from the pure boron rod, the sintering process is utilized under different aspects
to develop the boron structure under optimum conditions. The crystallographic structure of boron can be
changed by the sintering process under different operating and processing parameters. The synthesis of bor
ophene from various crystallographic structures of boron will provide the new insight of borophene for its use in
large scales. This new method of borophene synthesis is practically conducted at a limited level, still needs more
analysis by using advanced characterization techniques. The Raman spectrum of fabricated borophene is eval
uated and stability of this borophene is tested by using zeta potential. This method can be considered as a most
promising and potential method in comparison with the other available techniques.
* Corresponding author.
E-mail addresses: [email protected], [email protected] (M.A. Chowdhury).
https://doi.org/10.1016/j.apsadv.2022.100308
Received 15 July 2022; Received in revised form 5 September 2022; Accepted 20 September 2022
Available online 23 September 2022
2666-5239/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
Boron is the only semiconductor element in Group IIIA, the fifth Beyond graphene, synthetic organic chemists are still trying to figure
element in the periodic table, with valence orbitals comparable to car out a way of making scalable synthesis of elemental two-dimensional
bon and adjacent to it. Because of these similarities, borophene, a lit 2D (2D) materials [21]. The manufacturing of borophene is troublesome
metal, could have interesting properties similar to graphene. Because of since 3D boron bonding configurations are accompanied by a high en
its unique electrical structure, complicated bonding mechanisms, and ergy difference as compared to the 2D form. In addition, borophene
strong resemblance to carbon components, borophene is expected to synthesis usually requires extremely low pressures and advanced
have great qualities similar to graphene and even it can perform better equipment. Even back then, borophene synthesis was achievable using
as a new super material. Pure crystalline boron is a black, glossy semi the bottom-up approach, top-down approach, exfoliation techniques (i.
conductor, which conducts electricity like a metal at high temperatures e., sonochemical, liquid phase, and micromechanical exfoliation),
but acts as a near-insulator at low temperatures. The properties of boron deposition techniques such as chemical vapor deposition (CVD) and
are atomic number: 5, atomic weight: [10.806, 10.821], melting point: physical vapor deposition (PVD), ion-intercalation, solvothermal/hy
2,200◦ C, boiling point: 2,550◦ C, specific gravity: 2.34 (at 20◦ C), drothermal methods and so on [13,14,7]. It resulted in a variety of
oxidation state: +3 and electron configuration: 1s22s22p1. In the elec borophene complexes that were either supported by a substrate or
trochemical exfoliation method, boron is designed to utilize as a cathode freestanding. Due to the bonding topologies in bulk boron, synthesizing
material. Platinum is a favored anode material due to its low con borophene is still a major issue. A triangular lattice with periodic holes
sumption rate and strong electrical conductivity. Platinum is preferred and the ability to grow on metal substrates, in particular Ag (111), Au
for an anode’s outer surface because it is corrosion resistant and can (111), and Cu (11) should theoretically be more stable. Borophene has
maintain current flow in most electrolyte solutions without forming an previously been produced on single crystals of silver or copper, but these
insulating layer, resulting in a lower consumption rate. In fused salts and substrates are tiny, costly, and unsuitable for studying transport
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M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
properties or electronics applications [15]. The overview of the existing 2.3. Proposed novel method
methods is illustrated in Fig. 1. The temperature range for producing
borophene is within the range of 300 to 1100◦ C with different structural This novel method for borophene is based on the concept of graphene
configurations, properties and applications [13,14,7,15–20]. synthesis from the electrochemical exfoliation process which is illus
As previously stated, the molecular beam epitaxy (MBE) method is trated in Fig. 2 which is completely different from the concept of
better for fabricating monolayer or few-layer high-crystallinity bor sonochemical exfoliation process [9,17–20]. Comparing with graphene
ophene, whereas the CVD method is better for controlling the layer or synthesis, graphite is used as a cathode material. In reality, graphite is a
structure configuration of large-area borophene with various standing carbon-based filler with an electrical conductivity of 104 S/cm at
directions to the substrate. The sonication-assisted liquid-phase exfoli ambient temperature, which is comparable to carbon fibers. Due to its
ation process, which has a more hopeful future in industry, is recom good electrical conductivity, it can produce a large amount of exfoliated
mended for high-yield borophene. Only a few borophene phases have graphene at low temperature, which makes the process less chemical
been successfully manufactured up to this point, significantly less than tedious, faster, easier, and scalable. However, in borophene synthesis
the many dozen predicted in theory. As a result, the researchers continue boron can be used as a cathode material in this proposed electro
to face a significant challenge. The wavy shape of borophene due to its chemical exploration process. The problem is that boron is not a good
unique atom packing, is making it labor intensive for researchers to conductor like a graphite at low temperature. Boron is nearly an insu
produce stable borophene using mechanical exfoliation methods. As a lator at low temperature; however, it conducts electricity similar to a
result, preparation tactics for borophene synthesis are shifting to alter metal at high temperature [22–24]. The electrical conductivity of boron
native techniques such as solvothermal method, liquid-phase exfolia at ambient temperature is only 0.0001 S/m. To resolve this constraint,
tion, BME, CVD, PVD. However, synthesis of borophene is still boron is designed in such a way so that the temperature of boron can be
challenging, because bulk boron has fairly complex spatial arrange varied.
ments and various chemical characteristics [16]. The sonochemical In this design, a hollow opening in the circular boron rod was
exfoliation process [9,17–20] is a distinct technique and fully different maintained and the electric heater coil was inserted in this opening. The
from the proposed novel process. In sonochemical synthesis, temperature controller was connected with this boron rod to control the
free-standing borophene sheets were made by dispersing 150 mg of temperature of boron at a desired level. In the electrochemical exfolia
boron in 40 ml each of the following: acetone, di-isonopropyl alcohol, tion process, the platinum as an anode and designated boron as a
di-methyl formamide, iso-propyl alcohol, and ethylene glycol. Every cathode were immersed in a suitable electrolyte solution. The temper
bottle was placed in an ultrasonic bath (Cole Parmer, 40 KHz), and the ature of the boron rod was increased at a certain level and conductivity
dispersion was ultrasonically treated for up to 24 h. In order to guar was measured to maintain the conductivity within the required level
antee the production of borophene sheets, samples were obtained which exfoliates borophene.
regularly, from every two hours to twenty-four hours, from each of the Afterwards, through the vacuum filtration, the exfoliated borophene
five vessels containing various solvents. Following centrifugation (Remi, flakes were congregated from the electrolyte solution. It was filtered
R-24) of the resultant fluids at a speed of 5000 rpm for three minutes, several times by porous nylon membrane and washed with demineral
optical and transmission electron microscopy were used to analyze the ized water for removing any trace of residual salts from the collected
supernatant. The technique was continued in order to produce few layer boron flakes.
borophene sheets as it was discovered that the supernatant includes Exfoliated boron flakes were sonicated for a minimum two hours in
fewer than 8 layers. The difficulty of filtering out borophene from the acetone so that flakes could disperse into it and produce a few atomic
reaction solution in sonochemical synthesis can be overcome with the layers of borophene. Subsequently, the sonicated solution was centri
help of the suggested technique. fuged for 30 min at 4000 rpm to separate the atomic layers of borophene
and boron flakes. As a result of that centrifugal force, boron flakes are
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M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
Fig. 2. Novel method of borophene production (all machines, such as temperature controller, heating coil, centrifuge and sonication are available in our laboratory).
deposited as a dross in the test tube where the supernatant part of the process is conducted without any vacuum conditions. In the future, the
solution contains only a few atomic layers of borophene. Finally, the synthesis of borophene by this novel process will be conducted under
supernatant solution of layered borophene was collected by decantation. vacuum conditions to avoid the adverse effects of environmental
The wet borophene was then dried and collected for further investiga contaminants.
tion. The advantage of this novel process is that the borophene can be
produced at various temperatures. The optimum temperature condition
for confirming better quality of borophene can be identified. This
method also exhibited the advantages of less chemical tiresome, faster,
easier and scalable similar to graphene manufacturing. The synthesis
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M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
3. Results and discussion the surface. The next is diffuse layer by which both positive and negative
ions are existed loosely. Considering all layers, the stability of any par
3.1. Physical observation and Raman spectroscopy analysis ticles is measure within the slipping plane. The stability level can be
positive or negative depending on the particle tested. The block diagram
This method is practically conducted recently in our laboratory, of surface charge zeta-potential is illustrated in Fig. 6.
temperature between 600 and 1000◦ C exfoliated boron and borophene For borophene sample, the zeta potential value is above +100mV,
flakes were noticed. After sonication, borophene particles are visible represents sample excellent stability. Where the borophene particle size
shown in Fig. 3 in acetone solution and this solution was collected in a was found 400 to 600 nm. The standard table of zeta potential for
centrifuge tube for centrifugation as seen in Fig. 4. The Raman spectrum confirming the stability is noted in Table 2.
of borophene obtained in this method is confirmed by literature [25]
and almost similar trend is observed as represented in Fig. 5. This test 4. Prospects and possible challenges
can be considered as a trial-and-error basis and more tests and analysis
are required for clear understanding of the prospect of this method for The challenges of this novel method are:
in-line mass production, stable borophone and commercial aspects. The
behavior of electrolyte solution with the increase of temperature in (i) Temperature management is necessary for situating the free en
terms of viscosity and conductivity is not examined during this initial ergy of boron growth between the nucleation obstacle of 3D
test. boron and 2D borophene. So far, there are no graphs or tables to
find the relationship between temperature and electrical con
3.2. Stability analysis ductivity of bulk boron. The temperature seems to be conductive
after 600◦ C (from a recent test) although the conductivity is not
Any particle in suspension, macromolecule, or material surface ex measured. However, there is a relationship graph of electrical
hibits the physical characteristic known as zeta potential. To evaluate conductivity and resistivity against temperature for boron-
the potential stability of the colloidal system, zeta potential is used. In undoped (NCM-1) and boron-doped (NCM-2) nanoceramic pel
zeta potential, the first inner layer of the electric double layer, which lets depicted in Fig. 7 [26]. This Figure may provide some insight
occurs at a charged surface in an ionic solution, is known as the Stern of the temperature behavior on boron but this may not be the
layer. The Stern layer, which is made up of a layer of ions charged in naked truth.
opposition to the surface and adhering to it, is stationary with respect to (ii) Despite the electrochemical exfoliation process, boron was
designed with the electrical coil for varying the temperature.
How the electrolyte solution will behave with increasing tem
perature is not examined in this preliminary analysis. Neverthe
less, it can be noted from previous results and confirmed that the
amount of an electrolyte dissolved in solution is influenced by
temperature. Higher temperatures improve electrolyte solubility
and thus, ion concentration, resulting in greater electrolytic
conduction [27]. Fig. 8 illustrated the trends of the results where
electrolyte solution is a function of molar concentration and
temperature. The quality of the electrolyte solution and their
viscosities change cannot be assured before application of this
new method.
(iii) The quality, structure and properties of produced borophene by
this method is expected to be better but these can be assured after
TEM, FESEM, EDS, Zeta Potential, XPS, XRD, FTIR, AFM, UV,
Particle size analysis and other related observations.
(iv) According to earlier research [25], borophene can be anisotropic,
and as a result, their electrical conductivity varies depending on
the crystallographic orientation. This is another challenging issue
and also it can be considered as a hopeful consequence since it
exhibits higher carrier density and mechanical stiffness in
preferred direction because of this property.
5. Conclusions
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M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
Fig. 5. Raman spectrum of borophene (a) present study (b) literature [25].
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M.A. Chowdhury et al. Applied Surface Science Advances 11 (2022) 100308
Fig. 7. Electrical conductivity and resistivity against temperature for boron-undoped (NCM-1) and boron-doped (NCM-2) nanoceramic pellets [26].
Declaration of Competing Interest aptasensors for point-of-care cancer diagnostics, Nano-Micro Lett. 14 (1) (2022)
1–34.
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interests or personal relationships that could have appeared to influence biomedical applications: current challenges and future prospects, J. Mater. Chem.
the work reported in this paper. B (2022).
[8] Andrew J. Mannix, Zhuhua Zhang, Nathan P. Guisinger, Boris I. Yakobson, Mark
C. Hersam, Borophene as a prototype for synthetic 2D materials development, Nat.
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