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SMC-Bulletin-April 2020
SMC-Bulletin-April 2020
1) April 2020
ISSN 2394-5087
Special Issue on
CARBON-BASED MATERIALS
Front cover shows microscopic images of a nitrogen implanted diamond (top left) and a graphene-nanodiamond hybrid films (top middle
and right) along with a schematic of a coaxial gated CNTFET device structure with doped source and drain extension (bottom).
a
SMC Bulletin Vol. 11 (No. 1) April 2020
Executive Committee
President Members Co-opted Members
Dr. V. K. Jain Dr. Neeraj Agarwal Prof. S. Basu
UM-DAE Centre for Excellence in Basic UM-DAE Centre for Excellence in Basic CSIR-Institute of Minerals and Materials
Sciences, University of Mumbai, Sciences, University of Mumbai, Technology,Bhubaneswar-751013
Kalina Campus, Mumbai-400098 Kalina Campus, Mumbai-400098
jainvk@cbs.ac.in Dr. (Smt.) Aparna A. Banerjee Prof. Lalita Ledwani
Bhabha Atomic Research Centre Department of Chemistry
Vice-Presidents Trombay, Mumbai-400085 Manipal University Jaipur
Dr. A. K. Tyagi Jaipur-303007
Bhabha Atomic Research Centre Dr. (Smt.) Vinita Grover Gupta
Trombay, Mumbai, 400 085 Bhabha Atomic Research Centre Dr. K. I. Priyadarsini
aktyagi@barc.gov.in Trombay, Mumbai-400085 Bhabha Atomic Research Centre
Dr. Rajesh Ganesan Trombay, Mumbai, 400 085
Prof. G. Mugesh Indira Gandhi Centre for Atomic Research
Indian Institute of Science Kalpakkam-603102 Dr. V. Sudarsan
Bangalore - 560 012 Bhabha Atomic Research Centre
mugesh@iisc.ac.in Dr. P.A. Hassan Trombay, Mumbai-400085
Bhabha Atomic Research Centre
Trombay, Mumbai-400085 Dr.A. K. Tripathi
Dr. (Smt.) Daisy Joseph Bhabha Atomic Research Centre
Bhabha Atomic Research Centre Trombay, Mumbai-400085
Trombay, Mumbai-400085
Secretary Dr. S. Kannan
Dr. R. K. Vatsa Bhabha Atomic Research Centre
Bhabha Atomic Research Centre Trombay, Mumbai-400085
Trombay, Mumbai, 400 085
rkvatsa@barc.gov.in Shri. R. Manimaran
Bhabha Atomic Research Centre
Trombay, Mumbai-400085
Treasurer
Shri R. K. Mishra Dr. Ranjan Mittal
Bhabha Atomic Research Centre Bhabha Atomic Research Centre
Trombay, Mumbai, 400 085 Trombay, Mumbai-400085
rkmishra@barc.gov.in
Dr. SandeepNigam
Bhabha Atomic Research Centre
Trombay, Mumbai, 400 085
Prof. Sri Sivakumar
Indian Institute of Technology
Kanpur, 208016
Dr. Deepak Tyagi
Bhabha Atomic Research Centre
Trombay, Mumbai-400085
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Contact address
Society for Materials Chemistry
C/o Chemistry Division
Bhabha Atomic Research Centre, Trombay, Mumbai, 400 085, India
Tel: +91-22-25592001, E-mail: socmatchem@gmail.com
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SMC Bulletin Vol. 11 (No. 1) April 2020
SMC BULLETIN
A Publication of the Society for Materials Chemistry
Special Issue on
Carbon-Based Materials
i
SMC Bulletin Vol. 11 (No. 1) April 2020
SMC Bulletin
Vol. 11 No.1 April 2020
Guest Editor
Dr. Padmnabh Rai
School of Physical Sciences
UM-DAE Centre for Excellence in Basic Sciences
University of Mumbai, Kalina Campus
Santacruz (E), Mumbai-400098
e-mail: padmnabh.rai@cbs.ac.in
Editorial Board
Dr. Arvind Kumar Tripathi
Chemistry Division
Bhabha Atomic Research Centre
Trombay, Mumbai, 400 085
e-mail: catal@barc.gov.in
Dr.Manidipa Basu Dr. Rajesh Ganesan
Chemistry Division Materials Chemistry Division
Bhabha Atomic Research Centre Indira Gandhi Centre for Atomic Research
Trombay, Mumbai, 400 085 Kalpakkam, 603102
e-mail: deepa@barc.gov.in e-mail: rajesh@igcar.gov.in
Published by
Society for Materials Chemistry
C/o. Chemistry Division
Bhabha Atomic Research Centre, Trombay, Mumbai, 400 085
E-mail: socmatchem@gmail.com,
Tel: +91-22-25592001
Please note that the authors of the paper are alone responsible for the technical contents of papers and references cited therein.
Front cover shows microscopic images of a nitrogen implanted diamond (top left) and a graphene-nanodiamond hybrid films (top middle and right)
along with a schematic of a coaxial gated CNTFET device structure with doped source and drain extension (bottom).
ii
SMC Bulletin Vol. 11 (No. 1) April 2020
Guest Editorial
The allotropes of carbon exist in form of graphite (sp2), carbon nanotube (sp2), graphene (sp2),
fullerene (sp2) and diamond (sp3). The current issue is focussed on advanced development in
carbon-based materials for their potential applications in green energy, photonics and quantum
technologies. Researcher from India and abroad were invited to contribute their article on thematic
topic.
The current issue of bulletin includes research and development work on carbon nanotube,
graphene and diamond. An energy storage application of carbon nanomaterials is discussed for
next generation technology. Growth mechanism of vertically aligned graphene-nanodiamond
is discussed. Nanocrystalline diamond shows better electron field emission when implanted
with nitrogen ion. Simulation of electroluminescent short-channel carbon nanotube field effect
transistor is presented.
It has been my great pleasure to act as a guest editor for special issue on “Carbon-based
Materials. My sincere thanks to Prof. V. K. Jain, President, SMC and all the office bearers of
executive committee and editorial board of SMC bulletin for giving me the opportunity. I also
thank all the authors for their contribution of the current issue of SMC bulletin.
I wish that the articles of the current issue attract broad audience and the readers will find it
useful and informative.
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SMC Bulletin Vol. 11 (No. 1) April 2020
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SMC Bulletin Vol. 11 (No. 1) April 2020
Dear colleagues,
Warm greetings from Executive Council of Society for Materials Chemistry (SMC).
The Editorial Board of SMC Bulletin is making consistent efforts to bring out special issues on cutting
edge research on contemporary subjects. The current issue presents some aspects of R & D work on “Carbon-
Based Materials” pursued by different research groups in India and abroad.
The topics covered in this thematic issue include work on energy storage, display application and simulation
studies in carbon nanotube, graphene and diamond. A supercapacitance application of carbon nanotube is
reviewed by the group from Rice University.There is an enhanced focus on using CNT forests and arrays
for flexible and micro-supercapacitors for possible use in cell phones and sensors. Storing hydrogen in solid
state materials is a challenge for green energy technology. Metal nanoparticle decorated carbon materials is
showing satisfactory result for storing hydrogen. Non-catalytic direct growth of few layered vertical graphene-
nano-diamond hybrid structure has been demonstrated by thermally activated hot filament chemical vapor
deposition. Nitrogen ion implanted nano-crystalline diamond is showing enhanced electron field emission
properties. Electroluminescent property of short-channel (~20 nm) single-walled carbon nanotube field effect
transistor is demonstrated by simulation using non-equilibrium Green’s function method (NEGF).
We place on record our sincere appreciation to Dr. Padmnabh Rai, Guest Editor, who has taken efforts
and an interest to bring out this special issue on ‘Carbon-based Materials” in a timely manner. We also thank
all the members of SMC for their continued support and cooperation in the growth of the Society.
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SMC Bulletin Vol. 11 (No. 1) April 2020
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SMC Bulletin Vol. 11 (No. 1) April 2020
CONTENTS
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SMC Bulletin Vol. 11 (No. 1) April 2020
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SMC Bulletin Vol. 11 (No. 1) April 2020
Keywords: Carbon nanotube, supercapacitor, energy in 2018 is about 20 TW-years of which 0.5TWY (2.5%) is
density, power density, green energy from solar (EIA data).
According to the UN World Energy Outlook Report of electrodes, it is noted that each electrode develops a
2019, “By 2040, low-carbon sources provide more than half Helmholtz layer of opposing charge within a few microns
of total electricity generation. Wind and solar PV are the thereby forming a capacitor at each electrode [4]. The
star performers, but hydropower (15% of total generation thickness of this Helmholtz layer is defined as Electric
in 2040) and nuclear (8%) retain major shares”. Double Layer and depends on the surface porosity of the
electrodes (normally made of carbon) as well as the size of
2. Energy storage solvated ions of the electrolyte. The distance between the
The energy from the renewable energy sources such as opposing charges (dictated by the electrode /electrolyte
solar and wind vary with time of the day and the season of interface) falls to less than a micron (Fig. 3) and thereby
the year. It is necessary to store the excess energy during providing large capacitance at each electrode [5].
peak energy production cycles and release it during peak The supercapacitor (Electric Double Layer Capacitor)
demand cycles. A variety of energy storage methods have is therefore in principle a combination of two very thin
been used including mechanical (Flywheel, compressed capacitors and can only operate at low voltages (2 or 3V)
air, pumped hydroelectric, etc.), thermal (Molten salt, ice but has capacitance values of the order of tens of Farads.
chest, cryogenic liquids, etc.) and electrochemical (Battery, Also, the supercaps exhibit very low equivalent series
supercapacitor, fuel cell, etc.). Batteries and supercapacitors resistance (ESR) enabling them to charge fast (few seconds
have become very common storage media for a majority of compared to few hours in case of batteries) and can provide
portable power devices including cell phones, automobiles large number of charge-discharge cycles (several million
and aeroplanes. Normally, batteries provide high energy cycles). Inorder to obtain high energy supercapacitors, the
density (200 Wh/kg) whereas supercapacitors provide adopted strategy should be to increase the capacitance and
high power density (10,000 W/kg) and with quick recycling to increase the operating voltage since the stored energy is
capability. Elon Musk [3] stated at the Cleantech Forum proportional to voltage square. The capacitance depends
2011 in San Francisco about the future of electric vehicles “If mostly on the electrodes and the energy depends on the
I were to make a prediction, I’d think there’s a good chance electrolyte. Commercial supercapacitors normally use
that it is not batteries, but super-capacitors.” organic electrolytes that can operate at voltages close to 3V
compared to aqueous electrolytes at about 2V. Recently,
3. Supercapacitor Tomiyasu et al. [6] reported a remarkably high 3.2 V
The supercapacitor, also known as ultracapacitor supercapacitor containing a saturated aqueous solution
has orders of magnitude larger capacitance (order of of sodium perchlorate and observed high energy density
several Farads) than a regular capacitor which normally of 36.3 Wh/kg.
has capacitances of several microfarads. Capacitor stores
energy by means of a static charge stored in a medium 3.1 Pseudo-capacitor
between two electrodes and its capacitance increases with The EDLCs however suffer from low energy density.
area and is inversely proportional to distance between the To rectify these problems, transition metal oxides (RhO2,
charged electrodes. When an ion conducting electrolyte is MnO2, TiO2, …) and transition metal sulphides were tried
used with a porous insulating separator material between in the carbon electrodes. It was noted that the electrode
- electrolyte interface now undergoes redox reactions
enhancing the capacitance 10 to 100 times more than
EDLCs. This new type of supercapacitor is called pseudo-
capacitor and it behaves like a battery with slow charging
rates and limited number of cycles.
rcapacitor (Electric Double Layer Capacitor) is therefore in principle a combination of two very
2
s and can only operate at low voltages (2 or 3V) but has capacitance values of the order of tens of
the supercaps exhibit very low equivalent series resistance (ESR) enabling them to charge fast
compared to few hours in case of batteries) and can provide large number of charge-discharge
SMC Bulletin Vol. 11 (No. 1) April 2020
and co-workers [7] provided a review of asymmetric and have diameters of the order of a nm and lengths
supercapacitors and their version of Ragone’s plot (Fig. are normally in the range of microns there by becoming
4) compares the different electrochemical energy storage ideal structures for large aspect ratio materials. The
carbon nanotube (CNT) can be visualized as a graphene
sheet rolled into a tube forming single wall (SWCNT) or
multiwall carbon nanotube, MWCNT (coaxial tube with
different layers) and Fig. 6 shows images [8] of different
CNTs. The discovery of CNTs can be attributed to three
researchers Endo, Bethune and Iijima even though larger
Energy Density (Wh/kg)
Fig. 5:Fig.
Classification of supercapacitors
5: Classification of supercapacitors and possibleelectrode
and possible electrode materials
materials [7]. [7].
4. Carbon nanotubes 3
Carbon nanotubes are 1-D nanostructures of carbon and have diameters of the order of a nm and lengths are
normally in the range of microns there by becoming ideal structures for large aspect ratio materials. The carbon
SMC Bulletin Vol. 11 (No. 1) April 2020
Fig. 6:A family of CNTs: (a) schematics of armchair, zigzag, and chiral SWCNTs (from left to right); (b) SWCNT; (c-d)
MWCNT with no catalyst; and (e) MWCNT with a catalyst particle [8].
The twist of the graphene sheet while it is being rolled into CNTs dictates the chirality of the CNTs
resulting semiconducting and metallic nanotubes. Normally, the synthesized CNTs contain a variety of these
semiconducting and metallic CNTs in a statistical ratio of 2:1 and form bundles because of strong van der Walls
interactions between individual tubes. There are a vast number of papers and books about the identifying the
Fig. 6:A family of CNTs: (a) schematics of armchair, zigzag, and chiral SWCNTs (from left to right); (b) SWCNT; (c-d)
6: A family
Fig.de-bundling
chirality, of CNTs:
and separating (a) schematics
the individual CNTs by tubeof armchair,
type zigzag, and Recent
chiral
SWCNTs (from left to right); (b) SWCNT; (c-d) MWCNT with no
(Semiconducting or metallic).
research was focused on growing CNTs of specific chirality for applications such as nanosensors. The reader is
MWCNT with no catalyst; and (e) MWCNT with a catalyst particle [8].
catalyst; and (e) MWCNT with a catalyst particle [8].
referred to a recent report from a biennial conference on CNT nucleation and growth [10] for the status of these
issues. In addition, this conference series has identified the appropriate development trend for SWCNT growth
for a variety of applications (Fig. 7).
The twist of the graphene sheet while it is being rolled into CNTs dictates the chirality of the CNTs
partial list of these properties [11] for SWCNTs. The values
resulting semiconducting and metallic nanotubes. Normally, the synthesized CNTs contain a variety of these
for MWCNTs will be off by a factor of 2 or more.
semiconducting and metallic CNTs in a statistical ratio of 2:1 and form bundles because of strong van der Walls
Degree of Chirality/Diameter Control
interactions between individual tubes. There are a vast number There is a vast
of papers and amount of research
books about carried the
the identifying out
chirality, de-bundling and separating the individual CNTsover the last
by tube typethree decades on these
(Semiconducting properties
or metallic). and a
Recent
research was focused on growing CNTs of specific chirality concentrated effortsuch
for applications in the synthesis, purification
as nanosensors. The readerandis
processing of CNTs for a variety of applications
referred to a recent report from a biennial conference on CNT nucleation and growth [10] for the status of these ranging
issues. In addition, this conference series has identified thefrom aerospace,
appropriate automobile, trend
development electronics to medicine
for SWCNT [12].
growth
for a variety of applications (Fig. 7). For some applications it is necessary to have individual
SWCNTs of specific tube type (semiconducting or metallic)
and chirality. However, for energy storage applications
in batteries and supercaps, the requirements are not so
stringent, and the CNT material should have large surface
area and porosity as well as high electrical conductivity.
SWCNTdiagram
Fig. 7: Structure−property relationship Organization / Packing
showing the application spaceDensity
of SWCNTs with respect to tube
Majority of energy storage studies were done using bundles
diameter/helicity and architecture. The horizontal axis shows the organization of the SWCNTs from a random network to
highly aligned architectures (vertically aligned, fibers, etc.), while the vertical axis shows the degree of diameter/helicity
of SWCNTs and MWCNTs. Recent research focused on
Fig. 7: Structure−property relationship diagram showing the
control from mixed to single helicity. Existing and emerging SWCNT applications are shown in the square and oval boxes,
using vertically aligned CNTs (VACNTs) aka CNT forests
respectively. The diagonal arrow in the graph shows the general direction of developments in synthesis over time [10].
application space of SWCNTs with respect to tube diameter/helicity as 2D mats and 3D structures for energy storage.
and architecture. The horizontal axis shows the organization of the
SWCNTs from a random network to highly aligned architectures
5. CNT applications in supercapacitors
(vertically aligned, fibers, etc.), while the vertical axis shows the degree
of diameter/helicity control from mixed to single helicity. Existing and During the early years, the advancement of
emerging SWCNT applications are shown in the square and oval boxes, supercapacitors (SCs) was made possible by the porosity
respectively. The diagonal arrow in the graph shows the general direction and large surface area of activated carbon. The control
of developments in synthesis over time [10]. of porosity in SCs provides specific capacity of ion
Fig. 7: Structure−property relationship diagram showing the application space of SWCNTs with respect to tube
SMC Bulletin Vol. 11 (No. 1) April 2020
adsorption and the diffusion of ions in and out of the pores help to increase wettability of the normal carbon electrodes
during the charge/discharge processes. The discovery resulting in 50% enhancement of capacitance. It has been
and availability of CNTs with much better thermal and a great challenge to increase SC’s energy density without
electrical conductivities in addition to mechanical strength compromising its power density.
helped enhancements of capacitance as well as energy
density. A recent review [11] provides valuable information 5.1 Combining CNTs with other nanomaterials
on the applications of CNTs in supercapacitors. The table It is noted that pure CNTs did provide a large
2 summarizes some of the results. enhancement of the SC performance compared to regular
carbon based SCs. Additional improvements are possible
Table 2 Performance of different bare CNT- by adding other nanomaterials (NMs) such as graphene,
based supercapacitors [11] graphite oxide, carbon nano-cones, carbon nano-onions
and carbon sponge. A recent review [14] focuses on how
S. Electrode Specific Energy Power to improve the performance of SCs by using a combination
No. capacitance density density of materials with CNTs. One scenario will use CNTs
(F/g) (Wh/kg) (kW/kg) utilized as the scaffolds and metal oxides are deposited
in situ. Another scenario suggests using nanocomposites
1 SWCNT film 180 7 20
(Fig. 5) with CNTs and conducting materials including
2 Nitric acid 102 0.5 – polymers such as polyaniline (PANI). Chen and co-workers
treated reported [15] a study of comparing disordered CNTs and
MWCNTs vertically aligned CNTs (VACNTs) for SCs. They studied
5.1 Combining CNTs with other nanomaterials
3 It is noted
Rolled 35 43.7 197.3
that pure CNTs did provide a large enhancementhigh-performance
of the SC performance supercapacitor
compared based on polyaniline/
to regular carbon
SWCNT
based SCs. film
Additional improvements are possible by adding vertical-aligned carbon nanotubes
other nanomaterials (NMs) such(PANI/VA-CNTs)
as graphene,
4 graphite
Stacked
oxide, carbon20–160
nano-cones, 17.5–94 43–210
carbon nano-onions nanocomposite
and carbon sponge.electrodes
A recent where
review the[14]vertical-aligned-
focuses on
how to SWCNT structure is formed by the
improve the performance of SCs by using a combination of materials with CNTs. One scenario will use electrochemical-induction
CNTs arrayutilized as the scaffolds and metal oxides are deposited (0.75 V). in Thesitu.
supercapacitor
Another scenario displayed
suggestslarge specific
using
5 nanocomposites
Stacked (Fig. 5) with
11–22 CNTs and
2.3–5.4 conducting
19.6– capacitance
materials including of 403.3
polymers F/g,
suchwhich
as is 6 times
polyaniline higher
(PANI). than
ChenMWCNTand co-workers reported [15] a study35.4 of comparing disordered
disordered CNTs CNTs and 4vertically
in HClO electrolyte.aligned CNTs the
Additionally,
(VACNTs) for SCs. They studied high-performance supercapacitor based on
supercapacitor polyaniline/vertical-aligned
can also present high specific carboncapacitance
array
nanotubes (PANI/VA-CNTs) nanocomposite electrodes where the vertical-aligned-structure is formed
(314.6 F/g), excellent cycling stability (90.2% retention by the after
The first comprehensive study
electrochemical-induction [13]The
(0.75 V). of space charge displayed
supercapacitor large specific capacitance of 403.3 F/g,
3000 cycles at 4 A/g) and high energy density (98.1 Wh/kg) which
is 6 timesinhigher
distributions EDLCs than disordered
based CNTs in
on polarizable HClO4 electrolyte.
nanoporous Additionally,
in EMIBF organic theelectrolyte.
supercapacitor
Theycan also present
claimed that the key
4
high specific capacitance (314.6 F/g),
electrodes, containing carbon nanotubes (CNTs) as excellent cycling stability (90.2% retention after 3000 cycles at 4 A/g) and
to high-performance lies in the vertical-aligned-structure
high material
electrode energy wasdensity
done(98.1 Wh/kg) in EMIBF
in 2007. It was noted 4 organic electrolyte. They claimed that the key to high-
that CNTs
performance lies in the vertical-aligned-structure providing for faster ion diffusion and high electrochemical
capacitance of polyaniline for better ion accommodation.
Fig.
Fig. 8: 8:
(a) (a) Cycle
Cycle testing
testing of supercapacitors
of supercapacitors underofa3 voltage
under a voltage of 3 Vdensity
V at a current at a current density
of 4 A g−1. of 4 Adensity
(b) Energy g−1. versus
(b) Energy
power
density
density versus power [15].
of supercapacitors density of supercapacitors [15].
It was concluded that composite materials can improve the performance of supercapacitor electrodes
much better than a single material ever could. It is also possible to design 3D structures using a combination of 5
materials to provide the needed surface area, accessibility to nano size pores and quick ion adsorption and
desorption. One recent study reported using CNT scaffolds, graphene nanosheets and PANI. Jin and co-workers
SMC Bulletin Vol. 11 (No. 1) April 2020
providing for faster ion diffusion and high electrochemical the role of an ion reservoir, while the incorporated CNTs
capacitance of polyaniline for better ion accommodation. are believed to provide greater area for the ions to adhere
to and fast channels for charge transport”. The performance
It was concluded that composite materials can improve
enhancement is shown in Fig. 9.
the performance of supercapacitor electrodes much better
than a single material ever could. It is also possible to Zhang and co-workers [18] developed an asymmetric
design 3D structures using a combination of materials supercapacitor (ASC) with 3D cobalt sulfide encapsulated
to provide the needed surface area, accessibility to nano carbon nanotube/carbon nanofiber (Co9S8@CNT/CNF)
size pores and quick ion adsorption and desorption. One composite, which showed a capacitance of ~1580 F/g at
recent study reported using CNT scaffolds, graphene a current density of 1 A/g. They report a maximum energy
nanosheets and PANI. Jin and co-workers [16] constructed density of 58 Wh/kg at a power density of 1000W/kg
a three-dimension (3D) conductive network by CNTs and and even after 10,000 cycles, the ASC still retains 93% of
graphene nanosheets on the polyester fabric via a “dipping- the initial capacitance at a current density of 5 A/g. They
drying” process and electrophoretic deposition method, claim that the aligned CNT/CNF nanochannels increase
which significantly increased the electron transportation the ion transfer speed and shorten the ion transfer distance,
rate and reduced the electrolyte ion diffusion path. The thereby boosting both power density and energy density.
resulting composite fabric provided a promising substrate
for flexible supercapacitor’s textile-based electrode 5.2 CNTs for flexible supercapacitor
preparation. A recent review on CNT based fibers for energy storage
In 2018, Zhou et. al. [17] reported a 3D structure with focuses on the possibility of flexible and wearable energy
the addition of graphitic nanofibers (GNFs) to CNTs storage [19]. The flexible energy storage devices assembled
to improve the SC performance. The CNT/GNF-based from carbon nanotube fiber-based electrodes has the
symmetric device showed a maximum specific energy advantages of being bendable, lightweight, and invisible
Fig. 9:Electrochemical properties of the CNTs/GNFs- and CNTs-based supercapacitors in 6 mol/L KOH electrolyte. CV
of 72.2 Wh/kg at a power density of 686.0 W/kg.curves Theof (a) encapsulation,
CNT/GNFs and (b) CNTs which will be
under various scanthe foundation
rates. (c) The specific of the wearable
capacitance of CNTs/GNFs and CNTs
smart textiles and promotes the rapid development of
calculated at various current densities. (d) EIS measurements of CNTs/GNFs and CNTs based EDL supercapacitors [17].
supercapacitor showed a very good cycling stability of 96%
after 10 000 charge/discharge cycles. According to them, Zhang flexible
and energy
co-workers [18]storage
developeddevices.
an asymmetric supercapacitor (ASC) with 3D cobalt sulfide
encapsulated carbon nanotube/carbon nanofiber (Co9S8@CNT/CNF) composite, which showed a capacitance of
“the GNFs have open edges and large interlayer spacing The
~1580 F/g at a current relatively
density low
of 1 A/g. They specific
report capacitance
a maximum energy density ofand yield
58 Wh/kg at a power density
which will ensure ion transportation at high rates andofplays
1000W/kg and even after 10,000 cycles, the ASC still retains 93% of the initial capacitance at a current
have been the most drawbacks of carbon nanotube
density of 5 A/g. They claim that the aligned CNT/CNF nanochannels increase the ion transfer speed and
shorten the ion transfer distance, thereby boosting both power density and energy density.
6
the wearable smart textiles and promotes the rapid development of flexible energy storage devices.
The relatively low specific capacitance and yield have been the most drawbacks of carbon nanotube
based fibers, but it is theoretically possible to overcome these by using appropriate nano-structured materials
and improving the fiber fabrication methods. Some of the CNT fiber fabricationSMC methods used to study SCs is
Bulletin Vol. 11 (No. 1) April 2020
shown in Fig. 11.
Fig. 11: Schematic illustration of (a) solid-spun carbon nanotube fiber with internal graphene sheets, (b) Co-spinning of
Fig.CNT/graphene
11: Schematic illustration of (a)
hybrid fiber solid-spun
with carbon
solid-spun andnanotube
electro fiber with internal
spinning methods,graphene sheets, (b) Co-spinning
(c) Hydrothermal proceduresof CNT/graphene
of rGO/SWCNT hybrid
fiber with solid-spun and electro spinning methods, (c) Hydrothermal procedures
composite fiber, (d) Super-acid exfoliated graphene sheets co-spun with CNTs [19]. of rGO/SWCNT composite fiber, (d) Super-acid exfoliated
graphene sheets co-spun with CNTs [19].
There were a few articles on co-spinning CNTs with other materials to prepare a fiber based SC. Ray
Baughman and co-workers [20] developed a novel method that bi-scrolled CNT sheets with drop casting of
MnO2 dispersion into a fiber (shown in Fig. 12). The strategy of biscrolling can dramatically expand the loading
mass of active nanoparticles as high as 99 wt% without any influences on the mechanical properties of fiber.
The bi-scrolled MnO2/CNT fiber was able to achieve an areal specific capacitance of 889 mF/cm2 (or 155
F/cm3) and possessed an energy density of 35.8 μWh/cm2 (or 5.41 mWh/cm3).
Fig. 12: Schematic showing (a) Preparation and structure of biscrolled CNT/MnO2 hybrid fiber, SEM morphologies of (b,
Fig. 12: Schematic showing (a) Preparation and structure of biscrolled CNT/MnO2 hybrid fiber, SEM morphologies of (b, c) as spun biscrolled
c) as spun biscrolled hybrid fiber and (d, e) two-ply coiled yarn integrated in a fabric [18].
hybrid fiber and (d, e) two-ply coiled yarn integrated in a fabric [18].
Jeffrey Glass and co-workers [21] reported highly stretchable supercapacitors based on crumpled CNT-
7
forests that are transferred onto pre-strained elastomer substrates. The crumpled CNT has demonstrated superior
electrochemical performance under large uniaxial or biaxial strains (Fig. 13). Little variation in CV, charge–
SMC Bulletin Vol. 11 (No. 1) April 2020
corresponding
5.3 Computational CV work
curvesonofCNTthe PANI/CNTs/G/PETC
applications of SCs electrode under various twisting times [16].
Computational work on supercapacitors has a long history. Most of the earlier work focused on EDLC aspects
of the supercapacitor. Analytical techniques as well as atomistic computations have been used to provide a
8 theoretical basis for understanding the dependence of capacitance on the electrode and electrolyte. In recent
years molecular modelling has contributed greatly to the understanding of charge storage mechanisms and
dynamics in EDLCs. Calculations based on “Molecular Dynamics” seemed to provide a better understanding of
the SCs. In majority of the cases, the computations did not match the experimental measurements. However,
SMC Bulletin Vol. 11 (No. 1) April 2020
to sustain a stretchability of 800% and possess a specific capacitive effect for electrified CNTs with different
capacitance of 5 mF/cm2 (≈1.25 F/cm3) at the scan rate diameters, as shown in Fig. 15. The MD simulations
of 50 mV/s. According to the authors, these stretchable indicated that the ions do not flow through the CNT when
supercapacitors can also be modified to hybrid SCs by the diameter of CNT is small (Fig. 16).
adding metal oxide nanoparticles.
Compared with the outer surface, the narrow region
Another recent article [16] reports the stability of of the inner surface leads to the reduction in capacitance
composite electrodes for bending and stretching for with the decrease in radius at sub-nanometer scale. This
hundreds of cycles. The results (Fig. 14) show excellent phenomenon is due to the decreasing accessibility of the
resiliency and paves the way for future wearable electronic inner region for electrolyte ions, leading to the reduction
applications. in the number of adsorbed ions and effective active surface
area. The obtained curve of capacitance versus diameter is
5.3 Computational work on CNT applications of consistent with the experimental results.
SCs In 2013, Younghee Lee [23] and coworkers published
Computational work on supercapacitors has a long a paper on a theoretical model based on transmission
history. Most of the earlier work focused on EDLC aspects line combined with pore size distribution. The model
of the supercapacitor. Analytical techniques as well as successfully explained how pores length, and pore radius
atomistic computations have been used to provide a of active materials and electrolyte conductivity can
theoretical basis for understanding the dependence of affect capacitance and dynamic performance of different
capacitance on the electrode and electrolyte. In recent capacitors. The powerfulness of the model was confirmed
years molecular modelling has contributed greatly to by comparing with experimental results of a micro-
the understanding of charge storage mechanisms and supercapacitor consisted of vertically aligned multiwalled
dynamics in EDLCs. Calculations based on “Molecular carbon nanotubes (v-MWCNTs), which revealed a linear
Dynamics” seemed to provide a better understanding of current increase up to 600 V/s scan rate demonstrating
the SCs. In majority of the cases, the computations did not an ultrafast dynamic behavior, superior to randomly
match the experimental measurements. However, these entangled single walled carbon nanotube device, which
calculations did provide an overview of the critical role is clearly explained by the theoretical model.
of the morphology as well as reactions of the electrodes
In 2014, Burt et. al. [24] presented the status of
with electrolytes.
molecular modelling of EDLC. They reviewed and
In 2010, Shim et al. [22] employed the Molecular compared different computational methods. According
Dynamics (MD) technique to study the double-layer to them the Monte Carlo (MC) and molecular dynamics
Fig. Two
Fig.15:15: surfaces
Two of CNTs
surfaces in CNTinanodes
of CNTs CNTofanodes
a supercapacitor with a room temperature
of a supercapacitor ionic temperature
with a room liquid (RTIL) as electrolyte.
ionic liquid (a) The outer
(RTIL) as
surface of CNTs. (b) The inner surface of CNTs. Red and blue dots represent the center-of-mass positions of EMI and BF4 ions of the RTIL
electrolyte. (a) The outer surface of CNTs. (b) The inner surface of CNTs. Red and blue dots represent
+ the center-of-mass
-
Compared with the outer surface, the narrow region of the inner surface leads to the reduction in
9
capacitance with the decrease in radius at sub-nanometer scale. This phenomenon is due to the decreasing
accessibility of the inner region for electrolyte ions, leading to the reduction in the number of adsorbed ions and
Fig. 15: Two surfaces of CNTs in CNT anodes of a supercapacitor with a room temperature ionic liquid (RTIL) as
electrolyte. (a) The outer surface of CNTs. (b) The inner surface of CNTs. Red and blue dots represent the center-of-mass
positions of EMI + and BF4- ions of the RTIL electrolyte, respectively [22].
Compared with the outer surface, the narrow region of the inner surface leads to the reduction in
capacitance with the decrease in radius at sub-nanometer scale. This phenomenon is due to the decreasing
SMC Bulletin Vol. 11 (No. 1) April 2020
accessibility of the inner region for electrolyte ions, leading to the reduction in the number of adsorbed ions and
effective active surface area. The obtained curve of capacitance versus diameter is consistent with the
experimental results.
desorption.
6 Conclusions
In summary, CNTs have become indispensable in
the development of supercapacitors. Most of the earlier
research was carried out using SWCNTs and MWCNTs.
Using CNT forests in the electrodes helped to improve
the accessible surface area, porosity and ion diffusion
resulting in enhanced SCs. Combining the CNTs with
other nanomaterials such as graphene and metal oxides
to form nanocomposites, provided additional capacitance
as well as larger energy densities. The CNT forests and
fibers helped to advance the upcoming field of wearable
energy storage media. On the computational side, the
Fig. 16:Snapshots of internal room temperature ionic liquid (RTIL) ions associated with the radial distributions inside the
Fig. 16: Snapshots of internal room temperature ionic liquid (RTIL)
+ -
CNT anodes. Red and blue dots represent the center-of-mass positions of EMI and BF4 ions, respectively [22]. EDLC calculations have progressed considerably during
ions associated
In 2013, Younghee with Lee the
[23] radial distributions
and coworkers published a paperinside the CNT
on a theoretical modelanodes.
based on the last decade. However, computations of complex
electrode structures, such as three-dimensional hierarchical
transmission line combined with pore size distribution. The model successfully explained how pores length, and
Red andof blue
pore radius dots represent
active materials and electrolyte the center-of-mass
conductivity positions
can affect capacitance and dynamicof performance
EMI+ and of
BF4- ions, respectively [22]. porous networks are lacking. It becomes more challenging
to include the redox reactions of pseudocapacitors.
Experimentally, the push is towards achieving increased
(MD) are the two most favored molecular simulation energy density while maintaining high power density and
techniques used. They state that the MC simulations are with high charge-discharge cycles. The role of CNTs in this
limited to calculating equilibrium properties whereas MD burgeoning field is unambiguous and it is critical to have
simulations can calculate dynamic properties (such as ionic reliable inexpensive industrial scale supply of CNTs to
diffusion) of a molecular system and therefore is more meet the 21st century challenges of energy storage.
useful for EDLC computations.
In 2018, Bo et. al. [25], reported the design of SC Acknowledgement:
electrodes using MD simulations. According to them, Thanks to my colleagues at NASA-JSC in Houston
“Molecular dynamics (MD) simulations could provide for initial work on CNT based supercapacitors and to my
theoretical guidelines for the optimal design of electrodes students and postdocs at Sungkyunkwan University in
and the improvement of capacitive performances, e.g., Suwon who helped to probe EDLC and pseudocapacitor
energy density and power density. The enhancement structures. Encouragement from Rice University to sustain
of power density can be achieved by the intensified ion my interest in energy studies is well appreciated.
dynamics and shortened ion pathway. Rational control of
the electrode morphology helps improve the ion dynamics References
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Dr.
Dr.Arepalli is with
Arepalliis withDepartment
Department of Materials Science
of Materials and NanoEngineering,
Science and NanoEngineering, Rice University
Rice in Houston
since
University in Houston since 2016. He was the Vice President of Graduate Education at of Aerospace,
2016. He was the Vice President of Graduate Education at the National Institute
Hampton,
the NationalVA Institute
from 2013oftoAerospace,
15. Prior to Hampton,
that, he wasVA
a Professor
from 2013underto the
15. World
Prior Class University
to that, he program
in theaDepartment
was of Energy
Professor under the Science at Sungkyunkwan
World Class University
University program (SKKU)
in the in Suwon,
Department of South Korea.
He was the
Energy ChiefatScientist
Science of the Applied
Sungkyunkwan Nanotechnology
University (SKKU) in Suwon,Program and Korea.
South ReentryHePlasma
was Diagnostics
Program
the Chiefat Scientist
NASA-Johnson
of the Space Center
Applied and worked forProgram
Nanotechnology 22 years before moving Plasma
and Reentry to Korea in 2009. Dr.
Arepalli received
Diagnostics his Ph.D.
Program in Physics from
at NASA-Johnson the Center
Space Indian Institute
and worked of Technology
for 22 years(IIT) Kanpur in 1979.
before
He did postdoctoral
moving to Korea inwork2009.atDr.
U Penn andreceived
Arepalli Cornell his
University.
Ph.D. in His current
Physics frominterests include synthesis
the Indian
and processing
Institute of Nanomaterials
of Technology (including
(IIT) Kanpur CNT,
in 1979. HeBNNT and graphene)
did postdoctoral workfor atenergy
U Pennapplications
and such as
fuel cells, solar
Cornell cells, batteries
University. and supercapacitors.
His current He also
interests include focuses on
synthesis andexperimental
processingandofcomputational
research for material
Nanomaterials development
(including for subsonic
CNT, BNNT to hypersonic
and graphene) flows in
for energy addition tosuch
applications aerospace
as structures,
environmental sensors and bioimplants.
fuel cells, solar cells, batteries and supercapacitors. He also focuses on experimental
and computational research for material development for subsonic to hypersonic flows
in addition to aerospace structures, environmental sensors and bioimplants.
11
SMC Bulletin Vol. 11 (No. 1) April 2020
Abstract
On-board hydrogen (H2) storage is a quite time-appropriate research topic attracting heavy attention
throughout the globe for last a few decades for resorting to greener energy alternatives aiming maximization
of specific storage capacity for higher fuel efficiency. Though pure carbon nanomaterials are able to
demonstrate moderate H2 storage capability at low temperature and high-pressure conditions those are
not suitable for practical scenario. However, decoration with suitable metal nanoparticles might raise H2
storage potential of carbon nanomaterials even at ambiance to a great extent, satisfying requirement of
Department of Energy (DoE), USA. This review presents the current perspective covering theoretical and
experimental studies in that direction.
Keywords: Hydrogen storage, Carbon Nanomaterials, storage medium can adsorb a large amount (∼6.5 wt %)
Decorated Carbon Nanomaterials, Binding energy, Release of hydrogen and can release them easily as recommended
temperature by Department of Energy, USA (DoE) [6]. H2 storage by
adsorption within solid substance may happen through
1. Introduction either chemical or physical means. An illustration showing
Since the last few decades, it became necessary various H2 storage methods has been shown in Fig. 1.
to find suitable substitute to conventional fossil fuels The conventional H2 storage materials used over last few
towards a cleaner environment. Among all alternative decades are mentioned below with merits and demerits.
fuels, hydrogen is a promising energy carrier with zero
• Metal alloys with compositions: A2B (e.g., Mg2Ni), AB
emission while burnt with oxygen. Usage of hydrogen
(e.g., TiFe), AB2 (e.g., ZrMn2) and AB5 (e.g., LaNi5) were
(H2), as a fuel, involves release of only water and not any
subject to much experimental and theoretical research
greenhouse gas like carbon di-oxide (CO2) to environment.
for development of solid state H2 storage devices.
Hence, in the current depleting fossil fuel scenario since
Although those alloys seem to be quite viable for H2
last a few decades, huge money is being spent for achieving
storage, their wt% is not promising [7].
enormous abundance of H2 through advancement of
its production technologies [1]. Simultaneously, it is • Metal hydrides are excellent choice for on-board H2
also critical to establish suitable storage routes, as being storage. But their desorption temperature is very high
extremely lightweight, H2 is difficult to store in gaseous [8]. Thus, availability of stored H2 from them is an
form at large quantum [2]. Compressed and liquid-state energy intensive step. Also, recharging them with H2
H2 storage technologies are quite matured mostly for static for reuse involves incorporation of huge energy in the
applications and rocket propulsion systems [3]. However, form of heat. Hence, they are still not favourable choice
for mobile applications, in order to fuel a car with H2 for on-board H2 storage.
instead of gasoline, they are not that advantageous till • Zeolite suffers from less specific storage capacity and
date for need of robust storage containment adding huge thus not a suitable choice for mobile purpose [9] despite
weight into the storage device and vast energy for cooling highly reversible H2 sorption kinetics and storage
and maintaining cryogenic condition of the contained H2 attributes.
[4]. By contrast, solid-state H2 storage devices are preferred
for their ability to capture and retain H2 efficiently through • Ammonia borane, though a promising storage
adsorption at or near ambient conditions without any vital candidate, has the same set of drawbacks as metal
need of containment’s structural integrity [5]. Solid state hydrides [10].
storage may become a viable technology provided the • Aluminium, though is very much promising as a H2
12
SMC Bulletin Vol. 11 (No. 1) April 2020
Fig.Fig.
1: 1:
Different
Differenthydrogen storage
hydrogen storage methods
methods
•source, is still
Metal withfor
too costly
alloys compositions:
recycling dueAto2B (e.g., Mg2Ni),
expensive AB outstanding
received (e.g., TiFe),consideration
AB2 (e.g., ZrMn 2) and H
as potential AB (e.g.,
storage
2 5
LaNi5) wereprocess
electro-winning subject to much experimental and theoretical
[11]. materials forresearch
their lowfor development
cost, good recycling ofcharacteristics,
solid state H2
storage devices. Although those alloys seem to easybeaccessibility,
quite viable lowfor H2 storage,
densities, reasonablytheirgoodwt% is not
chemical
• Organinc frameworks or popularly known as
promising [7].
coordination polymers are synthetic crystalline
stability, wide diversities of bulk and pore structures, and
Metalwhich
•materials hydrides are excellent choice for on-board amenability
H2 storage.toBut synthesize variants or
their desorption post-synthetically
temperature is very
are somewhat analogous to zeolites.
highlinker
[8]. Thus, availability of stored H2blocks engineer traits using an extensive range
from them is an energy intensive step. Also, recharging them of manufacturing,
Organic molecules form the building
with H for reuse involves incorporation
of organic 2frameworks, coordinatively binding of hugeactivation
energy in and carbonization
the form of heat. routes [16]. they
Hence, In general, at any
are still not
favourable choicetofor on-board H2 storage. subzero temperature, room temperature and above, up to
to inorganic clusters form a porous framework
ZeoliteDespite
•structure. suffersgood fromHless specific storageatcapacity 400°C or so, thermal stability of pristine and
and thus not a suitable choice for mobile purpose [9]functionalized
storage capacity low
despite highly reversible
2
H sorption kinetics and CNMs
storage are quite good, and there is no significant concern.
attributes.
temperature, even after enough2 research progress,
Though in general, room temperature H2 storage capacity of
•theyAmmonia
suffer with unacceptably
borane, though low storage capacity
a promising at
storage candidate, has the same set of drawbacks as metal
pure carbon nanomaterials (CNM) is poor, decoration with
ambiance
hydrides[12-13].
[10].
metal nanoparticles through chemical functionalization
Aluminium,
• •Organic polymers can though is veryabove
circumvent much promising
limitations in asmight source, their
a H2 improve is still too costly for recycling due to
storage capacity to great extent for
expensive electro-winning process [11].
future for their lightweight advantage, but it is still in ambiance, satisfying DoE’s requirements. As physisorption
•earlyOrganinc
developmental stage [14]. or popularly known is
frameworks as the
coordination
key mechanism polymers
behindare synthetic
hydrogen crystalline
storage with
With discovery of nanomaterials and emergence of CNMs, and they are appreciably stable, theoreticallyblocks
materials which are somewhat analogous to zeolites. Organic linker molecules form the building they
of organic frameworks, coordinatively
nanotechnology, remarkable improvement in development binding to
can inorganic
serve clusters
infinitely large to form
number of a porous framework
absorption-desorption
structure.
of material has been Despite
achieved good H2 storage
at every sphere ofcapacity
life [15].at low temperature,
cycles without anyeven afterdepreciation.
apparent enough research progress,
they suffer with unacceptably low
In nutshell, remarkable rise in surface to volume ratio in storage capacity at ambiance [12-13].
In this review, theoretical studies regarding H2 storage
nanostructured
• Organicmaterials polymers cantocircumvent
leads above limitations
unusual properties by in carbon in future for their lightweight advantage, but it is
nanomaterials will be considered first in section
still in early developmental stage [14].
virtue of more and more open structures. These are thus 2. Primarily, important aspects regarding mechanism of H
2
With discovery
helpful in betterof nanomaterials
utilization and emergence
than conventional of nanotechnology,
crystalline remarkable
capture and retention improvement
by pure in development
and functionalized CNMs
ofcounterparts.
material hasWith beendiscovery
achievedofat graphene,
every sphere fullerene
of lifeand[15]. will
In nutshell, remarkable
be highlighted. rise in
The next surface towill
subsections volume
follow ratio
to
carbon nanotubes, it was realized that suitable engineering
in nanostructured materials leads to unusual properties byimpart virtueinsights
of moreofand more open
theoretical structures.
simulation These are
for evaluation
of carbon
thus helpfulnanostructures might leadthan
in better utilization to enhancement
conventionalof crystalline
of bindingcounterparts. With discovery
energy, desorption temperature of etc.
graphene,
which
properties
fullerene of carbon.
and carbonThe carbon-based
nanotubes, it wasnanomaterials
realized thathave suitable engineering of carbon nanostructures might lead to
enhancement of properties of carbon. The carbon-based nanomaterials have received outstanding consideration
as potential H2 storage materials for their low cost, good recycling characteristics, easy accessibility, low 13
densities, reasonably good chemical stability, wide diversities of bulk and pore structures, and amenability to
synthesize variants or post-synthetically engineer traits using an extensive range of manufacturing, activation
SMC Bulletin Vol. 11 (No. 1) April 2020
determine efficacy of a particular CNM as a H2 storage as Kubas interaction [22] where the chemical bond in H2
substance. Selected research works regarding theoretical molecule interacts with transition metal (TM)s leading to
calculation of H2 storage performance will be discussed in relatively strong adsorption of molecular H2 for charge
detail for both pure and functionalized CNMs. In section donation from highest occupied orbital of the ligand (H2) to
3, experimental studies regarding H2 storage in carbon the empty metal orbitals and a subsequent back-donation
nanomaterials will be covered mentioning synthesis from filled d orbitals into the lowest unoccupied orbital of
methods and tools for characterization. Both pure and the ligand. Adopting such a method, it is possible for CNM
functionalized CNM cases will be considered separately +TMs to retain appreciable H2 even at room temperature
in the following subsections. Pertinent conclusions and with ease in release. Precisely, binding interactions must
future scopes of studies in this direction will be described fall within an optimum range in order to maximize
in section 4. reversible storage at or close to room temperature. They
can neither be too high nor too low, and the optimum
2. Hydrogen storage in carbon nanomaterials: range defines the thermodynamic constraints of the sorbent
theoretical studies system. At or near room temperature, the desirable range
Theoretical simulations lead an important job in for the binding energy of hydrogen, regardless of modality,
predicting the interaction mechanism of H2 molecules is between 0.1 and 0.6 eV/H2 (10 and 60 kJ/mol). This
with the nanomaterials as well as with functionalized range was determined from an analysis based on entropic
atoms or groups for functionalized Nanomaterials. arguments that the reference entropy values for H2 are
Simulation techniques can bestow vital information like between 0.1and 10MPa, and temperature ranging −20 to
adsorption energy, preferred adsorption configuration, 85°C. At−20°C, the enthalpy of adsorption ranges 21 to
charge transfer etc. which are difficult or impossible 32 kJ/molH2 and at 85°C, the enthalpy increases to 51–71
to obtain from experiment. With the invention of large kJ/molH2. On this basis, one can determine that the ideal
memory, high speed supercomputers, extensive computer binding affinity falls in the range between 20and 70 kJ/
simulations are now very much feasible. Also, so many molH2, leading to a conservative upper range of 58 kJ/
well-established computer codes, both commercial and molH2 (0.6 eV/H2).
open access (e. g. VASP [17], quantum espresso [18],
WIEN2K [19]) are now available to compute theoretical 2.2 Importance of theoretical simulations for
data for H2 storage. So, the availability of supercomputers hydrogen storage
and trusted software packages make it possible to produce Theoretical simulations can present nice picture
H2 storage database for a large number of systems and on charge transfer and orbital interactions which may
suggest the experimentalist the potential systems to not be possible or is difficult to get from experimental
attempt in experiments. measurements. From the simulations data, it is easy to
conclude whether specific H2 is having chemisorptions,
2.1 Mechanism of hydrogen capture and retention physisorption, or Kubas [22-23] types of interactions. The
structural stability and desorption temperature can also be
2.1.1 Interaction of hydrogen with pure carbon predicted from theoretical simulations. Keeping above in
and ‘carbon in presence of heteroatoms’ mind, the role of theoretical simulations for determining
When H2 in atomic form (H) combines with CNMs hydrogen storage parameters and the limitation of
with covalent bonding, it is called chemisorption. Being simulation methods, the following sub-sections will
very strong bond, binding energy for chemisroption is highlight overview of quantum simulations, important
quite high (~1 ev) [20]. Thus, much energy is needed parameters obtained from theoretical data, importance of
to release chemisorbed H2 from carbon. On the other dispersion corrections and sensitivity of theoretical data.
hand, adsorption of molecular H2 by CNM is termed as
physisorption and being van der Waals type interaction 2.3 Overview of quantum simulations
it involves very less binding energy (~0.1 ev) [21] at room Quantum simulation is very useful in terms of
temperature. Hence, capture and retention of appreciable providing physical insight of the system as well as
amount of H2 by carbon is thermodynamically possible only producing data that can be compared with experimental
at high pressure and low temperature condition. Between data. Quantum simulations need numerical solution
these two extremes, decoration of carbon with hetero atoms to Schrodinger’s equation for the system in question
(specially transition and alkali metal elements) leads to a containing too many electrons and ions. Thus, the need of
moderate binding energy situation (0.3-0.5 ev), known sophisticated numerical techniques and approximations
14
SMC Bulletin Vol. 11 (No. 1) April 2020
have given birth to a variety of quantum simulation polarization is necessary for systems containing transition
methods, e.g., Density functional theory (DFT) [24-26], metal with magnetic signature. Accuracy of configuration
Quantum Monte Carlo [27-29], Hatree-Fock [30-31], Multi- depends also on setting parameters such as energy cut
reference Configuration Interaction [32], Coupled cluster off for the plane wave as well as K-points for sampling
[33-34], etc. Each of the methods has their own merits and the Brilloiun zone. Hence, convergence needs to be tested
demerits. In the following, we will discuss the role of DFT with respect to energy cut off for the plane wave as well
method in context of H2 storage. as number of K-points. The distance of the H2 molecule
with the nearest atom of the host or the dopant might
2.4 Density functional theory impart idea regarding bond strength. Lower distance
Density functional theory (DFT) is one of the fast and (bond length) signifies stronger adsorption. To investigate
powerful quantum
Density functional simulation
theory methods
(DFT) [24-26], that Monte
Quantum are widely adsorption properties of hydrogen molecules on metal-
Carlo [27-29], Hatree-Fock [30-31], Multi-reference
used in many Interaction
Configuration branches [32],of engineering and[33-34],
Coupled cluster science.etc. Each doped
It is zeolitehas
of the methods template
their owncarbon (ZTC), more than 10
merits and
demerits. In the following, we will discuss
based on two theorems given by Hohenberg and Kohn the role of DFT method inadsorption
context of H configurations
2 storage. have been simulated by Han et
[35] in 1964 and followed by few equations formulated by al. [39]. It is found that H 2
molecules tend to symmetrically
2.4 Density functional theory locate around Sc, Ti or V atoms doped on C39H15 surface
Kohn
Density and Sham [36].
functional theory (DFT) is one of the fast and powerful quantum simulation methods that are widely
used in many branches
[40]. Therefore, while building the initial model of H2
The ground stateofdensity
engineering
can and science. It is
be obtained basedthe
from on two theorems given by Hohenberg and Kohn
[35] in 1964 and followed by few equations formulated by Kohn and adsorption Sham [36]. configuration, the H2 molecules are uniformly
solution of Koh-Sham equation given by
The ground state density can be obtained from the solution of Koh-Sham loaded around
equation giventhebydoped metal atoms in almost symmetric
h positions, with a gradually raised loading number of
ˆ ( rr ) ψ (r)=ε
2
r r .........................(1) H molecules. First-principles geometric
- ∇ +V eff i i ψ i (r) (1) optimization
2m e
2
has been individually performed for each additional H2
with
r ˆ ˆ molecule to obtain all the relaxed and stable adsorption
ˆ (r)=V
V +V +Vˆ .........................(2) (2) configurations after
eff H xc ext structures. Representative adsorption
and Vˆxc and VˆH are given by geometry optimization of three and six H2 molecules at
r A1-A10 sites of Sc-C39H15 are shown with the top (left)
ˆ δE xc [ρ] ˆ e2 ρ(r / ) r / .........................(3) and side (right) views in Fig. 2.
V =
xc
δn
,V =
H
4πε 0 r r dr
r-r /
(3)
15
SMC Bulletin Vol. 11 (No. 1) April 2020
computational
Where cost and
E Host + H is the energy
2
of theaccuracy in quantum plus
host (nanostructure+dopant) chemistry
H2, EHost is the taken
energy for
of thethe
hostsimulation.
and Bader charge analysis [42]
EH methods
2
is the energy (Table
of an 1).
isolated H 2 molecule. As per convention, negative value of and
adsorptionMulliken’s
energy indicatescharge analysis [43] are two powerful
techniques
that binding is energetically favorable. All three energies in the above equation should be computed with same to find the amount of charge transfer during
simulation condition as the computed energy may vary with setting parameters. Adsorption energy is very much
orbital interactions. To visualize the spatial variation of
sensitive Table
to choice1 Adsorption energyenergy
of basis set. The adsorption andmay bond length
also be different of
for different adsorption sites. Ganji
et al.low energy configuration systems in H2-coronene
[41] demonstrated that adsorption energy values and bond lengths obtained are chargeto density,
sensitive the pictorial plot of charge density can be
choice of basis
sets, e.g. SVP, TZVP or TZVPP. The results generated through dispersion corrected
system (Ref.: Ganji et al.and2015 [41], with permis- obtained using
approaches visualizing
display softwares like XCRYSDEN [44],
excellent agreement between the theory experiment, especially for the large basis set. Meanwhile, the
VESTA [45] etc. The orbital interactions and hybridization
moderate basis set (TZVP) gives a reasonably sion.) good result compromising computational cost and accuracy in
quantum chemistry methods (Table 1). can be obtained qualitatively from the plot of partial
Basis set C-H bond Eads (kJ mol ) -1 density of states which describe the contribution of Density
length (Å) of states from each orbital of each atom. There should be
consistency between the charge transfer from Bader charge
SVP 3.394 +2.11 analysis, partial density of states, and charge density plot.
TZVP 3.294 +1.97 Wong et al. [46] compared hydrogen adsorption capability
of graphene decorated with different metals. In the charge
TZVPP 3.295 +1.91 density difference isosurfaces, yellow indicates regions of
vdW-SVP 3.301 -4.73 charge gain and blue indicates regions of charge loss (Fig.
3). The Al atoms, a light metal, show greater charge loss
vdW-TZVP 3.288 -4.97
and a smaller region of remaining charge density than
vdW-TZVPP 3.289 -5.013 the heavy metal Ni atoms. This might be one reason for
heavier metal atoms possessing stronger hydrogen binding
16
ed hydrogen adsorption capability of graphene decorated with different metals. In the charge
isosurfaces, yellow indicates regions of charge gain and blue indicates regions of charge loss
oms, a light metal, show greater charge loss and a smaller region of remaining charge density
tal Ni atoms. This might be one reason for heavier metal atoms possessing stronger hydrogen
they have greater charge which can interact with hydrogen molecules. SMC Bulletin Vol. 11 (No. 1) April 2020
17
carbon fullerenes Cn (20 ≤n ≤82) as H2 storage media. The theorized enhanced binding is delocalized in nature,
surrounding the whole surface of a charged fullerene. The enhanced binding is attributed to the polarization of
the H2 molecules by the high electric field generated near the surface. At full H2 coverage, these charged
SMC Bulletin
fullerenes Vol.gain
can 11 (No. 1) April
storage 2020
capacities of up to 8.0 wt % (Fig. 5).
Fig. 5: (a) Binding energy of molecular hydrogen on charged or neutral fullerenes. The DFT calculations (data points)
Fig. 5: (a) Binding energy of molecular hydrogen on charged or neutral fullerenes. The DFT calculations (data points) are compared with
are compared with semiclassical calculations (solid lines), and for both cases the binding energy increases quadratically
semiclassical calculations (solid lines), and for both cases the binding energy increases quadratically with the3+net charge. (b, c) Structurally
with the net charge. (b, c) Structurally optimized hydrogen-fullerene complexes of (b) 12H2-C28 and (c) 43H2 -C826+, with
optimized hydrogen-fullerene complexes
a hydrogen uptake of 6.67 wt % and 8.04 of (b) 12H 2
-C wt
3+
and (c) 43H -C
28 %, respectively.
2 82
6+
, with
(d) aElectric
hydrogenfields
uptakeassociated
of 6.67 wt % with
and 8.04 wt %, and
neutral respectively.
charged (d)
Electric fields associated
q with neutral and charged fullerenes, C28q (q=-2, 0, +2), at the center of a hydrogen molecule located on top of a hexagonal
fullerenes, C28 (q=-2, 0, +2), at the center of a hydrogen molecule located on 10top of a hexagonal ring. (b, c) Charge
ring. (b, c) variations
density Charge density
of variations
a hydrogen of a hydrogen
moleculemolecule
induced induced
by anby an electricfield
electric field ofof2×10
2×10V/m
10 applied (b) parallel and (c) perpendicular
V/m applied (b) parallel and (c)
toperpendicular
the molecule axis, respectively. (From Yoon et al., 2007 [53], With permission.)
to the molecule axis, respectively. (From Yoon et al., 2007 [53], With permission.)
TableTozzini
2 An account of noteworthy
et al. [54] proposed atheoretical
multilayer works for assessing
graphene-based H2 storage
device. in pure
There the CNMs
storage [55-62] of
and release
hydrogen are obtained by controlling the corrugation of individual layers of graphene. Their DFT calculation
Carbon
quantifies Storage
the tunability condition
of the Hydrogen
hydrogen-graphene storage
binding Remarks the sheet’s Reference
energies by changing out-of-plane
nanomaterial
deformation up to 0.2 Å. The binding capacity (wt %)
energy is found to be varied by more than 2 eV, with the convex regions
Temperature Pressure
typethe energetically favored hydrogen binding sites. The corrugation of the graphene sheet and the
allocating
controlled inversion of 300
Fullerene its curvature
K yield fast storage and
Ambient >8release of hydrogen, indicating
Fullerene nanocagea maximum storage
[55] of
8 wt% H2 (Fig. 6).
Graphite 300 K 70 MPa 8 Fullerene-intercalated [56]
graphite
Table 2 An account of noteworthy theoretical works for assessing H2 storage in pure CNMs [55-62]
Graphene
Carbon Ambient
Storage Ambient
condition Up to 8
Hydrogen Graphene multilayer Reference
Remarks [57]
nanomaterial Temperature Pressure storage
type capacity (wt
Carbon 77 K 4 MPa %)7.1 SWCNT [58]
nanotube
Fullerene 300 K
Ambient 50 Ambient
atm >8 ~1 FullereneSWCNT
nanocage [55] [59]
Graphite 300 K 70 MPa 8 Fullerene-intercalated [56]
200 K 100 atm 0.9-1.4 SWCNT [59]
graphite
Nanoporous 77 K 3.8 MPa 6 Quasi-periodic [610]
carbon icosahedral
material
Graphene
Carbon Ambient
293 K Ambient
10 MPa Up1.21
to 8 Graphene multilayer [57] [61]
nanoscroll
enhanced
Carbon binding is77 delocalized
K in nature, surrounding
4 MPa 7.1 layers of graphene.
SWCNTTheir DFT calculation [58] quantifies the
the whole surface of a charged fullerene. The enhanced tunability of the hydrogen-graphene binding
nanotube Ambient 50 atm ~1 SWCNT [59] energies by
binding is attributed to the polarization of the H2 molecules changing the sheet’s out-of-plane deformation up to 0.2
200 K 100 atm 0.9-1.4 SWCNT [59]
by the high electric field generated near the surface. At Å. The binding energy is found to be varied by more than
full H2 coverage, these
Nanoporous 77charged
K fullerenes3.8
canMPa
gain storage
6 2 eV, with the convex regions allocating
Quasi-periodic the energetically
[610]
capacities of up
carbon material to 8.0 wt % (Fig. 5). favored hydrogen binding
icosahedral sites. The corrugation of the
graphene sheet and the controlled inversion of its curvature
Tozzini et al. [54] proposed a multilayer graphene-
yield fast storage and release of hydrogen, indicating a
based device. There the storage and release of hydrogen
maximum storage of 8 wt% H2 (Fig. 6).
are obtained by controlling the corrugation of individual
Carbon 293 K 10 MPa 1.21 [61]
18
nanoscroll
SMC Bulletin Vol. 11 (No. 1) April 2020
(a) (a)
(b) (b)
19
SMC Bulletin Vol. 11 (No. 1) April 2020
(b) (b)
(a) (a) (b)
Fig. Fig.
7: Two7: possible
Two possible (a)
adsorption
adsorption site ofsite
Y onof graphyne
Y on graphyne (a) Hexagonal
(a) Hexagonal sitemetal
site with with binding
metal binding energy
energy of -3.15ofeV;
-3.15
the eV; the
configuration
configuration of 9 Hof2 9molecules
H 2 molecules
it canitadsorb
can adsorb
and (b)andTriangular
(b) Triangular
site with sitemetal
with binding
metal binding
energy energy
of -4.05ofeV;
-4.05
the eV; the
configuration
configuration of 5 Hof 5 H 2 molecules
2 molecules it can it can adsorb.
adsorb. (From (From
Gangan Gangan et al.,[63],
et al., 2019 2019With
[63], With permission.)
permission.)
Chakraborty Fig.
Chakraborty
Fig.
7:alpossible
et
et al [64]
7: Two
Two
[64]
have have
also possible
also reported
reported
adsorption
adsorption
hydrogen
hydrogen
sitestoragestorage site
capability
of Ycapability
on graphyneofof
capability Yof(a)Yon
Y doped dopedgraphyne
single walled
Hexagonal walled(a)
single carbon
site
Hexagonal
carbon
with
site with metal binding energy of -3.15 eV; the
metal binding energy of -3.15 eV; the configuration of 9 H2 molecules
nanotubes. TheyThey
nanotubes. presented the structural
presented
configuration stability,
the structural
of 9 HH2 adsorption
stability, H2 adsorption
molecules and H2and
capability
it can desorption kinetics
H2 desorption
adsorb and of(b)
Y- of
kinetics Y-
Triangular site with metal binding energy of -4.05 eV; the
decorated
decorated itwalled
canwalled
singlesingle adsorb
carbon andnanotube
nanotube
carbon (b) Triangular
(Fig. 8) 2
through
(Fig. siteprinciple
first
8) through with
first metal binding
simulations.
principle It was energy
simulations. found
It was thatofA -4.05
found that A eV;
single singlethe configuration of 5 H2 molecules it can adsorb. (From Gangan et
Y atom attached
Y atom configuration
on SWCNT
attached on SWCNT is shown of 5 H
to physisorb
is shown molecules
2 up to six
to physisorb H2six
up to it can
molecules. adsorb.
The interaction
H2 molecules. (From Gangan
of H2 with
The interaction of Hmetal et
2 with metal al., 2019 [63], With permission.)
atomatom
is through al.,
Kubas
is through
2019 [63],
type of
Kubas
With
interactions.
type
permission.)
of interactions.
Fig. 9: Theoretical DFT study of zirconium-doped graphene, capable of storing 11 wt% H2 (From Yadav et al., 2017 [65],
Fig. 9: Theoretical DFT study of zirconium-doped graphene, capable of storing 11 wt% H2 (From Yadav et al., 2017 [65], with permission.)
with permission.)
Table 3 A few noteworthy theoretical works regarding H2 storage on functionalized CNMs [62, 66-75]
Apart from above, there are many more theoretical studies reported available for predicting H2 storage
of CNMs in presence of heteroatoms. A brief account of a few such works is summarized in Table 3 [62, 66-75].
Carbon Storage condition Hydrogen storage Remarks Reference
To fortify with a few recent interesting studies, Deniz et al. [76] showed through grand canonical Monte Carlo
nanomaterial capacity (wt %)
(GCMC) simulations
type
that the total Pressure
Temperature gravimetric Decorating
adsorption capacity of Li-doped fullerene pillared graphene
nanocomposites (Li-FPGNs) with doping ratio of Li:C=15:100
element could reach 9.1 wt% at 77 K and 1 bar, which
corresponds to about two times rise in the hydrogen storage performance of pristine FPGNs.
Fullerene Ambient Ambient Ca >8.4 [66]
TableGraphene 77 K theoretical
3 A few noteworthy 10 works
bar andregardingLiH storage on functionalized
2
>5 Pillared
CNMs graphene
[62, 66-75][68]
above oxide
Carbon Storage condition Hydrogen Remarks Referenc
nanomaterial Temperature
Ambient Ambient
Pressure Ca
Decorating storage
~5 Zigzag graphene e [69]
type element capacity (wt nanoribbon
%)
Ambient 20 bar Li 6.5 Pillared graphene [70]
Fullerene Ambient Ambient Ca >8.4 [66]
sheet
Ambient Ambient Ti 7.5 [67]
Graphene 77Ambient
K 10 bar and LiLi
Ambient >512.8 Pillared [68]
[71]
above graphene
Ambient Ambient Al 13.79 [72]
oxide
Carbon 300 K 10 MPa Li 1.27 Single walled [73]
nanotube
Ambient Ambient Si 2.5 Single walled [74]
Graphyne Ambient
Ambient -
Ambient Ca
Ca ~57 Zigzag [75]
[69]
graphene
Carbon 293 K 10 MPa Li 3.78 [62]
nanoscroll
nanoribbon
21
Graphyne Ambient - Ca 7 [75]
Carbon 293 K 10 MPa Li 3.78 [62]
nanoscroll
(a) (b)
Fig. 11: (a) Raman spectra of pure and nitrogen and palladium decorated hydrogen exfoliated graphene (HEG): rise in
Fig. 11: (a) Raman spectra of pure and nitrogen and palladium decorated hydrogen exfoliated graphene (HEG): rise in intensity of D band
intensity of D band suggesting accumulation of strain due to exfoliation. (b) XRD: extra peaks on top curve showing
suggesting accumulation of strain due to exfoliation. (b) XRD: extra peaks on top curve showing incorporation of Pd nanoparticles. Pressure−
incorporation of Pd nanoparticles. Pressure−composition isotherms of (c) N-HEG and (d) Pd- N-HEG in the temperature
composition isotherms of (c) N-HEG and (d) Pd- N-HEG in the temperature range 25−100° C and 0.1 − 4 MPa pressure. (From Parambhath et
range 25−100° C and 0.1 − 4 MPa pressure. (From Parambhath et al., 2012 [89], with permission.)
al., 2012 [89], with permission.)
(a) (b)
Fig. 12: (a) Adsorption isotherm of hydrogen at 77 K on different carbons:C1-C5 denote carbon samples treated with
Fig. 12: (a)
KOH, K2Adsorption
CO3 , NaOH,isotherm
H3PO of hydrogen at 77 K on different carbons:C1-C5 denote carbon samples treated with KOH, K2CO3(b) , NaOH, H3PO4
4 and ZnCl2 respectively for activation. (From Sun et al., 2010, With permission.), Year-on-
tosamples
300 °Ctoand
and
300removal
°C
ZnCl and of the
removal
respectively
year experimental
2
catalyst
of
for thetips
activation.may
catalyst
(Fromincrease
tips
Sunmay
et the
al., H
increase
2010,
2 storage
the
With H capacity
storage up to 13
capacity
permission.),
2 (b) wt%
up to and
Year-on-year13 wt% and
scatter in hydrogen storage for single walled carbon nanotubes (From Hirscher et al., 2003 [91], Withfor
experimental scatter in hydrogen storage
the pressure
decrease therequired
pressure
single walled
permission.)for storage
required
carbon (Fig.
for 13).
storage
nanotubes (Fig.Hirscher
(From 13). et al., 2003 [91], With permission.)
3.1 Experimental studies aiming hydrogen storage in pure CNMs gravimetric methods [90] (Fig.
Chen et al. [92] synthesized aligned (CNTs) with diameters of 50–100 nm, by12a). For issues related
plasma-assisted hotwith purity,
filament
chemical vapor deposition. Using quadruple mass spectroscopy and thermogravimetric analysis they found oa nH2o f
c l u s t e r i n g , a g g l o m e r a t i
decorating
storage capacity of 5–7 wt% reproducibly at room temperature under modest pressure of ~10 nanoparticles
atm. Heating the and
oxygen interference, experimentally
observed results seldom match with
theoretical predictions (Fig. 12b)
[91].
Lueking etLueking
al. [93]etexhibited
al. [93] exhibited that exfoliation
that selective selective exfoliation
of a carbonof nanofiber
a carbon nanofiber
is a meansisby
a means
which byH2 which H2
on with the carbon structure can be controlled. This in turn results in control of binding energy to tune to tune
interaction with the carbon structure can be controlled. This in turn results in control of binding energy 23
the operative
ative adsorptionadsorption
temperaturetemperature
(Fig. 14). (Fig.
Rise 14). Rise in exfoliation
in exfoliation temperature
temperature and timeinresulted
and time resulted in huge lattice
huge lattice
expansion causing many folds increase in surface area and a consequent uplift
on causing many folds increase in surface area and a consequent uplift in H2 uptake. 2 in H uptake.
SMC Bulletin Vol. 11 (No. 1) April 2020
(d)
Fig. 14: SEM micrographs indicate the changes in surface structure upon various stages in the exfoliation process. (a)
Fig. 14: SEM micrographs indicate the changes in surface structure upon various stages in the exfoliation process. (a) GNF1 has relatively smooth
GNF1 has relatively smooth surfaces; (b) EGNF-700 shows roughened surfaces, variations in fibre termination (arrows),
surfaces; (b) EGNF-700 shows roughened surfaces, variations in fibre termination (arrows), and the appearance of disk-like carbon structures
and the appearance of disk-like carbon structures indicating partial destruction of the GNFs; (c) EGNF-1000 shows
indicating partial destruction of the GNFs; (c) EGNF-1000 shows roughened surfaces, surface defects (arrows), and expanded regions. (d) H2
roughened surfaces, surface defects (arrows), and expanded regions. (d) H2 uptake
uptake for the various GNFs at 77 K and up to 20 bar (From Lueking et al., 2005 [93], with
for the various GNFs at 77 K and up to
permission.)
20 bar (From Lueking et al., 2005 [93], with permission.)
in turn results in control of binding energy to tune the highest capacity of H2 adsorption was detected for nitric
In another temperature
operative adsorption elegant work(Fig.regarding fabrication
14). Rise of graphene-based
in acid-modified materials
carbon. It appears having hierarchical
that experimental findings
nanopore,
exfoliation temperature and time resulted in huge lattice regarding H2 storage performance are often oxide.
Guo et al. [94] developed suitable oxidative heat treatment of exfoliated graphene It is
less reliable
conceived from their
expansion causing many work
foldsthat escape
increase of oxygen
in surface area functional
and for lackgroups through formation
of reproducibility, of CO
as judged leaves
by2many pores of
researchers
assorted varieties (Fig. 15).
a consequent uplift in H2 uptake. This leads to wave-like structure between individual graphene layers causing
[120-121]. The chief reason behind such diverse observation
enhanced H2 storage (4 wt %). is variation of sample quality in terms of purity across
In another elegant work regarding fabrication of
different laboratories and variety of processing routes for
graphene-based materials having hierarchical nanopore,
preparation and characterization of the samples. Practical
Guo et al. [94] developed suitable oxidative heat treatment
achievable H2 adsorption for pure CNM is often less than
of exfoliated graphene oxide. It is conceived from their
1 wt% at ambiance. With lower temperature and higher
work that escape of oxygen functional groups through
pressure however, better results could be achieved [103,
formation of CO2 leaves pores of assorted varieties (Fig.
106, 109, 111], sometimes even exceeding the theoretical
15). This leads to wave-like structure between individual
prediction [113].
graphene layers causing enhanced H2 storage (4 wt %).
Table 4 [95-118] is a compilation of a few more notable 3.2 Experimental studies aiming hydrogen storage
experimental results to show H2 storage performance of in functionalized CNMs
various physical CNMs of known purity. Recently, in an Reyhani et al. [122] studied H2 storage performance
elegant report, Jokar [119] showed that acidic vapor has of MWCNT decorated with Ca, Co, Fe, Ni, and Pd. H2
no deleterious effect on stability of the structure of CNT molecules are adsorbed on the defect sites and transported
formed by a special CVD method involving Co-Mo/MgO to the spaces between adjacent carbon via diffusion
catalyst, and nanoporous activated carbon. Additionally, through both defect sites and opened tips into the layers.
24
In another elegant work regarding fabrication of graphene-based materials having hierarchical
nanopore, Guo et al. [94] developed suitable oxidative heat treatment of exfoliated graphene oxide. It is
conceived from their work that escape of oxygen functional groups through formation of CO2 leaves pores of
assorted varieties (Fig. 15). This leads to wave-like structure between individual graphene layers causing
SMC Bulletin Vol. 11 (No. 1) April 2020
enhanced H2 storage (4 wt %).
mesoporous
carbon
Templated 298 K 10 MPa 1.43 [114]
carbon
Carbon xerogel 298 K 20 1.0 [115]
Carbon sphere 298 K 9 0.25-0.43 [116]
Carbon 298 K 0.11 0.1-0.26 [117]
nanosheet
Carbon cloth 298 K 90 bar 0.5 [118]
Reaction path
Fig. 16:ofMechanism
Fig. 16: Mechanism of hydrogen
hydrogen adsorption adsorption
in a metal in amultiwalled
decorated metal decorated
carbon multiwalled carbon
nanotube through nanotube
molecular throughdissociation into
hydrogen
molecular hydrogen dissociation into atoms at metal surface and M-C-Hx complex formation (From Reyhani
atoms at metal surface and M-C-Hx complex formation (From Reyhani et al., 2011 [122], with permission.)
et al., 2011 [122], with permission.)
Improvement in storage capacity through decoration temperatures as compared to C-H chemical bonds (Fig. 16).
is through eitherWang et al. [123] concluded upon detailed analysis of H2 isotherms and isosteric heat of adsorption,
Kubas interaction or dissociation of
that doping with an appropriate amount of Ni–B nanoalloysWang et al. dissociative
can cause [123] concluded upon detailed
chemisorption of H2 analysis of
H2 molecules
molecules by spilloverparticles,
on the metal to achievei.e., spillover.
hydrogen Pdcapacity
storage is
H(> 4 wt %). This
isotherms and can be threeheat
isosteric timesofhigher than its that doping
adsorption,
found to be mostcounterpart
pristine effective catalyst
(Fig. 17). for H2 storage process. with an appropriate amount of Ni–B nanoalloys can cause
2
25
SMC Bulletin Vol. 11 (No. 1) April 2020
Table 4 A versions of remarkable experimental works for measuring H2 storage in pure CNMs [95-119]
Temperature Pressure
Carbon nanotube Ambient 0.067 MPa 3.5–4.5 High purity single walled [100]
Nanoporous carbon Ambient 207 bar 8.13 Valid for a pore density of 1 [109]
material cm3/g and size of 0.9 Å
Carbon nanofiber 77–300 K 1.5 MPa 1–1.8 Purified GNF herringbone [110]
26
SMC Bulletin Vol. 11 (No. 1) April 2020
27
SMC Bulletin Vol. 11 (No. 1) April 2020
(c) (c)
(d) (d)
(c)
(c) of GPFig.
Fig. 17: SEM images (a) pristine
17: SEMgraphene (GP)
images of GP and (b) GP-Ni
(a) pristine 0.83B1.09, (GP)
graphene (c) TEM
and image
(b) GP-Niof GP-Ni
0.83B1.09 , B(c) , and image
1.09TEM (d) of GP-Ni0.83B1.09, and (d)
Fig. 17: SEM images of GP (a) pristine graphene (GP) and (b) GP-Ni B , (c)0.69
TEM image B1.39of GP-Ni ,B 1.09 ,at
and
77 K(d) H adsorption and desorption
0.83
H2 adsorption and desorption isotherms of GP,
H2 adsorption and0.83 GP-Ni
1.092.41Bisotherms
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1.51GP, and
GP-Ni GP-Ni
2.41B0.69
0.83
0.83 B
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1.51 B1.39 and2GP-Ni0.83B1.09 at 77 K (adsorption data
isotherms of GP, GP-Ni B , are GP-Ni
2.41 0.69
B and GP-Ni
shown as closed shapes, are
1.51 1.39
shownB as
desorption data
atas77
closed Kshapes).
open
(adsorption
shapes,
0.83 1.09
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(From data
desorption Wang
are
asetopen shown
al., 2011 [123],
shapes). aswith
(From closed shapes,
et al., 2011desorption
permission.)
Wang data as open
[123], with permission.)
(a)
(a)
(a) (a)
(b) (b)
(c) (c)
Fig.Fig.
18: (a)
18: TEM
(a) TEM
imagesimages (b)Pt-decorated
of oxidized,
of oxidized, Pt-decoratedsingle
single
(b)
wallwall
carboncarbon
nanohorns.
nanohorns. (c)
(b) Experimental
(b) Experimental INS INS
datadata
of 1% of mass
1% mass
fraction
fraction
H2 on H2Pt-SWCNHs
on Pt-SWCNHs before
before
(solid
(solid
circles)
circles)
and and
afterafter
(solid(solid
squares)
squares)
cycling
cycling
the temperature
the temperature of the the (c)
of closedclosed
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to to
Fig.295
295 (a)
K. TEM
18:(c)
K. images of oxidized,
Experimental
(c) Experimental INS INS
dataPt-decorated
data
of 1% 1%single
of mass mass wall
fractioncarbon
H2 on
fraction nanohorns.
H 2 Pt-SWCNHs (b) Experimental
on Pt-SWCNHs before
before INS
(black data
(black of 1%and
circles) mass
circles) fraction
and
after (redH2
after (redon squares)
Pt-SWCNHs
squares)
ig. 18: (a) TEM
before
cycling the images
(solid
cycling circles) and
temperature
the ofafter
temperature oxidized,
of (solid
the
of closed
the Pt-decorated
squares)
closed cycling
system to the
system 150 K. single
totemperature
150 All wall
K.measurements carbon
Allofmeasurements
the closed system
werewerenanohorns.
to 295
taken atK.4(c)
taken at K.(b)
4(From Experimental
K.Experimental
(From
Liu INS
et data
Liual., of 1%
et 2012
al., 2012 INS
mass
[124], data of 1% m
fraction
[124],
action H2 2on Pt-SWCNHs before (solid circles) and after (solid squares) cycling the temperature of the were
H
withon
withPt-SWCNHs
permission.)
permission.) before (black circles) and after (red squares) cycling the temperature of the closed system to 150 K. All measurements closed syste
95 K. (c) taken at 4 K. (From Liu
Experimental INSet al.,
data2012 of
[124],
1% with permission.)
mass fraction H2 on Pt-SWCNHs before (black circles) and after (red squa
A few
A few
moremoreimportant
important
ycling the temperature of the closed system to 150observational
observationalefforts
efforts
K. aremeasurements
All are
tabulated
tabulated
(Table
(Table
5) [89,
were 5)taken
[89,
91, at
91,
125-141]
4125-141]
concerning
K. (From concerning
Liu et al., 2012 [1
experimental
experimental studies
studies
for forevaluating
evaluatingactual
actual
H2 H storage
2 storage
capacity
capacity
of various
of variousdecorated
decorated
CNMs.
CNMs.
Compared
Comparedto to
ith permission.)
graphene
grapheneand and
other
other
minorminorderivatives
derivatives
suchsuch
as CNF,
as CNF,porous
porous
carbon
carbon
etc.,etc.,
decorated
decorated
CNT CNT
appears
appears
to demonstrate
to demonstrate
28
superior H2 storage
superior H2 storage
performance
performance
in ain
few
a few
instances
instances
[130-131,
[130-131,
133,133,
139].
139].
However,
However,
thatthat
trend
trend
is not
is not
reproducible
reproducible
A few
by all more[92,
byobservers important
all observers [92,
135-136, observational
135-136,
138]138]
duedue
to various efforts
to various
issues
issues are tabulated
described
described
in section 3.1.(Table
in section 3.1. 5) [89, 91, 125-141] concer
SMC Bulletin Vol. 11 (No. 1) April 2020
A novel inelastic neutron scattering based hydrogen overcoming obstacles like oxidation or oxygen interference,
quantification method has been developed by Liu clustering etc. of the decorating substance.
et al [124] to find advantage over traditional Sievert
4. Conclusions and future direction
type measurement. The developed method involves
temperature-cycling. Measurements on single-wall Carbonaceous nanomaterials constitute an important
carbon nanohorns (SWCNHs) decorated with 2–3 nm category of candidates for solid-state H2 storage for on-
Pt nanoparticles showed 0.17% mass fraction of metal- board application. Although storage performance of pure
assisted H2 storage (at ≈0.5 MPa) at room temperature. CNMs are practically not that promising at near-ambient
When measured using Sievert’s apparatus, a hydrogen conditions, theoretically it has been proved reproducibly
adsorption of ≈0.08% mass fraction at 5 MPa at room that functionalized CNMs are capable of storing greater
temperature is achieved. The obtained excess storage quantum of H2 satisfying DoE requirements even at
ranging 0.3-0.5 wt % is believed to be attributed to metal- ambient condition. However, actual technical barrier
assisted H2 spillover (Fig. 18). of properly decorating CNMs with transition metal
nanoparticles is not yet greatly successful for want of
A few more important observational efforts are
suitably optimized methods. Secondly, experimental
tabulated (Table 5) [89, 91, 125-141] concerning experimental
scattering till date prevails for practical limitations and
studies for evaluating actual H2 storage capacity of various
thus development of such substance is still ongoing. In
decorated CNMs. Compared to graphene and other minor
future, with technological improvement, this can be one
derivatives such as CNF, porous carbon etc., decorated CNT
of the possible options for switching to greener energy
appears to demonstrate superior H2 storage performance
alternatives.
in a few instances [130-131, 133, 139]. However, that trend
is not reproducible by all observers [92, 135-136, 138] due
Acknowledgements
to various issues described in section 3.1.
GS wishes to thank all crew members of Materials
3.3 Challenges and issues in experimental studies Group, BARC in general Dr. R. N. Singh Head, MMD and
Dr. V. Kain AD, MG in particular for their keen interest
Tonnage scale commercial production of carbonaceous
in this research. B. C. would like to thank Brahmananda
nanomaterials is till date unachieved for difficulty in
Chakraborty would like to thank Dr. Nandini Garg, Dr.
scaling up of laboratory findings. With progress of
T. Sakuntala, Dr. S.M. Yusuf and Dr. A. K. Mohanty for
technology, it is anticipated to be realized in coming time.
support and encouragement.
Once that is done, demand of such material for various
applications including H 2 storage is bound to grow.
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Physics 16 (2014) 26725.
Mr.Gopal
Mr. Gopal Sanyal
Sanyalis is a Research
a Research Scientist
Scientist at the Mechanical
at the Mechanical MetallurgyMetallurgy Division, Bhabha Atomic
Division, Bhabha
Research
Atomic
Mr. GopalCentre,
Research Trombay,
Centre,
Sanyalis Mumbai
Trombay,
a Research 400085,
Mumbai
Scientist India. He
at the400085, earned
India.
Mechanical He aearned
Master
Metallurgy a ofMaster
Division, Technology
of
Bhabha in Metallurgical
and Materials
Technology
Atomic in
ResearchEngineering
Metallurgical from IIT Mumbai
and
Centre, Trombay, Kharagpur
Materials in 2007.
Engineering
400085, from His primary
IIT
India. Kharagpur
He earned research
in interest
2007.
a Master of is in the evaluation
His
primary research
of the mechanical
Technology interest is inand
properties
in Metallurgical the evaluationEngineering
of materials.
Materials of the mechanical properties
from IIT of materials.
Kharagpur in 2007. His
primary research interest is in the evaluation of the mechanical properties of materials.
Keywords: Graphene, vertical structure, nanodiamond, hybrid structure as a filler material for the enhancement of
thermal activation, non-catalytic thermal conductivity of Poly (vinylidene fluoride) (PVDF)
composites in order to increase the heat dissipation for the
1 Introduction electronic devices.
Carbon nanomaterials in its various forms have Few layered vertical graphene (FLVG), commonly
drawn significant interest in the field of nanoscience and termed as carbon nanowall (CNW), have been achieved
nanotechnology because of their extraordinary mechanical, on both catalyzed [16] and non-catalyzed [17] substrates
electrical and optical properties. The C-C sp3 network of using various plasma-assisted CVD techniques. It has been
diamond nanostructure is known to be an excellent material shown that vertical growth of carbon nanowalls using
for various applications [1-6]. The newly born graphene, plasma assisted CVD techniques is due to the aligned
a two-dimensional sheet of hexagonally arranged sp2- electric field caused by the plasma and highly dense
bonded carbon form, has exhibited wide range of superior carbon-based ionic species [16-24]. However, plasma-
properties as compared to its counterparts, and thus assisted CVD synthesized carbon nanomaterials materials
considered to be a potential material for the advanced are always limited to a small area (restricted by plasma size)
technology [7-10]. However, the planar structure of and prone to contain large amount of defects due to the
graphene with respect to the flat substrates limits its true ion bombardment from the high density plasma. On the
potential. The effective surface area of planar structured other hand, thermally assisted hot filament CVD (HFCVD)
graphene is comparatively smaller than its vertical technique offers large area and defect free growth of carbon
structure (bottom surface of graphene is inactivated by nanomaterials. Nonetheless, very limited literatures exist
the presence of substrate). The field emission property of on the growth of FLVG/CNW using HFCVD technique
planar graphene is limited by its in-plane shape, whereas [25-27]. Recently, carbon nanotubes [28] and carbon
vertical graphene is more potential for this purpose. As papers [29] have been used as templates to grow carbon
compared to the nearly in-active basal plane the edge nanowall using HFCVD technique. The vertical growth
plane of vertically graphene is highly reactive, and thus of graphene/carbon nanowall has been achieved either
considered to be an excellent electrode material for electro- by using plasma assisted discharge technique or specially
catalysis applications [11]. In addition, large surface area of treated substrates (substrate biasing /metal catalyzed
vertical graphene is favorable for the fabrication of various substrate). The catalyst-free vertical growth of FLVG
nanostructured materials, biosensors, and electrodes for using HFCVD technique is very rare and far from clear
batteries or capacitors [12-14]. Nonocrystalline diamond understanding. In addition, a non-catalytic direct growth
films are very promising nanostructured carbon materials of graphene on a semiconducting or dielectric substrate is
owing to their unique physical properties [1-6]. Hence, extremely challenging and advantageous for the electronic
the diverse properties of graphene and nanodiamond device applications. The mechanism for vertical growth of
could be combined together in order to open an avenue graphene along a two-dimensional vertical plane, rather
for the unexplored basic science and emerging technology. than the expected one-dimensional vertical plane (in form
Recently, Yu et al. [15] have used nanodiamond − graphene of vertical wire/rod structure) is still open and need to be
understood.
33
SMC Bulletin Vol. 11 (No. 1) April 2020
In this work, we report a simple method for the growth carried out at a chamber pressure 7.5 Torr. The substrate
of FLVG and nanodiamond composite using a single-step temperature was measured by a thermocouple (Pt–Rh) put
HFCVD
2. Experimental technique without using any metal catalysts/ in contact with the substrate surface, while the filament
details
The verticalsubstrate
graphene films wereor
biasing synthesized
any other on special
Si substrate using HFCVD technique.
instrumental temperature The details
was of the
measured by an optical pyrometer
-3
HFCVD chamber are given in [28]. The reaction chamber was initially evacuated
arrangements. The onsets of vertical growth of FLVGs (Minolta TR 630 A, withto a pressure 3×10 Torr, and the emissivity adjusted to that
subsequently a gas mixture of 2% CH4 and 15% nitrogen in H2/Ar mixture was introduced to the chamber, while
keeping totalhave been
flow rate of analyzed carefully
the gas-mixture constantusing a cross-sectional
at 100 SCCM of thecentimeter
(SCCM denotes cubic tungstenper∼ minute
0.33 [28].
at The microstructural analysis
HRTEMtemperature
STP). The filament analysis and wastheir
slowlypossible growth
increased mechanisms
from room temperature of the predetermined
to the grown films growthwere carried out by high resolution
temperatureareby discussed.
varying the alternating current (AC) source. The desired substrate scanning electron
temperature 750 microscopy
°C was (HR-SEM, FEI Nova Nano
achieved by keeping the filament temperature at 2200°C. The synthesis was carried SEM out 200), Ramanpressure
at a chamber spectroscopy (Jobin Yvon model
7.5 Torr. The
2. substrate temperature
Experimental was measured by a thermocouple (Pt–Rh) putT64000,
details in contact with the substrate
wavelength of the laser: 514.5 nm), high resolution
surface, while the filament temperature was measured by an optical pyrometer (Minolta TR 630 A, with the
Thetovertical graphene transmission electron microscopy (HR-TEM, FEI Titan,
emissivity adjusted that of the tungsten films
∼ 0.33were synthesized
[28]. The on Sianalysis
microstructural of the grown films were
substrate using HFCVD technique. The details
carried out by high resolution scanning electron microscopy (HR-SEM, FEI Novaof the operating
Nano SEM voltage: 300 kV), and X-ray photoelectron
200), Raman
spectroscopyHFCVD chamber
(Jobin Yvon modelareT64000,
given in [28]. Theofreaction
wavelength 514.5 nm), high resolution transmission PHI 5800: using Al Ka source).
chamber
the laser: spectroscopy (XPS, ESCA
electron microscopy
was initially evacuated to a pressure 3×10 Torr, and
(HR-TEM, FEI Titan, operating voltage: 300
-3 kV), andX-rayThe sample forspectroscopy
photoelectron TEM analysis was prepared by focused ion
(XPS, ESCA PHI 5800: using Al Ka source). The sample for TEM analysis was prepared by focused ion600)
beamfor thinning it, and then mounted
subsequently a gas mixture of 2% CH and 15% nitrogen beam (FIB, FEI Nova
(FIB, FEI Nova 600) for thinning it, and then mounted on4 a platinum-coated TEM on grid.a platinum-coated TEM grid.
in H /Ar mixture was introduced to the chamber, while
2
3. Results keeping total flow rate of the gas-mixture constant at 100
and discussion
Fig. 1 showsSCCM
the low(SCCM denotes cubic
and high-resolution centimeter
SEM (HR-SEM) per minute at STP).
micrographs 3. Results
of the FLVG/CNW and discussion
samples grown at a
substrate temperature
The filamentof 750°C /H2/Ar/N
using CH4was
temperature 2 mixture.
slowly The morphology
increased from room of the samples
Fig. 1 exhibits
shows atheuniform
low and high-resolution SEM (HR-
coating of flake-like
temperaturenanostructures standing vertically
to the predetermined on to
growth the substrateby
temperature surface
SEM)with micrographs
lots of open space in FLVG/CNW samples grown
of the
between them. The HRSEM image of the sample grown for 10 minutes (Fig. 1b) shows that some of the flakes
varyingfaster
are grown relatively the alternating current
than the others (AC)
and have source.
popped out ofThe
the desired at a substrate
film matrix flaunting temperature
their sharp edges. As of 750°C using CH4/H2/Ar/
substrate temperature 750 °C was achieved by keeping
the growth further increased to 30 minutes, the surface morphology of the FLVG film N mixture. The morphology of the samples exhibits a
2 (Fig. 1c and d) shows an
thedensity
increase in the filament temperature
of flakes at height.
at a uniform 2200°C. TheThe synthesis
overall was uniform
inter connectivity coatingnanoflakes
of the individual of flake-like nanostructures standing
increases, albeit, they are randomly oriented with respect to each other. vertically on to the substrate surface with lots of open space
in between them. The HRSEM image of
the sample grown for 10 minutes (Fig.
1b) shows that some of the flakes are
grown relatively faster than the others
and have popped out of the film matrix
flaunting their sharp edges. As the
growth further increased to 30 minutes,
the surface morphology of the FLVG
film (Fig. 1c and d) shows an increase in
the density of flakes at a uniform height.
The overall inter connectivity of the
individual nanoflakes increases, albeit,
they are randomly oriented with respect
to each other.
The surface morphology of the
current FLVG film shows that the
graphene flakes are sheet-like structured,
spreading only two-dimensionally (can
be envisioned as a portion of the petal-
like structure sliced from the middle),
whereas in case of a petal/cone-like
structured nanoflakes, the edge of the
walls are usually connected around all
the directions forming a 3D structure.
Fig. 1: The Fig. 1: The
surface surface morphology
morphology of the nanostructured
of the nanostructured film grown for film grown for
two different two(a)
times different
Low andtimes (a) −The
(b) High
flakes are laterally compressed by
resolution
SEM imagesLow andminute
for 10 (b) High−resolution SEM
grown film, and (c) Lowimages
and (d)for 10−minute
High grown
resolution film,
images and
of 30 (c)grown
min. Low and
film.(d) other flakes during their vertical growth
High−resolution images of 30 min. grown film. and thus curled in lateral direction. This
34
2
during their vertical growth and thus curled in lateral direction. This leads to a large number of side edges and
short top edges in the film, which provides an increased effective surface activation. From the cross-sectional
SEM images (Figure 2) of the FLVG film (grown for 30 min) the height of the flakes is found to be ∼ 77 nm,
and the thickness is in the range of ∼ 3 −7 nm. SMC Bulletin Vol. 11 (No. 1) April 2020
leads to aWelargefurther
numberprobed
of side the
edges and short
onset top edges
of FLVG anisotropically
film growth throughinto a two-dimensional
cross-sectional form, exhibiting
transmission electrona
in the film, which
microscope (TEM) provides
imagingan increased effective surface
of the substrate-film nanowall-like
interface as shownstructure.
in Figure The3.spacing between the graphene
The high-resolution TEM
activation.
image From the
(HRTEM) cross-sectional
image SEM images interface
of the film-substrate (Figure (Figure
layers is3b)
∼ 0.34 nm. From
reveals that the HRTEM
during picture, the regions
the initial-stage of the
2) of the FLVG
growth, film (grown
the graphene for lying
layers 30 min)parallel
the height of the
to the show surface.
substrate a lattice spacing of ∼ 0.21the
Subsequently, nm,outer
whichplanes
indicates
of the
the
flakes is found
horizontal to be ∼
graphene 77 nm,preferentially
surface and the thickness is in the
curls-up presence of nanocrystalline
and progressively turned into thediamond
vertical in the film followed
direction matrix.
range
by theofinner
∼ 3 −7planes.
nm. Then, the growth transforms into one-dimensional wire-like and
structure
Raman spectroscopy X-rayupphotoemission
to a height of
∼5−7Wenm. Finally, the wire-like carbon structures branched anisotropically into a two-dimensional
further probed the onset of FLVG film growth spectroscopy (XPS) analysis are employed to study further form,
exhibiting a nanowall-like
through cross-sectional structure.electron
transmission The spacing betweenthe
microscope thedetails
graphene
of thelayers is ∼ 0.34
crystalline nm. From
structure of thetheFLVG
HRTEM
film
(TEM) imaging
picture, of the substrate-film
the regions show a lattice interface
spacingas shown in nm,
of ∼ 0.21 grown for 30indicates
which minutes. theFigure 4a shows
presence of ananocrystalline
typical Raman
Figure 3. The
diamond high-resolution
in the film matrix. TEM image (HRTEM) image spectrum of the FLVG film. The spectra consist of two
of the film-substrate interface (Figure 3b) reveals that during prominent peaks at 1340 cm-1 and 1580 cm-1, commonly
the initial-stage of the
growth, the graphene
layers lying parallel to
the substrate surface.
Subsequently, the outer
planes of the horizontal
graphene surface
preferentially curls-
up and progressively
turned into the vertical
direction followed
by the inner planes.
Then, the growth
transforms into one-
dimensional wire-like
structure up to a height
of ∼5−7 nm. Finally,
the wire-like carbon
structures branched (a) 3:
Fig. 3:Fig. TEM and (b)
(a) TEM andHRTEM images
(b) HRTEM of the
images FLVG-nanodiamond
of the FLVG-nanodiamondhybrid
hybridfilm.
film.
Raman spectroscopy and X-ray photoemission spectroscopy (XPS) analysis are employed to study
further the details of the crystalline structure of the FLVG film grown for 30 minutes. Figure 4a shows a 35 typical
Raman spectrum of the FLVG film. The spectra consist of two prominent peaks at 1340 cm-1 and 1580 cm-1,
commonly known as D- and G-mode, 3 respectively, which are characteristics features of graphitic structures
can be deconvoluted into three distinct peaks. The peak at binding energy (BE) of 284.1 eV is closely
resembling with the BE of silicon carbide (Si-C) [29] believed to be formed at the substrate- film interface,
which resembles with the HRTEM observation (Figure 3b). The peaks at 284.5 eV and 285 eV are corresponds
2
toSMC
the Bulletin
C-C spVol. 11 (No. graphitic
bonded and C-C sp3 bonded diamond nanostructures, respectively [32, 33].
1) April 2020
Fig. 4: A typical (a) Raman and (b) XPS spectra of the FLVG-nanodiamond hybrid structure.
Fig. 4: A typical (a) Raman and (b) XPS spectra of the FLVG-nanodiamond hybrid structure.
known as D- and G-mode, respectively, which are graphene sheets parallel to the substrates in the form of
The possible
characteristics features growth mechanism
of graphitic structuresof[30].
theThe
FLVG structure
laterally can be
connected understood
carbon nanosheetsby orconsidering its
nanowalls [17-
microstructural evolution as a function of the critical growth parameters. In earlier reports, the
G-peak is established as an effect of E2g-phon vibration 26]. However, the present HRTEM observations of the mechanism for
centered at the graphene Brillioun zone. The D-peak FLVG film (Figure 3b) suggest that at the beginning of the
appeared due to the defect-induced double resonance growth, a thin amorphous carbon layer (3 nm) deposited at
inter-valley scattering of phonons at the K-point of the 4 the substrate surface, followed by the horizontal graphene
Brilioun zone. The broad peak at 2670 cm-1 is known as plane. The graphene planes on top of the amorphous
2D-mode of graphene, an overtone of D-mode, which is a carbon layer lying horizontally parallel to the substrate
defect free mediated two-phonon combination process [30]. surface, might have formed either by the coalescence of
The appearance of 2D- and G-mode signifies the presence graphene nanoislands [34] or due to the condensation of
of sp2crystalline carbon form. The small peak at 1146 cm-1 carbon cluster along one direction forming continuous
indicates the presence of trans-polyacetylene carbon form, parallel graphene layers [25].The subsequent transition
usually observed in the grain boundaries of nanocystalline of graphene plane from the horizontal plane to vertical
diamond [31]. It corroborates with the HRTEM results, plane proposed to be caused by many factors. Yoshimura
which again indicates the presence of nanocrystalline et al [35] have discussed that the formation of a new
diamond in the FLVG film. The high-resolution C1s XPS crystalline phases at a critical growth time changes the
spectra of the FLVG/nanodiamnd composite film shown orientation of graphene layers. Soin et al [36] have argued
in Figure 4b can be deconvoluted into three distinct that the release of stress at the grain boundary due to the
peaks. The peak at binding energy (BE) of 284.1 eV is collapse of carbon islands causes the vertical transition of
closely resembling with the BE of silicon carbide (Si-C) the graphene plane from its parallel direction. However, in
[29] believed to be formed at the substrate- film interface, the present study, the HRTEM micrograph analysis (Figure
which resembles with the HRTEM observation (Figure 3b). 3b) clearly indicates that the vertical growth succeeded
The peaks at 284.5 eV and 285 eV are corresponds to the by progressive curving of the graphene plane from the
C-C sp2 bonded graphitic and C-C sp3 bonded diamond horizontal surface rather than direct nucleation of carbon
nanostructures, respectively [32, 33]. atoms in perpendicular to the horizontal graphene plane.
The upwardly curled carbon edges serve as nucleation
The possible growth mechanism of the FLVG structure
sites for the vertical growth, which subsequently attracts
can be understood by considering its microstructural
more number of carbon atoms from the growth species
evolution as a function of the critical growth parameters. In
as compared to the planar ones, possibly due to the
earlier reports, the mechanism for the catalyst-free vertical
temperature gradients. Eventually, the growth transformed
growth of various carbon nanostructures are predicted to
in the vertical direction due to the high surface mobility
be either due to the highly directed electric filed caused
of incoming carbon-bearing species. Malesevic et al [37]
by the localized plasma or due the self-assembly of the
36
not a natural selection/direct nucleation from the horizontal surface. Therefore, we further inspected the growth
behavior of the FLVG film by carrying out the growth without adding nitrogen gas in the feed gas mixture of
Ar/CH4/H2 (78/2/20 SCCM), keeping all the growth parameters constant.
SMC Bulletin Vol. 11 (No. 1) April 2020
Fig.
Fig. (a) Low
5:5:(a) Lowand
and(b)(b)
High resolution
High SEM images
resolution SEMofimages
the carbon
ofnanostructured film grown withoutfilm
the carbon nanostructured nitrogen
growncontent in the nitrogen
without precursor gas−mixture.
content in
the precursor gas−mixture.
have observed a similar phenomenon, which suggest that pentagon defects create distortion and curving of the
the curling edges formed either by the ion bombardment graphene layers, which lead to graphene sheets of high
The SEM micrograph of the film shows that the grown carbon nanostructures are lying parallel to the
or due to the lattice mismatch between the substrate and curvatures and cross-linked structures. The curling of
substrate surface and rarely being vertical, as shown in Figure 5. It illustrates that the nitrogen induced defects
graphite planes serve as nucleation sites for the vertical carbon planes induced by the pentagon defects is due
might have stimulated the two-dimensional vertical growth.
growth.
It has been observed that the incorporation of
to the asymmetric behaviour of the free carbon atoms
nitrogen atoms into the hexagonal structure of graphene sheets attachedcreates pyrrolic-
to these defects,and pyridinic-like
where pentagonal
the three in-plane sp2-
However, up to now, it explains only the vertical
defects [38-41]. Chan et al [42] have shown that the nitrogen-induced pentagon defects create distortion and
bonds and a Pz orbital aligned perpendicular to this plane.
direction
curving of the
of the growth.layers,
graphene The vertical
whichgrowth of graphene
lead to graphene sheets of high curvatures and cross-linked structures.
This asymmetry not only conduce the curved structure,
Theincurling
a two-dimensional form, rather than in one-dimensional
of carbon planes induced by the pentagon defects is provides
but also due to the asymmetric
sites behaviour
for the damage of theand
of the surface free
form (vertical nanowire-like structure) is still puzzling 2
carbon atoms attached to these defects, where the three in-planethus the -bondsbranching
sp further and a Pz oforbital aligned perpendicular
the nanostructure; a process
and yet to be understood. It can be rememorized that the
commonly observed in the synthesis of carbon nanotube
HRTEM micrograph (Figure 3) indicated that the two-
[43]. Interestingly, the present experimental observations
dimensional vertical growth appeared only after few
depict a similar phenomenon. The basal planes of the few
nanometers of one-dimensional vertical growth from the
5 layered graphene get distorted and buckled by the nitrogen
horizontal graphene planes. This depicts that the two-
induced defects, and thus curled upward in order to inhabit
dimensional growth of graphene plane is not a natural
the vertical growth. Consequently, the vertical growth
selection/direct nucleation from the horizontal surface.
transformed into a two-dimensional nanostructure due
Therefore, we further inspected the growth behavior
to the bending of graphene layers in both the directions,
of the FLVG film by carrying out the growth without
and the subsequent nucleation of carbon atoms on top of
adding nitrogen gas in the feed gas mixture of Ar/CH4/
it adds more number of graphene layers on to it following
H2 (78/2/20 SCCM), keeping all the growth parameters
the existed bending pattern.
constant.
The presence of diamond nanoparticles in the matrix
The SEM micrograph of the film shows that the grown
of graphene planar structure is due to the presence of low
carbon nanostructures are lying parallel to the substrate
concentration of hydrogen in the plasma. A transition from
surface and rarely being vertical, as shown in Figure 5. It
hydrogen-rich plasma to argon-rich plasma decreases the
illustrates that the nitrogen induced defects might have
diamond stability from the macro- to the nano-scale, hence
stimulated the two-dimensional vertical growth. It has
favours growth of diamond nanoparticle [44, 45].
been observed that the incorporation of nitrogen atoms
into the hexagonal structure of graphene sheets creates
4. Conclusion
pyrrolic- and pyridinic-like pentagonal defects [38-41].
Chan et al [42] have shown that the nitrogen-induced In conclusion, I have demonstrated the growth of
37
SMC Bulletin Vol. 11 (No. 1) April 2020
38
Journal of Raman Spectroscopy 45 (2014) 642.
35. H. Yoshimura, S. Yamada, A. Yoshimura, I. Hirosawa, K. Kojima, M. Tachibana, Chemical Physics
Letter 482 (2009) 125.
36. N. Soin, S. S. Roy, C. Kane, J. A. D. McLaughlin, T. H. Limb, C. J. D. Hetherington, CrystEngComm
13 (2011) 312. SMC Bulletin Vol. 11 (No. 1) April 2020
37. A. Malesevic, R. Vitchev, K. Schouteden, A. Volodin, L. Zhang, G. V. Tendeloo, A. Vanhulsel, C. V.
Haesendonck, Nanotechnology 19 (2008) 305604.
39. D.
38.Wei,
H.Y. Liu,L.Y.Song,
Gao, Wang,W.H. Zhang,
Guo, L. Huang,
L. Huang, G. Yu,
D. Yang, F. Nano
Wang, Y. Zuo,H. X.C.Fan,
Shih, T. C.W.
Z. Liu, Lin, F. S.
Gao, R. Shieu,
Vajtai, K.
K. J. Chen, H. C. Cheng,
LetterHackenberg,
9 (2009) 1752.P. M. Ajayan, Carbon 50 (2012) 4476. Applied Physics Letter 82 (2003) 4334.
40. 39.Ghosh,
K. D. Wei,
M. Y. Liu, Y.T.Wang,
Kumar, H. Zhang,
Maruyama, Y. L. Huang,
Ando, G. Yu,48Nano43.
Carbon Letter 9 (2009)
S. C. Mu, H.1752.
L. Tang, S. H. Qian, M. Pan, and R. Z. Yuan,
40. K. Ghosh,
(2010) 191. M. Kumar, T. Maruyama, Y. Ando, Carbon 48 (2010) 191.
Carbon 44 (2006) 762.
41. S. Kar, D. R. Mohapatra, E. Feysez, A. K. sood , Phys. Rev. B 90 (2014) 165420.
41. S. Kar, D. R. Mohapatra, E. Feysez, A. K. sood , Phys. Rev. B 44. V. I. Konov, A. A. Smolin, V. G. Ralchenko, S. M. Pimenov,
42. L. H. Chan, K. H. Hong, D. Q. Xiao, W. J. Hsieh, S. H. Lai, H. C. Shih, T. C. Lin, F. S. Shieu, K. J.
90 (2014) 165420. E. D. Obraztsova, E. N. Loubnin, S. M. Metev, G. Sepold,
Chen, H. C. Cheng, Applied Physics Letter 82 (2003) 4334.
42. L. H. Chan, K. H. Hong, D. Q. Xiao, W. J. Hsieh, S. H. Lai, Diamond Relat. Mater. 4 (1995) 1073.
43. S. C. Mu, H. L. Tang, S. H. Qian, M. Pan, and R. Z. Yuan, Carbon 44 (2006) 762.
44. V. I. Konov, A. A. Smolin, V. G. Ralchenko, S. M. Pimenov, 45. E.D.D.M.Obraztsova,
Gruen, Annu.
E. N.Rev. Mater.S.Sci.
Loubnin, M.29 (1999) 211.
Metev, G. Sepold, Diamond Relat. Mater. 4 (1995) 1073.
45. D. M. Gruen, Annu. Rev. Mater. Sci. 29 (1999) 211.
Dr.Dipti
Dr. DiptiRanjan
Ranjan Mohapatra,
Mohapatra, working
working as Assistant
as Assistant Professor
Professor in the in the Department
Department of of Physics, Vikram
Deb (Autonomous) College, Jeypore, Koraput, Odisha-764001, since February 2015. He completed
Physics, Vikram Deb (Autonomous) College, Jeypore, Koraput, Odisha-764001, since
his Ph. D.
February 2015.degree in Condensed
He completed his Ph.Matter
D. degreePhysics from IIT
in Condensed Bombay
Matter in from
Physics 2010.Dr. D. R. Mohapatra
IIT Bombay in 2010.Dr. D. R. Mohapatra worked as a postdoctoral fellow
worked as a postdoctoral fellow under DST Nanomission postdoctoral fellowship under DST at Indian Institute
Nanomission postdoctoral fellowship at Indian Institute of Science, Bangalore, in the
of Science, Bangalore, in the group of Prof. Ajay kumar Sood (July 2011 – February 2015). Also, he
group of Prof. Ajay kumar Sood (July 2011 – February 2015). Also, he was a
was a postdoctoral
postdoctoral fellow in fellow in the department
the department of electronicofmaterial
electronic material
center, Korea center,
Institute Korea
of Institute of Science
and Technology,
Science SouthSouth
and Technology, KoreaKorea
(August 20102010
(August – June 2011).
– June Dr.Dr.
2011). Mohapatra
Mohapatra is is
an expert in synthesizing
carbon-based
an materials namely
expert in synthesizing single materials
carbon-based crystal diamond, graphene
namely single and diamond,
crystal carbon nanotubes using various
CVD techniques.
graphene and carbon These materials
nanotubes arevarious
using extensively studied forThese
CVD techniques. photo-sensors
materials andare transistor applications.
He has more
extensively than for
studied 20 research publications
photo-sensors in international
and transistor peerHereviewed
applications. has more journals.
than He has developed and
taught
20 various
research courses in
publications of international
Physics to postgraduate
peer reviewedand undergraduate
journals. students. He is also consulting
He has developed
industries for growing single crystal diamond.
and taught various courses of Physics to postgraduate and undergraduate students.
He is also consulting industries for growing single crystal diamond.
39
SMC Bulletin Vol. 11 (No. 1) April 2020
Keywords: Electron field emission, Nanocrystalline energy band [5,6]. A paradox is that diamond films with
diamond films, Chemical vapour deposition poor quality gives good electron field emission (EFE)
properties making the problem more complicated [7].
1. Introduction
In the present article we present a systematic study on
Field emission displays (FEDs) have the potential to the synthesis and electron field emission characterization
be low cost, high performance alternative to the currently of NCD films grown by microwave plasma CVD using
dominant cathode ray tube and liquid crystal display Ar/CH4 as precursors. Ion implantation technique has
technologies for flat panel displays. One of the key issues been used to induce defects in the NCD films and to create
in FEDs has been the development of reliable and efficient a structural transformation from diamond to graphite
cold cathode material for electron field emitters. Earlier to some extent. The electron field emission properties
field emitter typically employed metals (such as Mo) of NCD films are found to be highly dependent on their
or semiconductors (such as Si) with nanometer sized microstructure.
sharp tips. These emitters typically require complicated
fabrication steps and need high control voltage for emission 2. Experiment
(100 V) because of high work function associated with
NCD films were deposited by microwave plasma
these materials.
enhanced chemical vapor deposition process (2.45 GHz
Diamond and related materials have extensively ASTeX MPECVD system). The CH4 / H2 gases with flow
been studied for their novel mechanical, chemical and rate of 45/300 sccm (~55 Torr) were excited by 1500-W
electrical properties. Particularly because of low or negative microwave power. The diamond nuclei were formed on
electron affinity (NEA), diamond is optimum candidate mirror smooth silicon substrate by applying a negative bias
for field electron emission materials that has potential voltage (-135 V) to the substrate with respect to the plasma.
applications in the area of flat display and vacuum The bias current was around 45 mA at the beginning of the
microelectronic devices. Cold cathode field emission has application of bias voltage. The bias current value remained
been demonstrated in chemical vapour deposited diamond at such small value for about few minutes and increased
films, from which a prototype flat panel display has abruptly, indicating the onset of the formation of diamond
even been made [1]. However the mechanism of electron nuclei, and saturated after a few minutes, implying the
emission from chemical vapour deposition (CVD) diamond full coverage of the diamond nuclei on the substrates. The
films remains to be investigated, although several models depositions were carried out at methane concentrations
have been suggested such as surface morphology [2], back of CH4 / H2 ratio of 3/97 and 5/95 in balanced hydrogen
metal contact [3], surface diode [4] and defect induced atmosphere at a pressure of 55 Torr with a microwave
40
suggests that defects were generated in NCD film [10]. Broad D2 band around 1360 cm is more prominent in
all films after a dose of 1013 ions/cm2, indicating the increase in proportion of nano-sized grains due to N ion
implantation. Interestingly after 1015 ions/cm2 dose, the diamond signature line becomes weak (Figs. 2(aIII) and
2 (bIII)). The broad D2-band shifts towards lower value indicating formation of disorder chains.
SMC Bulletin Vol. 11 (No. 1) April 2020
were implanted with nitrogen ions of 100 keV at doses of The D1 and D2-bands are presumably contributed by the
1013 and 1015 ions/cm2. The penetration depth of the ions presence of nano-sized grains in these diamond films [9].
has been calculated by Stopping and Range of Ions in solids Both the films A & B showed increase9 in Full Width Half
(SRIM 2006) program. It was found to be around 120 nm. Maximum (FWHM) due to ion implantation (Figs. 2 (aII)
This shows that ions are stopping well inside the film as and 2 (bII)). This suggests that defects were generated
thickness of the film is around 250 nm. The energetic ions in NCD film [10]. Broad D2 band around 1360 cm is
-1
while passing through target material, loss energy either more prominent in all films after a dose of 10 ions/cm ,
13 2
by elastic or inelastic collisions. Thus the fast moving ions indicating the increase in proportion of nano-sized grains
are expected to create defects and structural damage in due to N ion implantation. Interestingly after 10 ions/
15
Fig. 1: SEM micrographs of nitrogen ion-implanted films grown at (a) 3% and (b) 5% CH4 / H2.
the target material [8]. Before and after ion implantation cm dose, the diamond signature line becomes weak (Figs.
2
NCD films were characterized by field emission scanning 2(aIII) and 2 (bIII)). The broad D2-band shifts towards lower
electron microscopy (FESEM, JEOL 6010) and Raman value indicating formation of disorder chains.
spectroscopy (Renishaw). Electron field emission was While Raman spectra illustrate clearly the modification
measured by a parallel-plate setup. The cathode to anode
9 on defect structure of nanocrystalline diamonds due to N
distance controlled by a micrometer attached to it. The ion implantation process, the quantitative analysis of the
chamber pressure during electron field emission was defects induced from these spectra is difficult due to the
maintained at 10-6 Torr. The current–voltage properties relatively different sensitivity of Raman scattering for sp2
were measured by an electron source unit (Keithley, and sp3 component. That initiated us to study the near
Model 237). The NEXAFs spectra were performed using edge X-ray absorption fine structure (NEXAFs) study of
the high energy spherical grating monochromator beam as deposited as well as implanted films, since NEXAFs is
line at National Synchrotron Radiation Research Center one of the best tool to quantify the sp2 and sp3 component
(NSRRC), Hsinchu, Taiwan. in diamond film. Figure 3 displays the C K-edge NEXAFs
spectra of as deposited and implanted films. The spectra
3. Result and discussion were normalized using the incident beam intensity Io and
The scanning electron microscopy (SEM) micrographs keeping the area under the spectra in the energy range
(Fig. 1) showed continuous films were deposited and the between 314 and 335 eV fixed. The NEXAFs energy range
crystal size increases with methane percentage. It varied for diamond generally can be divided into two regions
from 200 nm to 250 nm as the CH4 increases from 3% to characterized by specific features. One is a spike of C 1s core
5%. UV Raman (324 nm) spectra of the as deposited and excitation resonance at approximately 289.2 eV. Another
ion implanted films was studied (Fig. 2). An unambiguous is a relatively broad σ* feature in the energy between 288.6
signature of diamond is seen at 1332 cm-1 (D-band) in all and 302 eV for the sp3 bonded carbon. The relatively small
films suggesting the film of diamond. The spectra also peak at ∼285 eV can be attributed to graphite like π* state
showed a significant amount of graphitic carbon in the film of sp2 bonded carbon. The peak at 287 –288 eV, between
that is evident by G-band at 1580 cm-1. After Lorentzian π* and σ* features can be attributed to the C-H bond on the
peak fitting to Raman spectrum of as deposited NCD films, diamond surface.
two more peaks, one around 1140 cm-1 (D1-band) and the
41
SMC Bulletin Vol. 11 (No. 1) April 2020
42
implantation from the as grown turn-on field value for both films. In contrast, the EFE current density (Je) is
insignificantly altered due to low dosage (1013 ions.cm2). N ion-implantation but is markedly increased resulted
from the high dosage (1015 ions.cm2) N ion-implantation. The EFE current density increase in larger extent for
film A (3% CH4), as compared with that for film B (5% CH4).
SMC Bulletin Vol. 11 (No. 1) April 2020
one or more bands within the bulk diamond band gap gap
significant, the electronic states of the defects could form one or more bands within the bulk diamond band
[13]. Electrons can be excited from the defect bands to the surface states for emission. Thus, we observe
[13].
reduction Electrons
in the canthebe
turn-on field from excited
value from
of as grown the defects
film. These defect havebands to the
altered work function of as
surface states for emission. Thus, we observe reduction
in the turn-on field from the value 12 of as grown film. These
defects have altered work function of as deposited NCD
films. Such an argument is supported by the increase in
FWHM of diamond signature line after ion implantation
(Fig. 2 and Table 1). That the decrease in turn on field is
(Dotted
It should be notedlines
that Iindicates
sp2 / Isp3 ratioGuassian
for sample Afitting)
was found to be 0.004490, 0.004769 and 0.03441 for as
deposited films, ion dose 1013 ions/cm2 and to ion dose 1015 ions/cm2 respectively. Also noted that Isp2 / Isp3 ratio
Sample FWHM ∆ (Isp2/ Isp3) J (mA/ E (V/
for sample B was 0.004470, 0.004570 and 0.03029. This indicates that the ratio does not cha nge much for the
cm2) µm)films for low Thedoseinset shows
(1013 ions/cm 2
) butthe peak
increases associated
profoundly with
for the high dosesp
(10215bonding and
ions/cm2). The turn-on field
(E0) and emission current density (Je) and are then plotted against the (η) [η is defined as ∆ (Isp2/ Isp3) =
3% As 13 0.00449 0.151 18(Isp2/Isp3)Ion C-H
Implanted bonding.
2 3
It is] observed
– (Isp / Isp )As Deposited in Fig 5. The η that integral
is thus a measureintensity of C-H
of relative change in sp2 and sp3
Grown content before and after ion implantation. Fig. 6 shows that when N ion-implanted for low dosage (1013
bonding has direct correlation to turn on field of the films.
ions/cm2), there is no much change in η, but the turn-on field (E0) decreases drastically. On the contrary, when
1013 31 0.0047 0.196 13.33
N ion-implantedIt is observed
for high dosagethat the integral
(1015 ions/cm 2
intensity
), the η value isamore
increases in in case
large extend, of as
but there is not much
1015 - 0.03441 1.926 14 deposited film B than as deposited film A. As the integral
5% As 19 0.004470 0.0158 16 intensity is proportional to13C-H bonds present near the
Grown surface, it improves the negative electron affinity of the
1013 21 0.004570 0.1414 13.5 surface of the film [15]. This in turn reduces the turn on
1015 - 0.03029 0.3312 11.33 field that is observed in our as deposited films also (Table
43
SMC Bulletin Vol. 11 (No. 1) April 2020
phase results in more abundant electron conduction path. substrates to the diamond surface.
It should be reminded that the surface of diamonds The increase in current density
15 is very unlikely due to
can be converted into very conducting by forming the the nitrogen ion acquiring dopant site. If at all it acquires
hydrogen bonds on the diamond surfaces, which were it, Nitrogen is well known deep level impurity and
presumed due to the injection of electrons from the proton hence unsuitable for producing n type diamond [18[. The
to the diamonds [17]. The same mechanism is adopted to other reason to believe this is fact that the total amount
account for the increase in EFE current density due to the of nitrogen ions concentration varies from around 1017
increase in proportion of sp2-bonded phase. The possible cm-2 to 1019 cm-2 for implanted dose of 1 x 1013 ions/cm-2
44
SMC Bulletin Vol. 11 (No. 1) April 2020
and 1 x 1015 ions/cm-2, respectively. This concentration is to diamond has been proposed to explain the increase in
not sufficient to convert it into highly conducting n type the electron field emission property.
diamond film. Also earlier studies have shown following
conclusions about ion implantation [19-21]: (i) There exists Acknowledgement
a critical implantation dose 2 x 1014 – 1015 ions/cm-2 beyond The authors would like to thank National Science
which the damage cannot be healed out by annealing and Council, R.O.C. for the support of this research through
the damaged layer turns to graphite (ii) Graphitization the project No. NSC 95-2112-M-032-005.
can be avoided for implantation exceeding the critical
dose if the implantation are carried out at into heated References
(1400 oC) diamond. From all of the above discussion and 1. N. Kumar and H. Schmidt, Semicond. Sci. Technol. 71 (1995)
looking at our experimental conditions it can be clearly 73.
concluded that the nitrogen ion implantation has very 2. Y. H. Chen, C. T. Hu and I. N. Lin, J. Appl. Phys. 84 (1998)
unlikely doped the nanocrystalline diamond films to give 3890.
high current density. Whereas the graphitization created 3. M. W. Geis, J. C. Twichell, N. N. Efremow, K. Krohn and T.
due to ion implantation might have created conducting M. Lyszczarz, Appl. Phys. Letts 68 (1996) 2294.
channels for facilitating electron field emission property 4. T. Yamada, H. Ishihara, K. Okano, S. Koizumi and J. Itoh, J.
of nanocrystalline diamond film. The later may be the Vac. Sci. Technol. B 15, (1997) 1678.
dominant phenomenon working in our films. 5. W. Zhu, G. P. Kochanski and S. Jin, Science 282 (1998) 1471.
6. A. Wisitsoraat, W. P. Kang, J. L. Davidson and D. V Kerns,
For the films A grown in 3% CH4, the grains are Appl. Phys. Letts 71 (1997) 3394.
smaller (~ 200 nm) and the number density of electron 7. K. H. Park, S. Lee and K. H. Koh, Diam. Relat. Mater. 9 (2000)
conduction channels are abundant enough to form 1342.
conducting network. The increase in EFE current density 8. J. F. Morhange, R. Beserman and J. C. Bourgoin. Jpn. J. Appl.
due to N ion-implantation is thus prominent. In contrast, Phy. 14 (1975) 544.
for the films B grown in 5% CH4, the grains are larger (~ 9. T. Sharda, T. Soga, T. Jimbo and M. Umeno, J. Nanosci.
250 nm) and the number density of electron conduction Nanotec. 1 (2001) 287.
channels is insufficient to convert all the diamond films 10. B. Miller, R. Kallish, L. C. Feldman, A. Katz, N. Moriya, K.
conducting. The improvement on EFE current density is Short and A.E. White, J. Electrochem. Soc. 141 (1994) L41.
thus only moderate. 11. A.Laikhtman, I. Gouzman and A. Hoffman, Diamond Relat.
Mater. 9 (2000) 1026.
4. Conclusion 12. T. J. Lewis, Phys. Rev. 101 (1956) 1694.
13. W.V.M. Machado, J. Kintop, M. L. De Siqueria and L.G.
In summary, the field required for emission from
Ferreirra, Phys. Rev. B 47 (1993) 13219.
CVD diamond has been improved when diamond films
14. W. Zhu, G. P. Kochanski, S. Jin, L. Seibles, D. C. Jacobson, M.
are implanted by nitrogen ions. The impinging ions McCormack and A. E. White, Appl. Phys. Lett 67 (8) (1995)
have created structural modification on the surface of 1157.
the film. This was quantitatively studied using NEXAFs. 15. Z. Shpilman, Sh. Michaelson and R. Kalish, Diamond Relat.
It was observed that with ion implantation ∆ (Isp2/ Isp3) Mater. 15 (2006) 846.
ratio increased. This clearly indicates change in the 16. A. Laikhtman, A. Hoffman, R. Kalish, A. Breskin and R.
microstructure of the film near the surface. An enhancement Chechik, J. Appl. Phys. 88 (2000) 2451.
in electron field emission current density has been observed 17. A. Denisenko, A. Aleksov, A. Probil, P. Gluche, W. Ebert,
for both the films after implantation of high dose. The Diamond Relat. Mater. 9 (2000) 1138.
improvement has been seen more effectively for sample 18. Johan. F. Prins, Nucl. Instrum. and Methods in Physics Res
A 514 (2003) 69.
A. As nitrogen being deep donor, it could barely influence
the electron field emission property. A more prominent 19. G. Braunstein, A. Talmi, R. Kalish and T. Bernstein, Radiat.
Eff. 48 (1980) 139.
mechanism could be the conducting channels created due
20. G. Braunstein and R. Kalish, Appl. Phys. Lett. 38 (1981) 416.
to fast moving ions through the diamond films. A model
21. G. Braunstein and R. Kalish, Nucl. Instrum. Methods 182
based on injection of electron from these disordered carbon
(1981) 691.
45
16. A. Laikhtman, A. Hoffman, R. Kalish, A. Breskin and R. Chechik, J. Appl. Phys. 88 (2000) 2451.
17. A.
17. A.Denisenko,
Denisenko,A.A.Aleksov,
Aleksov, A.A. Probil,
Probil, P. Gluche,
P. Gluche, W. W. Ebert,
Ebert, Diamond
Diamond Relat.
Relat. Mater.
Mater. 9 (2000)
9 (2000) 1138. 1138.
18. Johan. F. Prins, Nucl. Instrum. and Methods in Physics Res A 514
18. Johan. F. Prins, Nucl. Instrum. and Methods in Physics Res A 514 (2003) 69. (2003) 69.
19. G.
19. G.Braunstein,
Braunstein,A.A.Talmi,
Talmi,R.R. Kalish
Kalish andand T. Bernstein,
T. Bernstein, Radiat.
Radiat. Eff. Eff. 48 (1980)
48 (1980) 139. 139.
20.
20. G.
G. Braunstein
Braunstein and
and R.
R. Kalish,
Kalish, Appl.
Appl.
SMC Bulletin Vol. 11 (No. 1) April 2020 Phys.
Phys. Lett.
Lett. 38 38 (1981)
(1981) 416.416.
21. G.
21. G.Braunstein
BraunsteinandandR.R.Kalish,
Kalish, Nucl.
Nucl. Instrum.
Instrum. Methods
Methods 182182 (1981)
(1981) 691. 691.
Dr.
Dr. Umesh
Dr.Umesh Palnitkar
UmeshPalnitkar
Palnitkarhashas
been
has been awarded
awarded
been Doctoral
Doctoral
awarded Degree
Degree
Doctoral inin2003
in 2003
Degree for
for his
2003 hishiswork
forwork workononmicrocrystalline
on
diamond films from
microcrystalline
microcrystalline IIT films
diamond
diamond Bombay. He
IIT did
fromfrom
films post-doctoral
Bombay.
IIT He did
Bombay. fellowship
He post-doctoral
did in Tamkang
fellowship
post-doctoral in University,
fellowship in Taiwan.
Presently,
Tamkang his
Tamkang research interest
University,
University, Taiwan.isPresently,
Taiwan. studying mechanical
Presently, his his researchproperties
research interest of
interest is is ultra-nanocrystalline
studying mechanical diamond films.
studying mechanical
properties
propertiesof of
ultra-nanocrystalline
ultra-nanocrystallinediamond films.films.
diamond
Dr. I-Nan Lin graduated from the Department of Materials Science, University of
Dr.
Dr.I-Nan
I-Nan
California Lin graduated
Lin graduated
at Berkeley
from the
in 1983.from
Department
theworked
He has Department of Materials
of
on electron
Materials Science,
Science, University
Universityofof California at
field emission of diamond,
Berkeley in
California 1983.
at He
Berkeley has
in worked
1983. He on
haselectron
worked field
on emission
electron of
field
diamond-like and carbon nanotube materials for more than 15 years. Presently, diamond,
emission ofdiamond-like
diamond,
his and carbon
nanotube
research materials
diamond-like
interestand for more
carbon
is studying than
nanotube
the 15 materials
years.
syntheses Presently,
for morehisthan
and characteristics research
of interest
15 years. is studying
Presently,
ultra-nanocrystalline his the syntheses
and characteristics
research
diamond interest isofstudying
films. ultra-nanocrystalline diamond
the syntheses and films.
characteristics of ultra-nanocrystalline
diamond films.
Prof. HuanNiu
Prof. Huan Niu is is working
working in Nuclear
in Nuclear Science
Science and Technology
and Technology Development
Development Center, Center, Accelerator
Division, National Tsing-Hua16University, Hsinchu, Taiwan since 2003. He hasHe
Accelerator Division, National Tsing-Hua University, Hsinchu, Taiwan since 2003. been awarded Ph.D. in
has been awarded Ph.D. in Atomic Physics from National Tsing Hua University,
Atomic Physics from National Tsing 16 Accelerator Division. His present interest is in Center’s Accelerator
Hua University, Taiwan. He is the leader of
Taiwan. He is the leader of Center's
Division.
studying magnetic properties of ion in
His present interest is studying
implanted magnetic properties of ion implanted nanodiamonds.
nanodiamonds.
46
Temperature influenced Electroluminescence in Carbon Nano-Tube Field Effect Transistors
47
18
∆z −∞ 2π q,s (4)
1 +∞ dE n
i) =
1 n+∞( zdE G ( E , q )
p ( zi ) =
q
Gqpq,(sE∆, zq)−∞ 2π
∆ z −∞ 2π
q ,s
1 +∞ dE p (5)
SMC Bulletin Vol. 11 (No. 1) April 2020
where, ∆z is the grid spacing and the summationpis ( zcarried
i ) = out∆zover
−∞ sub-band
2π
G q ( E , q )
and spin indexes, respectively. The
net current is calculated by using the following expressionq ,s[23, 26, 28].
Simulated CNTFET structure of coaxial where, gated
∆z is thedevice
grid spacing and the 4
summation
e is carried out over sub-band and spin indexes, respectivel
= following
structure is shown in the Fig. 1 below.net current is calculated by usingIthe ( E )[ f ( E[23,
dE Texpression S ) 28].
− E26, − f ( E − E D )] (6)
h (6)
4e the transmission
Source is doped N-type and is the
where, T(E)origin
is theoftransmission
electron coefficient
where, i.e.,IT(E)
T=( E+)is= dE(ΓGTΓ(G E+)[) fand
(E −f is coefficient
f ( E − E Di.e.,
) − Fermi-Dirac
E Sthe
)]distribution
carrier density (Nd) whereas drain contained P-type dopant T ( E ) = ( Γ G Γ G h ) and f
function. Radiative recombination rate [11, 16, 29] is calculated as follows: is the Fermi-Dirac distribution
with hole carrier density, Nd=1×109m-1where,
, tox=3nm (thickness function.
is the transmission Radiative
coefficient i.e., Trecombination
( E ) = (ΓG2ΓG +rate ) and [11,
f is 16,
the 29] is
Fermi-Dirac distri
of oxide layer), k=16 (dielectric constant),
T(E)
function.T=300K,
Radiative L calculated
recombination rate as
[11,
R =
follows:
16, 29]
β is
( np − n
calculated i
as
)follows: (7)
S/
=30nm (source/drain length) 3. and Lchand
=18nm (channel
D
length) is used.
Result discussion
Depending on carriers (e-/h+) energy they can occupy the certain R =number β ( np − ni2states
of energy ) [30]. The (7) local density
of states 3.(LDOS) spectrum
Result for the different temperature range is shown in the Fig. 2 below and respective
and discussion
We have used the non-equilibriumcurrent diagramGreen’s
is also
Depending carriers (e-/h3.
onfunction
plotted. + Result and discussion
) energy they can occupy the certain number of energy states [30]. The local d
N-type and method (NEGF)
is the origin method
of electron to solve
carrier the(NSchrodinger
density d ) whereas
of states equation.
drain
(LDOS)contained
spectrumP-type dopant
forDepending
the differenton carriers (erange
temperature -
/h+) is
energy
shownthey can
in the occupy
Fig. 2 below and resp
=1×109m-1and
r density, NdElectron hole functions
, tox=3nm are
(thickness of usedlayer),
oxide tocurrent
find out
k=16 the charge
(dielectric
diagram constant),
is also plotted. T=300K,
the certain number of energy states [30]. The local density
rce/drain length) and Ldensity
carrier’s ch=18nm on (channel
CNT length)
channelis [25].
used. The Green function
used the non-equilibrium Green’s function method (NEGF) method to solve theofSchrodinger states (LDOS) spectrum for the different temperature
is calculated by using the following equation [25]. range is shown in the Fig. 2 below and respective current
on and hole functions are used to find out the charge carrier’s density on CNT channel [25]. The
s calculated by using the following equation [25]. diagram is also plotted.
G ( E ) = [( E + i 0 ) I − H − Σ 1 − Σ 2 − Σ ineraction ] −1 (1)
+
The bright
(1) spikes in Fig. 2(a) represent the energy
+
dentity matrix, H is the tight binding Hamiltonian CNT, E is the energy of quantum states, is
density spike where total numbers of the charge carriers are
i0
where, I is the identity matrix, H is the tight binding
nt of the perturbation
Hamiltonianadded, Σ1 , ΣE2 is
CNT, arethe
theenergy
self-energy coupling states,
of quantum is distributed.
matricesi0of
+ source and drain It is observed that there is some fluctuation in
the density
Fig. 2: Plot of LDOS spectrum for (17,0) CNTFET
the small amount of the perturbation added, Σ , Σ are the
for (a) spikes
T=100K,at(c)
low temperature
T=200K, region
(e) T=300K they areEnergy
and respective not
defines theorigin
interaction self-energy position
matrices. resolved current diagram 2 is
1 contained are(b)used
T=100K (d) T=200K and (c) T=300K at VGS=0.475V and VDS=0.475V.
N-type
raction
and is self-energy
the
9 -1
of electron
coupling carrier density
matrices ofdSelf-energy
(N )source
whereas matrixes
drain
and drain (S/D) P-typetovery
consider
dopant clearthe for both electron and hole. As the temperature is
density, N =1×10 m , t =3nm (thickness of oxide layer), k=16 (dielectric constant), T=300K,
(S/D) on channel. represent theincreased fromspike 100K to 300Ktotal it is seenofthat the density spikesare
d ox
e/drain length) and andΣLint defineslength) theThe interaction
bright
used.spikes self-energy
in Fig. 2(a)matrices. energy density where numbers charge carriers
interaction is considered ch=18nm
eraction (channel
through the carrier isscattering mechanism [25-27]. Self-energy matrix
sed N-type Self-energy
theisnon-equilibrium matrixes
Green’s function are useddensity
distributed.
method to consider
It
(NEGF) is observed thethat effect
there is some grows
ofSchrodinger
fluctuation stronger in the causing
density to
spikesincrease
at low the current.
temperature This
region canare
they
ped
edure then and usedis thefororigin
treatment of electron
of the not carrier
carriers’ (Ndmethod
recombination ) whereas to solve
[11]. drain
Since the
contained
current P-type
lower dopant
down
rrierand density, contact
hole functionsN d=1×10 are (S/D)
9 -1
used , ttooxon
mcarrier find
=3nm channel.
out(thickness
the charge very clear
ofcarrier’s
oxide for both
density
layer), electron
on CNT
k=16 and
channel
(dielectric hole. be
As
[25]. explained
the
The27].
constant), temperature
T=300K, as follows:
is total
increased carriers
from 100K distribution
to 300K it is can
seen be
that
of scattering event and recombination density has almost
spikes grows samestronger
effect oncausing
the current
to [11,
increase the Tocurrent. This can be explained as follows: total carriers
calculated
source/drain
oherent by length)
transport using wethe and
havefollowing
Lconsidered
ch=18nm equation
(channel [25].length) is used.
thedistribution
electron-phonon scattering astheinteraction defined
mechanism. by the fermi-dirac distribution function [30]
Carrier’s +interaction is considered can be defined−1through
by tothe
fermi-dirac
solve thedistribution function [30]
gave used the
function G (non-equilibrium
for E ) = [( E + i 0transport
non-coherent )Green’s
I − Hare −function
Σ[25, − 27]:
Σ method
− Σ (NEGF) ] method Schrodinger 19
carrier (1)
in scattering
are usedmechanism n [25-27]. Self-energy matrix
1 2
[25]. The µ S / D − V S / D
ineraction
ectron and hole functions to find out the charge carrier’s density on CNT channel
ntity matrix, interaction Σusing
H isbythe ( E )the
tight D0 [(Hamiltonian
= following
binding + 1)G CNT,
N ω equation ( E +Ehω )the+ energy
N ω G of( Equantum
n
− hω )]states, i0 is f(2)
+
on is calculated procedure is then [25]. used isfor treatment of the S /D =
19
(8)
(8)
of the perturbation added,
()recombination
E=) [( ,+ are the[11]. −1self-energy coupling matrices (]Eof+source ω )] and drain (3) (1) k T
0 [( )H −(ΣE1 −− hΣω2 )−+Σlower
out p p 1
carriers’
G(E 1DΣ 2i 0N ω) I+ GSince current ω G down hdue
+ −
Σ =ΣE Nineraction B
At low temperature scale the (fs-fd ) region is very small and hence few numbers of densities of states are
he identity matrix,
ctron-phonon tocoupling
presence
H is the of
tight
constant, scattering
binding
h ω event
Hamiltonian
is covered
the phonon and
inside
carrier
CNT,
energythe E recombination
and is N
channel the energy
is number
region. of quantum
But of
at phonon
higher At lowi0temperature
states,
mode,
temperature
+
is more number scale the (fs-fd) region
of density of statesisarevery smallby
covered
defines the has interaction
almost self-energy
same effect matrices.
on the Self-energy
current [11, matrixes
27]. To
ω are
studyused the to consider the
ed by of
mount
tion
using
thethe Bose-Einstein
perturbation added, Σ1 , Σ 2the
distributions. are (f s-fdself-energy
Electrons
the ) region andcausing
holes
coupling both matrices
carrier electron
densitiesof and and
hole
aresource
definedhence
current
and few
as drain numbers of densities of states are
to increased [31]. It is observed that both electron and covered
S/D) on channel. non-coherent transport we 1 have
hole current+∞ considered
dE is very smallthe electron-
at 100K in Fig.2 (b),insidewiththe channel
temperature region. But at
enhancement more higher temperature
density of states aremorecovered
nteraction is considered through the
is thendefines
ureeraction
phonon
used for
scattering
thetreatment
interaction n ( zas
carrier
)
of self-energy
thei carriers’
by scattering
interaction
= (f -f )
matrices.
s d
mechanism
window
mechanism.
G
−∞ 2π Self-energy
recombination
q , s ∆z increase
drastic
q
n
(
and
in the
E ,
[11].
q [25-27].
)
hence due
matrixes
Since
current
Self-energy
to
incurrent
more
Fig. 2(f).
matrix excitation (the availability of large number of states) there is
carrier’s
usednumber
arelower to
down
Hence
consider of density
increase
the of states are covered by the (fs-fd) region
(4) in current is noticed with increase in temperature.
int
ftactscattering
(S/D) on event and
channel. carrier recombination
In/out scattering function has almost same
for non-coherent effect on the current [11, causing
27]. To both electron and hole current to increased [31].
Since temperature hastransport vital importance and it has the significant impact on the transport properties of
the1electron-phonon
+∞ dE
It is observed that both electron andfunction hole current
fs and is fd very
erent
function
transport we
r’s interaction
rocedurefor
is
is non-coherent
have
considered
are [25, 27]: considered
then used fortransport
through
p( zi ) = are [25,CNT
treatment∆ofz the
q ,s
the carrier
27]:
changed
− ∞ carriers’
scattering
scattering
Gq ( EDepending
[32]. p
, q)
recombination
as
mechanism interaction
[11].
2π and hence transport properties can be tuned (5)
[25-27].
Since
mechanism.
Self-energy
current
small lower
at
matrix
on the applied biases and temperature Fermi-distribution
down
100K in Fig.2 (b), with temperature enhancement
[31,32]. Since gate has vital importance in functioning of
can be
nce of scatteringΣ event in
( E ) and = Dcarrier [( N ωrecombination
+ 1)G the (FET
n
hhas
E + devices ω ) almost
+ Nand same
n
( E effect
ω Gis separated− hω )] on (2)
by thethe current
more
oxide [11,
(2)
layer 27].
density
of Toof states
particular are covered
thickness [33]. Based byon(fsthe
-fd)different
window and
thickness
n-coherent
grid spacing transport
andoutthewe have0 considered
summation is carried the electron-phonon
out over sub-band
ofpoxide used the gate pcontrol scattering
and spin (on as interaction
indexes,
CNTrespectively.
channel) mechanism.
can The
be altered, carrier injection rate be changed and in this way
( Efollowing
) = D0 [( transport (3) hence due to more carrier’s excitation (the availability
ring function
lculated by using for
Σ non-coherent
the ω + 1)G
Nexpression ([25,
are[23,
carrier 26, hω28].
27]:
E −transport ) + Nproperties
ωG (E + can hωbe)] changed [33]. (3)Hence effect of the temperature and different oxide thickness
4 of large number of states) there is drastic increase in the
where,Σ (E in
) = Dis e [(theNphonon
ω (+E1)[
variation )Genergy
n
( Ecoupling
on the ωN) ω+fconstant,
+ hradiative G ( E −ω
n
recombination hω )]rate (RRR) and(2)electroluminescence (EL) intensity is studied and is
ID=0 ishωelectron-phonon
Nnumber
ron-phonon coupling
by using theisBose-Einstein
the phonon
constant,
energy
distributions.
h
0 dE
and
T
presented
N
Electrons
f (in
is
E the
number
pand
− and
holes
Σ ( E ) = D0 [( N ω + 1ω)G ( E − hω ) + N ω G ( E + hω )]with increase
out
S ) − below.
EFig.3
of
is
( Eω − E D of
phonon
carrier
)] phononcurrent
p mode,
densities are defined
mode,
as
in Fig. 2(f). Hence increase in current is noticed
(6) (3)in temperature.
can becoefficient
determined by using 1 = the +∞ dE Bose-Einstein distributions.
( ) ( n ) and f is
+
the transmission
electron-phonon coupling constant, i.e., T E
n( zi ) = hω is the phonon Γ G Γ G
Gq ( Eenergy the Fermi-Dirac
, q) and Nω is number of phonon distribution
Electrons and16, holes carrier −densities
∞ 2π are defined as Sincemode, temperature has vital importance and it has the
ive recombination rate [11, 29] is calculated
∆ z as
mined by using the Bose-Einstein distributions. Electrons and holes carrier densitiessignificant
, follows: are (4)
defined as
q s
2 impact on the transport properties of CNT [32].
1 R+∞= dEβ p( np 1 +∞ −dE n )n (4) Depending on the applied biases and temperature Fermi-
p( zi ) = n( zi ) =G q (E, q−)∞ iGq ( E , q) (7)
discussion q , s ∆z
−∞ 2π q , s ∆z 2π distribution function fs and fd can be changed and hence
(4)
(5)
arriers (e-/h+) energy they can occupy the certain number of energy states [30]. Thetransport properties can be tuned [31,32]. Since gate has
local density
1 range dE The
rid spectrum
spacing andforthethe
summation
= out over
p( zisi temperature
)carried sub-band
( Eand
, q)inspintheindexes,
Fig. 2 respectively.
+∞
S) different Gis qpshown below and respective
vital importance in functioning of the FET devices and is
ulated by using the following expression [23, 26, 28].
2π 20
is also plotted. q , s ∆z
− ∞
(5) separated by the oxide layer of particular thickness [33].
4e (5)
h expression
the grid spacing and where,
the ∆z is dE
I =summation the T
is (
grid
E )[
carriedf (
spacing
E
out− E
over S )
and − f (
the
sub-bandE − E
and D )]
summation
spin is
indexes, Based on
respectively. the
The different thickness of oxide used the gate
carried
calculated by using the outfollowing
over sub-band and spin
[23, 26, indexes,
28]. respectively. control (6) (on CNT channel) can be altered, carrier injection
Thecoefficient
he transmission net current i.e., T4 is
(eEcalculated
) = (ΓGΓG +by ) and using theFermi-Dirac
f is the followingdistribution
rate be changed and in this way carrier transport properties
expression
e recombination rate [11, 16,[23,
I
29]26,
= 28]. dE Tas( Efollows:
is hcalculated
)[ f ( E − E S ) − f ( E − E D )]
can be changed (6) [33]. Hence effect of the temperature
2 +
is the transmission coefficient = Tβ((Enp
R i.e., )=− (ΓG niΓ)G ) and f is the Fermi-Dirac (7) distribution
48
diative
iscussionrecombination rate [11, 16, 29] is calculated as follows:
riers (e-/h+) energy they can occupy the certain
R = β (
number
npof −
energy
n 2 states [30]. The local density
)
i
spectrum for the different temperature range is shown in the Fig. 2 below and respective (7)
SMC Bulletin Vol. 11 (No. 1) April 2020
Fig. 2: Plot of LDOS spectrum for (17,0) CNTFET for (a) T=100K, (c) T=200K, (e) T=300K and respective Energy
Fig. 2: Plot of LDOS spectrum for (17,0) CNTFET for (a) T=100K, (c) T=200K, (e) T=300K and respective Energy position resolved current
position resolved current diagram is (b) T=100K (d) T=200K and (c) T=300K at VGS=0.475V and VDS=0.475V.
diagram is (b) T=100K (d) T=200K and (c) T=300K at VGS=0.475V and VDS=0.475V.
The bright spikes in Fig. 2(a) represent the energy density spike where total numbers of the charge carriers are
and different oxide thickness variation on the radiative
distributed. It is observed that there is some fluctuation in the It is found out that RRR get enhanced with decrease in
density spikes at low temperature region they are
recombination rate (RRR) and electroluminescence (EL) the thickness of dielectric material used in Fig. 3(c). This is
not very clear for both electron and hole. As the temperature is increased from 100K to 300K it is seen that
intensity is studied and is presented in the Fig.3 below. due to increased carrier’s injection rate (inside the channel
density spikes grows stronger causing to increase the current. This can be explained as follows: total carriers
region) which cause more electron-hole pairs to accumulate
The RRR
distribution cangetbe
enhanced
definedwith increase
by the in the temperature
fermi-dirac distribution function [30]
inside the channel and hence increased number of carriers
in the Fig. 3(a). The involvement of a greater number of the
density of states at higher temperature range made available
µ S / D − VScause
recombination / D RRR to enhance with decrease of the
thickness. It is observed that there is exponential
f S / D =oxide (8)
large number of the electron-hole pairs inside the channel k T
fall in RRR with thickness enhancement of oxide layer
B
region, and recombination of increased number of carriers
At low temperature scale the (fs-fd ) region is very smallused and(inset
hence few
Fig. numbers
3(c)). of densities
It is noticed that there of states are
is exponential
cause the RRR to increase with increase in temperature.
covered inside the channel region. But at higher temperature fall more
in thenumber of density
EL intensity of states are
with increasing thecovered
oxide layerby
Hence an enhancement in RRR is noticed with increase
the (fs-fd) region causing both electron and hole current tothickness increased(inset
[31].Fig.3
It is(d)).
observed
Since thethat
gateboth electron
distance and
increased
in temperature in Fig. 3(a) and it is observed that there is
hole current is very small at 100K in Fig.2 (b),
exponential increase in RRR with increase in temperature
with temperature enhancement
with increasing more
the oxide density
thicknessofwhich
states are
resultscovered
in the
(fs-fdof) Fig.
by(inset window and hence due to more carrier’s excitation
3(a)). Respective EL intensity profile is shown
(the availability
degradation of large
of gate control onnumber
channel ofandstates)
hencethere is
carrier’s
drastic injection rate is affected, hence
increase in the current in Fig. 2(f). Hence increase in current is noticed with increase in temperature. decrease in EL intensity is
in the Fig. 3(b). The EL intensity grows stronger with
Since temperature has vital noticed with increased
impactthickness
on the of the oxideproperties
layer. Effectof of
strengthening of temperature and importance
exponential and it has the
increase significant transport
CNT [32]. Depending on the applied biases and the temperature
temperature variation on function
Fermi-distribution drain current
f of
and thef simulated
can be
in EL intensity is noticed with temperature enhancement s d
changed and hence transport properties can be tuned device
[31,32]. structure
Since gate is shown
has vital in the Fig. 4 in
importance below.
functioning of
(inset of Fig. 3(b)).
the FET devices and is separated by the oxide layer of particular thickness [33]. Based on the different thickness
of oxide used the gate control (on CNT channel) can be altered, carrier injection rate be changed and in this way
carrier transport properties can be changed [33]. Hence effect of the temperature and different oxide thickness49
variation on the radiative recombination rate (RRR) and electroluminescence (EL) intensity is studied and is
SMC Bulletin Vol. 11 (No. 1) April 2020
Plot of
Fig.3:3:Plot
Fig. of(a)(a)Radiative
Radiativerecombination rate versus
recombination rateposition
versus(inset RRR versus
position (insetT), (b) Electroluminescence
RRR intesity versus energy (inset
versus T), (b) Electroluminescence EL
intesity
Intensity
versus versus
energy T) forEL
(inset the different
Intensity value of B, (c)
versus T)Radiative
for the recombination rateof
different value versus position
B, (c) (inset RRR
Radiative versus tox) andrate
recombination (d) Electroluminescence
versus position
intesity
(inset RRR vs energy
versus(inset
t ox) EL
andIntensity versus tox) for (17,0) CNT
(d) Electroluminescence at VGSvs
intesity =0.475V,
energyVDS =0.475V.
(inset EL Intensity versus t ox) for (17,0) CNT at
VGS=0.475V, VDS=0.475V.
It is noticed that there is decrease in the drain current
The RRR get enhanced with increase in the temperature in the Fig.
with increase in the3(a). The involvement
temperature. This is of a greater
because of
number of the density of states at higher temperature range made available large number of
increased number of carrier recombination inside thethe electron-hole
pairs inside the channel region, and recombination of increased channelnumber of carriers
with increase cause the RRR
in temperature. Due totoincreased
increase
with increase in temperature. Hence an enhancement in RRR is noticed with increase in temperature
participation of more number of densities of states more in Fig. 3(a)
and it is observed that there is exponential increase in RRR with increase in temperature (inset
electron hole pairs get injected in the channel and henceof Fig. 3(a)).
Respective EL intensity profile is shown in the Fig. 3(b). The EL intensity grows stronger with strengthening of
increased recombination of more electron-hole pair’s
temperature and exponential increase in EL intensity is noticed with temperature enhancement (inset of Fig.
results in decrease of drain current at higher temperature.
3(b)).
It is found out that RRR get enhanced with decrease in the thickness of dielectric material used in Fig.
4. Conclusion
3(c). This is due to increased carrier’s injection rate (inside the channel region) which cause more electron-hole
pairs to accumulate inside the channel and hence increased number We haveofstudied
carrierstherecombination
light emissioncause properties
RRR of to
enhance with decrease of the oxide thickness. It is observedMOSFET-like
that there iscoaxial gated CNTFET
exponential structure.
fall in RRR withThe NEGF
thickness
method
enhancement of oxide layer used (inset Fig. 3(c)). It is noticed thatis there
used isto exponential
simulate the falldevice
in characteristics
the EL intensity of
(17,0) CNT.
with increasing the oxide layer thickness (inset Fig.3 (d)). Since It was
the gate found increased
distance out that temperature has vital
with increasing the
significance
oxide thickness which results in the degradation of gate control in functioning
on channel and hence of the device injection
carrier’s and thickness
rateofis
affected, hence decrease in EL intensity is noticed with increased
oxide layerthickness of the
used is equally oxide as
important layer.
well. Effect of the
Improvement
temperature variation on drain current of the simulated device structure
in RRR and EL is intensity
shown inisthe Fig. at
noticed 4 below.
higher temperature
Fig. 4: Plot of output-characteristics for (17,0) CNTFET at VGS=0.475V for different temperature range. region whereas downfall in RRR and EL intensity is found
Fig. 4: Plot of output-characteristics for (17,0) CNTFET at VGS=0.475V with reduction of oxide layer thickness. Due to increased
for different temperature range. recombination of carriers large number of carriers gets
It is noticed that there is decrease in the drain current with increase in the temperature. This is because
of increased number of carrier recombination inside the channel with increase in temperature. Due to increased
participation of more number of densities of states more electron hole pairs get injected in the channel and hence
50
ncreased recombination of more electron-hole pair’s results in decrease of drain current at higher temperature.
4. Conclusion
SMC Bulletin Vol. 11 (No. 1) April 2020
annihilated and hence downfall in drain current is found 16. D. L. McGuire, D. L. Pulfrey, Nanotechn. 17 (2006) 5805.
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Gordon, M. Lundstrom, H. Dai, Nano Letters 4 (2004) 447.
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Dr.
Dr. Tapender
Tapender Singh received B.Sc.
Singh received B.Sc. degree
degreeininScience
Sciencefrom fromHimachal
Himachal Pradesh
Pradesh University, Shimla, India, in
2012.
Dr. M.Sc.Shimla,
Tapender
University, degree
Singh in condensed
received
India, matter
B.Sc.
in 2012. Physics
degree
M.Sc. degreein from
Science Central
in condensed from University
Himachal
matter of Himachal
Pradesh
Physics from Pradesh, Dharamshala,
University, Shimla, India, in 2012. Pradesh,
India,
Centralin 2014. He has
University of completed
Himachal hisM.Sc.
Ph.D.degree
degree in condensed
from Central
Dharamshala, matter
India,UniversityPhysicsHefrom
in 2014. of Himachal
has Pradesh, Dharamshala,
Central
completedUniversity
his Ph.D. of Himachal
degree from Pradesh, Dharamshala,
Central University India, in 2014. Pradesh,
of Himachal He has
India, in
completed July 2020
his India, and his
Ph.D. indegree research
fromand interests
Central includes
University nano-scale
of Himachal device simulations.
Pradesh,
Dharamshala, July 2020 his research interests includes nano-scale
Dharamshala,
device simulations.India, in July 2020 and his research interests includes nano-scale
device simulations.
Dr. Padmnabh Rai is a Reader (F) in School of Physical Sciences at UM-DAE
Dr.
Dr. Padmnabh
Padmnabh
Centre Raiisis ain
Rai
for Excellence a Reader
Basic (F)
Reader (F)ininSchool
Sciences, School of of
Physical
Mmbai-400098 Physical Sciences
Sciences
since at UM-DAE
March at UM-DAE
2018. He Centre for Excellence in Basic
Sciences,
received his M. Tech. and Ph. D. degree in Condensed Matter Physics from IIT Delhidegree in Condensed Matter
Centre forMmbai-400098
Excellence in since
Basic March
Sciences,2018. He received
Mmbai-400098 his M.
since Tech.
March and Ph.
2018. D.
He
Physics
received from
in 2004 his
andM.IITIIT Delhi
Tech.
Bombayandin in2004
Ph. and
D. degree
2009, IIT Bombay
in Condensed
respectively. Dr. in 2009,
Matter
Rai respectively.
has Physics
served from
as anIITDr.Delhi
Rai has served as an Assistant
Assistant
Professor
in 2004 and
Professor (UGC) ininDepartment
IIT Bombay
(UGC) in 2009,Physics
Department andand
respectively.
Physics Astronomical
Dr. Rai hasSciences
Astronomical served asat an
Sciences Central University of Himachal Pradesh
atAssistant
Central
(HP) during
Professor
University ofJuly
(UGC) 2014 toPradesh
March 2018.
in Department
Himachal He
Physics
(HP) has
andworked
during as postdoctoral
Astronomical
July 2014 Sciences
to March fellow at National
at Central
2018. He has University Singapore,
Singapore
worked as(December
University of Himachal
postdoctoral 2013fellow
– May at
Pradesh 2014),
(HP) University
during
National July of Bourgogne,
2014
University to March
Singapore, France
2018. He(October
has
Singapore 2010 – September 2013)
worked
and
(December as 2013
Sunkyunkwanpostdoctoral
– University,
May 2014),fellowSouthat Korea
National
University University
of(October
Bourgogne, –Singapore,
2009France August Singapore
2010).
(October He was
2010 – Research and Development
(December
September 2013 –and
2013) May 2014), University
Sunkyunkwan of Bourgogne,
University, South Korea France
(October (October
2009 –2010
August–
manager in Diamond Division of Nozomi Technotron Pvt. Ltd., Singapore (January 2009 – August 2009).
September
2010). He 2013) and Sunkyunkwan
was Research University,
and Development South in
manager Korea (October
Diamond 2009 of
Division – August
Nozomi
Dr. RaiHeis was
2010). experienced
Research in synthesizing carbon based materials Division (single crystal diamond, carbon nanotube and
Technotron Pvt. Ltd., and Development
Singapore manager
(January 2009 in–DiamondAugust 2009). Dr. of Nozomi
Rai is
graphene).
Technotron Carbon-based
experienced Pvt. materials
Ltd., Singapore
in synthesizing are
carbon (January being explored
2009 (single
based materials for
– August photonics
2009).
crystal and
Dr. Rai
diamond, plasmonics
is
carbon applications. Dr. Rai is
also involved
experienced in in teaching
synthesizing physics
carbon courses
based at graduate
materials and
(single
nanotube and graphene). Carbon-based materials are being explored for photonics undergraduate
crystal diamond, level. He
carbon has consulted industries to
develop
nanotube laboratory
and graphene).
and plasmonics for growing
applications. Dr.single
Rai iscrystal
Carbon-based materials diamond
also involved are in for gem
being and
explored
teaching scientific
for
physics coursesapplications.
photonics at He has more than
35
and research
plasmonics
graduate andpublications
applications.
undergraduate in international
Dr.
level.Rai
Heishas peer
also reviewed
involved
consulted journals
in teaching
industries and books
to physics
develop and at
courses
laboratory 02 patents.
graduate andsingle
for growing undergraduate level. He
crystal diamond forhas
gemconsulted industries
and scientific to developHe
applications. laboratory
has more
for growing single crystal diamond for gem and scientific
than 35 research publications in international peer reviewed journals and books applications. He has moreand
than 35 research publications in international peer reviewed journals and books and
02 patents. 51
02 patents.
SMC Bulletin Vol. 11 (No. 1) April 2020
52
SMC Bulletin Vol. 11 (No. 1) April 2020
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