SMC-Bulletin-April 2020

SMC Bulletin Vol. 11 (No.
1) April 2020
ISSN 2394-5087
A Publication of the Society for Materials Chemistry

Figure to be inserted in Red colour box on Front Cover Page
Volume 11 No. 01 April 2020
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
Society for Materials Chemistry

Society for Materials Chemistry was mooted in 2007 with following aims and objectives:
(a) to help the advancement, dissemination and application of the knowledge in the field of materials chemistry,
(b) to promote active interaction among all material scientists, bodies, institutions and industries interested in achieving the advancement,
dissemination and application of the knowledge of materials chemistry,
(c) to disseminate information in the field of materials chemistry by publication of bulletins, reports, newsletters, journals.
(d) to provide a common platform to young researchers and active scientists by arranging seminars, lectures, workshops, conferences on
current research topics in the area of materials chemistry,
(e) to provide financial and other assistance to needy deserving researchers for participation to present their work in symposia, conference, etc.
(f) to provide an incentive by way of cash awards to researchers for best thesis, best paper published in journal/national/international
conferences for the advancement of materials chemistry,
(g) to undertake and execute all other acts as mentioned in the constitution of SMC.
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
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
Prof. Sri Sivakumar
Indian Institute of Technology
Kanpur, 208016
Dr. Deepak Tyagi
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Contact address
C/o Chemistry Division
Bhabha Atomic Research Centre, Trombay, Mumbai, 400 085, India
Tel: +91-22-25592001, E-mail: socmatchem@gmail.com
b
SMC BULLETIN
A Publication of the Society for Materials Chemistry
Volume 11 No. 01 April 2020
Special Issue on
Carbon-Based Materials
i
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
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
Dr. G. Kedarnath Dr. Sandeep Nigam

Chemistry Division Chemistry Division
Bhabha Atomic Research Centre Bhabha Atomic Research Centre
Trombay, Mumbai, 400 085 Trombay, Mumbai, 400 085
e-mail: deepa@barc.gov.in e-mail: snigam@barc.gov.in
Dr. Rajesh V. Pai Dr.Vivek Polshettiwar

Fuel Chemistry Division Department of Chemical Sciences,
Bhabha Atomic Research Centre Tata Institute of Fundamental Research,
Trombay, Mumbai, 400 085 Colaba, Mumbai 400005
e-mail: rajeshvp@barc.gov.in e-mail: vivekpol@tifr.res.in
Published by
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
Guest Editorial
Dr. Padmnabh Rai
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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From the desks of the President and Secretary
Dr. V. K. Jain Dr. R. K. Vatsa

President Hon. Secretary
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.
(Dr. V.K. Jain) (Dr. R.K. Vatsa)

President, SMC Hon. Secretary, SMC
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CONTENTS
Feature Articles Page No.
1. Recent developments of CNT based supercapacitors 1

Sivaram Arepalli
2. Hydrogen storage in carbon nanomaterials 12

Gopal Sanyal and Brahmananda Chakraborty
3. Study of vertical graphene-nanodiamond hybrid structure grown by 33

thermally activated chemical vapor deposition
Dipti Ranjan Mohapatra
4. Effect of nitrogen ion implantation on electron field emission 40

property of nanocrystalline diamond films
Umesh Palnitkar, Huan Niu and I-Nan Lin
5. Temperature influenced electroluminescence in carbon nanotube 47

field effect transistors
Tapender Singh and Padmnabh Rai
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Recent developments of CNT based supercapacitors

Sivaram Arepalli
Department of Materials Science and NanoEngineering, Rice University, 6100 Main Street, Houston, TX 77005
E-mail: Sivaram.arepalli@gmail.com
Abstract
Supercapacitors play an important role in meeting the energy storage requirements for portable as well as
rigid energy storage media. Carbon has been an integral part of the conventional electrodes and carbon
nanostructures provided enhanced surface area and porosity enabling higher capacities and lifetimes. Over
the last decade, considerable research has been done using single wall and multi wall carbon nanotubes
for supercapacitor applications. Recent work reported capacitances of the order of 2000 Farads and more
than a million cycles using symmetric as well as asymmetric design structures. There is an enhanced focus
on using CNT forests and arrays for flexible and micro supercapacitors for possible use in cell phones and
sensors. This review will provide the status and future of the CNT based supercapacitors.
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).
1. Introduction to energy U.S. energy consumption by energy source, 2018

In 2004, Nobel Laureate Rick Smalley [1] talked about
Terawatt Challenge and stated, “Energy is the number one
priority to solve global problems, including clean water
and poverty”. The ever-increasing demand for energy
across the globe has prompted considerable research in
the last few decades to improve energy production, storage
and transmission. Realizing the continual depletion of
fossil fuel energy sources and the detrimental impacts of
these sources to the environment focus has been shifted to
renewable energy sources such as solar and wind energy
in the last two to three decades. Tremendous progress has
been achieved in increasing the efficiency, cost effectiveness
and reliability of solar energy conversion via solar cells
and solar thermal processes. Harnessing wind energy
and wave energy is becoming cost competitive to the Fig. 1: Energy consumption in USA in 2018 (Energy Information
fossil fuels thereby reducing the dependence on these Administration [2])
environmentally harmful sources. These alternative energy
sources are renewable and can be sustainable over a long
period of time with minimal impact to the environment.
Work is in progress to increase the amount of renewable
energy compared to the fossil fuel sources. The Figures 1
and 2 depict the current energy consumption in US [2] in
2018 and projected global energy consumption by 2050.
The global energy consumption is expected to increase
by 50% (600 to 900 Quadrillion BTUs) and the renewals in
2050 will almost double compared to 2018. One Quadrillion
BTU aka Quad is equal to 1×1018 joules and about 293
terawatt-hours or 33 gigawatt-years. According to US
Energy Information Administration (EIA), in 2018, the US Fig. 2: Global energy consumption projected to 2050 (Source: US Energy Information Administration [2])
electricity generation was 4178 TWh (0.5TW-year) net and Fig. 2: Global energy consumption projected to 2050 (Source: US Energy
Information Administration [2])
67 TWh (1.6%) from solar. The global energy production According to the UN World Energy Outlook Report of 2019, “By 2040, low-carbon sources provide
more than half of total electricity generation. Wind and solar PV are the star performers, but hydropower (15%
of total generation in 2040) and nuclear (8%) retain major shares”.
1
2. Energy storage
The energy from the renewable energy sources such as solar and wind vary with time of the day and the season
of the year. It is necessary to store the excess energy during peak energy production cycles and release it during
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.
3.2 Asymmetric capacitor

A hybrid version of EDLC and pseudocapacitor
is an asymmetric capacitor which has EDLC on one
electrode (usually carbon coated) and the other with metal
oxide coated carbon electrode. Recent studies reported
asymmetric capacitors with capacitance of several hundred
Farads and with several hundred cycle lifetime for the
hybrid supercapacitors. A recent paper by Richard Kaner
Fig. TheThe
3: 3:
Fig. Gouy-Chapman-Stern model
Gouy-Chapman-Stern of Supercapacitor
model [5]. [5].
of Supercapacitor
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
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)
carbon filaments have been reported earlier. The reader

is referred to an editorial [9] in the journal “Carbon” for
more details about discussion about who discovered CNTs.
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
Power Density (W/kg)
Fig. 4:Ragone plot illustrating the performances of specific power vs specific energy for different electrical energy-
vast number of papers and books about the identifying
Fig. 4: Ragone
storage technologies. plot
Times shown illustrating
in the the performances
plot are the discharge of specific
time, obtained by dividing the energypower vsthe power
density by the chirality, de-bundling and separating the individual
specific energy for different electrical energy-storage technologies. Times
density [7].
CNTs by tube type (Semiconducting or metallic). Recent
showncapacitors
Hybrid in the plothaveare
comethetodischarge
be identifiedtime, obtained
as devices by dividing
in which thestores
one electrode energy charge by a
battery-type Faradaic process while the other electrode stores charge based on a capacitive mechanism.research A was focused on growing CNTs of specific
density by of the power densityis shown[7].
general classification supercapacitors in Fig. 5.
chirality for applications such as nanosensors. The reader
media. is referred to a recent report from a biennial conference
on CNT nucleation and growth [10] for the status of these
Hybrid capacitors have come to be identified as devices
issues. In addition, this conference series has identified the
inFig.which one electrode stores charge by a battery-type of specific appropriate
4:Ragone plot illustrating the performances development
power vs specific trend
energy for for SWCNT
different growth
electrical for a
energy-
Faradaic process while the other
shown electrode
in the plot storesare thechargedischargevariety
storage technologies. Times of applications
time, obtained (Fig.
by dividing the7).
energy density by the power
based
densityon[7].a capacitive mechanism. A general classification
of supercapacitors is shown in Fig. 5. The CNTs have unique mechanical, thermal, electrical
and optical properties in addition to morphology giving
Hybrid capacitors have come to be identified as devices in which one electrode stores charge by a
4. Carbon nanotubes rise to large surface area (hundreds of cm 2/g) and
battery-type Faradaic
Fig. 5: Classification process
of supercapacitors whileelectrode
and possible thematerials
other[7]. electrode nanometer stores charge based on a capacitive mechanism.
size porosity. The following table provides a
A
Carbon nanotubes are 1-D nanostructures of carbon
general classification of supercapacitors is shown in Fig. 5.
4. Carbon nanotubes
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
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 carbon filaments have been reported earlier. The reader is referred to an editorial [9] in the journal
“Carbon” for more details about discussion about who discovered CNTs.
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
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
Table 1 The major properties of CNTs [11]
S. No. Property Computational calculations Experimental measurements

1 Young’s modulus [TPa] 1.5 to 5.0 2.8 to 3.6
2 Tensile strength [GPa] 300 150
3 Electrical conductivity [S/m] 1 × 107 6.6 × 103
4 Thermal conductivity [W/m K] 80–9500 3500
5 Charge mobility [cm2/V-s] 1.2 × 105 1 × 103
6 Thermal stability in air [ °C] 750 420
7 Surface area [m2/g] 50–1315 619.1
Fig. 7: Structure−property relationship diagram showing the application space of SWCNTs with respect to tube
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
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.
Fig. 9:Electrochemical properties of the CNTs/GNFs- and CNTs-based supercapacitors in 6 mol/LFig.

KOH electrolyte. CV characterizations of the Co9S8@CNT/CNF//CNT/CNF ASC. (a) Schematic illustration of the ASC
10:Electrochemical
curves of (a) CNT/GNFs and (b) CNTs under various scan rates. (c) The specific capacitance of CNTs/GNFs
device. (b) CVand CNTs
calculated at various 9: Electrochemical
Fig.current propertiesofofCNTs/GNFs
densities. (d) EIS measurements the CNTs/GNFs-
and CNTs basedand
EDL CNTs- Fig.
supercapacitors
specific
10:
curves
Electrochemical characterizations of the Co9Sdevice @CNT/CNF//
of the ASC at various scan rates from 5 to 200 mV/s measured between 0 and 1.6 V. (c) Plot of the
[17].
capacitance as a function of scan rates. (d) Cycling performance of the ASC 8 at a current density of 5 A/g
based supercapacitors in 6 mol/L KOH electrolyte. CV curves [18]. of (a) CNT/CNF ASC. (a) Schematic illustration of the ASC device. (b) CV
Zhang CNT/GNFs
and co-workersand [18](b)developed an asymmetric
CNTs under various supercapacitor (ASC)
scan rates. (c) The with 3D cobalt
specific sulfide
curves of the ASC at various scan rates from 5 to 200 mV/s measured
ncapsulated carbon nanotube/carbon nanofiber (Co9S8@CNT/CNF) composite, which showed a capacitance of
capacitance
1580 F/g at a current density of
of 1CNTs/GNFs
A/g. They reportanda maximum
CNTs calculated at various
energy density current
of 58 Wh/kg between
at a power density 0 and 1.6 V. (c) Plot of the specific capacitance as a function
f 1000W/kg and densities. (d)10,000
even after EIS measurements
cycles, the ASCofstill
CNTs/GNFs
retains 93%and CNTs
of the based
initial EDL at ofa current
capacitance scan rates. (d) Cycling performance of the ASC device at a current
ensity of 5 A/g. They claim that the aligned CNT/CNF nanochannels increase the ion transfer speed and
supercapacitors [17]. density of 5 A/g [18].
horten 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–
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 fabrication methods
Specific Capacitance (mF/cm2)

used to study SCs is shown in Fig.
11.
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 Area strain (%)
fiber. The bi-scrolled MnO2/CNT
fiber was able to achieve anFig. 13: Performance Performance
areal Fig. 13:reported
comparison comparison
of the stretchable, of the stretchable,
all-solid-state, all-solid-state,supercapacitors
crumpled-CNT-forest crumpled-CNT-forest
with other
supercapacitors with
CNT supercapacitors other CNT
in literature. Thesupercapacitors
capacitances ofreported
this workinare
literature.
measuredThe
by capacitances of this
charge–discharge atwork
a rate of
specific capacitance of 889 mF/
50 mV s−1 [21].
are measured by charge–discharge at a rate of 50 mV s−1 [21].
cm2 (or 155 F/cm3) and possessed
an energy density of 35.8 μWh/Another recent article [16] reports the stability of composite electrodes for bending and stretching for
cm2 (or 5.41 mWh/cm3). hundreds of cycles. The results (Fig. 14) show excellent resiliency and paves the way for future wearable
electronic applications.
Jeffrey Glass and co-workers
[21] reported highly stretchable
supercapacitors based on crumpled
CNT-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–discharge, and specific
capacitance was observed even
when the electrodes are stretched to
a uniaxial strain of 300% or biaxial
strain of 300% × 300%. Moreover,
the electrode performance can
be maintained over thousands of
stretching–relaxing cycles. The
stretchable SCs that are assembled
by stacking two crumpled CNT-
Fig. 14: Capacitance retentions and CV curves of the PANI/CNTs/G/PETC electrode under different (a and its inset)
forest electrodes and separated by Fig. 14: Capacitance
bending retentions
angles and (b and its inset) and CVtimes.
bending curves(c) of
CVthe PANI/CNTs/G/PETC
curves electrode
of the PANI/CNTs/G/PETC under
electrode different
under (a
the twisting
a thin layer of PVA–KCl gel as the and its inset)
condition. bending
(d and angles
its inset) and (b and
Capacitance its inset)
retentions andbending times. (c) CV
their corresponding CV curves
curves ofof the
the PANI/CNTs/G/PETC
PANI/CNTs/G/
electrolyte and separator are able PETC electrode under the twisting condition. (d and its inset) Capacitance retentions and their
electrode under various twisting times [16].
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,
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
-
electrolyte, of EMI + and

positionsrespectively BF4- ions of the RTIL electrolyte, respectively [22].
[22].
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
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
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Ghosh, V.K.T.Kurosawatsu,
Le, J. J. Bae and Y. H. T.
M. Uota, Lee, Scientific M.
Karashima, Reports 3 (2013) 2939.
24. Otsubo,
R. Burt,C.G.Honda
Birkettandand Y.
X. M.
S. Zhao,
Sung, Phys.
Thin Chem. Chem.515
Solid Films Phys.25. Z. Bo, C. Li, H. Yang, K. Ostrikov, J. Yan and K. Cen, Nano-
16 (2014) 6519.
Micro Lett. 10 (33) (2018); https://doi.org/10.1007/s40820-
25. (2017)
Z. Bo, C. Li, H. Yang, K. Ostrikov, J. Yan and K. Cen, Nano-Micro Lett. 10 (33) (2018);
4234.
018-0188-2.
14. Z.https://doi.org/10.1007/s40820-018-0188-2.
Li, K. Xu and Y. Pan, Nanotechnology Review 8 (2019) 35.
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
Hydrogen storage in carbon nanomaterials

Gopal Sanyal1 and Brahmananda Chakraborty2,3*
1
Mechanical Metallurgy Divison, High Pressure &Synchroton Radiation Physics Division, Bhabha Atomic Research Centre,
2
Trombay, Mumbai-400085, India

3
Homi Bhabha National Institute, Mumbai-400085, India
*Corresponding author Email: brahma@barc.gov.in
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
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
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
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)
2.5.2 Adsorption energy

where, V̂H , V̂xc and V̂ext are the Hartree, Exhange-Correlation and external potentials respectively.
where, V̂ , V̂xc and V̂ext are the Hartree, Exchange- For practical H2 The
storage
From above, itHis clear that the only unknown term is the exchange correlation functional. abovedevice, H2 adsorption energy
equation
Correlation and external potentials respectively.
can be solved by a self-consistent method. Hence, the accuracy ofmust DFTfall
datawithin
dependsa on
window. DoE has
how superior the prescribed that the
exchange correlation
From above, it is functional
clear that can be formulated.
the only unknownLDA is binding
term (Local density energy of H2 must
approximation) [37]fall
andwithin
GGA the range 0.2-0.7 eV
(Generalized gradient approximation) [38] are two widely
the exchange correlation functional. The above equation used exchange-correlation
for practical functional.
implementation of H as fuel. The adsorption
2
can
2.5 be solved from
Properties by a theoretical
self-consistent method. Hence, the energy of H 2 on the host can be computed from the
simulations
accuracy of DFT data depends on
Theoretical simulations can provide very clear howand superior pictureexpression
beautifulthe concerning adsorption energy, adsorption
exchange correlation
configuration, functional
orbital interactions andcan be formulated.
charge transfer whichLDA
are difficult toEget from experiments.
ads = E Host + H 2 − E Host − E H 2 (4)
(Local density approximation) [37] and GGA (Generalized
2.5.1
gradient Adsorption site
approximation) [38] are two widely used W h e r e E Host + H 2 i s t h e e n e r g y o f t h e h o s t
It is vital for H2 storage simulations to find the adsorption configuration
exchange-correlation
with minimum energy.
(nanostructure+dopant) plus H, E
Geometry is the energy of
optimization might takefunctional.
longer for presence of weak Van der waal’s forces. Additional consideration of2 spinHost
the host and E H 2 is the energy of an isolated H2molecule.
polarization is necessary for systems containing transition metal with magnetic signature. Accuracy of
2.5 Properties
configuration fromalso
depends theoretical simulations
on setting parameters such as energy cut As off per convention,
for the plane wave negative
as well as value
K-pointsof adsorption energy
for sampling the Brilloiun zone. Hence, convergence needs to be tested with respect to energy cut off for the favorable. All three
indicates that binding is energetically
Theoretical simulations can provide very clear and
plane wave as well as number of K-points. The distance of the H2 molecule energies within the
thenearest
aboveatomequation should
of the host or be computed with
beautiful
the dopantpicture
mightconcerning
impart ideaadsorption
regarding energy, adsorption
bond strength. Lower distance (bond length) signifies stronger
same simulation condition as the computed energy may
configuration, orbital interactions
adsorption. To investigate and charge
adsorption properties transfer
of hydrogen molecules on metal-doped zeolite template carbon
vary with setting parameters. Adsorption energy is very
which
(ZTC),are difficult
more than 10 to adsorption
get from experiments.
configurations have been simulated by Han et al. [39]. It is found that H2
molecules tend to symmetrically locate around Sc, Ti or V atoms doped muchon sensitive
C39H15tosurface
choice[40].
of basis set. The adsorption energy
Therefore,
while building the initial model of H2 adsorption configuration, the may also be are
H2 molecules different forloaded
uniformly different adsorption sites. Ganji
around
2.5.1 Adsorption site
the doped metal atoms in almost symmetric positions, with a gradually et al. [41]
raised demonstrated
loading number of Hthat adsorption energy values
2 molecules.
It is vital for
First-principles H 2 storage
geometric simulations
optimization to find theperformed
has been individually and bondfor each additional
lengths obtainedH2 molecule to to choice of basis
are sensitive
obtain all the
adsorption relaxed and stable
configuration adsorption structures.
with minimum Representative adsorption configurations after geometry
energy. Geometry sets, e.g. SVP, TZVP or TZVPP. The results generated
optimization ofmight
optimization three and six H
take 2 molecules
longer at A1-A10 sites
for presence of Sc-C39H15 are shown with the top (left) and side
of weak
(right) views in Fig. 2. through dispersion corrected approaches display excellent
Van der waal’s forces. Additional consideration of spin agreement between the theory and experiment, especially
15
2.5.3 Charge transfer and orbital

interactions
The amount of charge getting
transferred between the bonded species
can be quantified from simulation data.
From charge transfer data, idea regarding
bonding mechanism can be obtained. The
bonding between H and host material
is strong for the chemisorption, weak
for physisorption and intermediate for
the Kubas type of interaction. Higher
charge transfer indicates stronger
bonding. For pure CNMs, the adsorption
mode is physisorption and charge
transfer is negligible. For chemisorption,
the H 2 atoms get dissociated charge
transfer is huge. Both physisorption and
chemisorption are thus not suitable for
practical implementation of H2 storage.
For metal doped carbon nanomaterials,
there is charge transfer from metal’s d
orbital to H’s s orbital followed by back
donation through Kubas interaction. In
this case the binding energy comes in
Fig.Fig. 2: Adsorption
2: Adsorption configurations
configurations of three
of three (above (above
panels) and panels)
six (belowand six (below
panels) panels)
H 2 molecules H molecules
on A1, A3, A4, A10 sites
respectively in Sc-doped-ZTC (Sc-C39H15). The top and side views are respectively shown by the left and2 right parts in each the range 0.2-0.7 eV as prescribed by
on A1, A3, A4,
theA10
grey,sites
whiterespectively inidentify
Sc-doped-ZTC (Sc-C39H15). Theatom.
top and side
Hanviews
schematic
[39],are
unit, and and violet balls carbon, hydrogen and scandium (From
DoE and is most suitable for practical
et al. 2019
Withrespectively
permission.) shown by the left and right parts in each schematic unit, and the grey, white
and violet balls identify carbon, hydrogen and scandium atom. (From Han et al. 2019 [39], implementation of H2 storage at ambient
2.5.2 Adsorption energy condition. Hence, type of interaction
For With permission.)
practical H2 storage device, H2 adsorption energy must fall within a window. DoE has prescribed that the
binding energy of H2 must fall within the range 0.2-0.7 eV for practical implementation of H2 as fuel. The operating can be determined from charge
for the
adsorption large
energy of Hbasis
2 on theset.
hostMeanwhile,
can be computedthe frommoderate
the expressionbasis set transfer data. To find the quantum of charge transfer, one
= E Host+ Hgives
Eads(TZVP) 2
− EHosta −reasonably
2
EH good result compromising need to take care (4) regarding number of valence electrons
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
2.8 Theoretical studies aiming hydrogen storage

in pure CNMs
Most theoretical research experience regarding H2
storage in pure CNM encompasses CNT, fullerene,
graphene, graphyne, pentagraphene etc. as the storage
2.6 Importance of dispersion corrections for hydrogen storage
material.
As H2 adsorption A few
involves weak notable
Van der theoretical
Waals interactions, observations
one must are corrections in
include dispersion
discussed
simulations as the below.
standard DFT with GGA exchange correlation functional can’t handle ‘long term electron
correlation’ effects. The dispersion correction increases the binding energy of H2 molecules slightly. There exist
Lee et al. the
various schemes for incorporating [51] demonstrated
dispersion corrections inthrough
DFT such asDFT calculation
Grimme’s DFT-D2 [47], Grimme’s
DFT-D3, vdW –DF [48-50], optPBE-vdW etc.The binding energy of H2 molecules will differ little bit for
that H
various dispersion schemes. atoms can be stored predominantly through the
tube wall by annihilating the C-C midbond. They also
2.7 Sensitivity of theoretical data
found that up to certain H content, the nanotube’s wall
The data obtained from DFT simulations depend on the exchange correlation functional, simulations parameters,
is stable.
dispersion correction schemesByandreviewing Lee et al.’s
simulation software. work,
So, one Froudakis
need to [52] choice of
be careful regarding
simulation parameters. As the binding
commented energy is computed
that maximum from difference
H2 storage of energy,
capacity simulations should be
is mainly
considered with identical setting parameters otherwise it may give erroneous result. Energy cut-off and k-point
governed
grid are important bybe the
parameters to taken steric interaction
care of for accuracy. among H2 molecules
and between H and the tube wall. Consequently, sorption
2
2.8 Theoretical studies aiming hydrogen storage in pure CNMs
Most theoreticalcapacity increases
research experience linearly
regarding withintube
H2 storage diameter
pure CNM (Fig.CNT,
encompasses 4). But,
fullerene, graphene,
too much
graphyne, pentagraphene etc. H storage
as the
2
storage will cause
material. A fewlarge
notablerepulsion energies
theoretical observations are discussed
below.
and ultimately break down the tube wall.
Lee et al. [51] demonstrated through DFT calculation that H atoms can be stored predominantly through the
tube wall by annihilating the C-C midbond. They also found that up to certain H content, the nanotube’s wall is
stable. By reviewing Using al.’sfirst-principles DFT calculations, Yoon et al.
of charge density and charge density difference for (a) Ni and (b) Al adatoms adsorbedLee onetgraphene. (From [52] commented that maximum H2 storage capacity is mainly
work, Froudakis
Fig. 3: Isosurfaces of charge density and charge density difference for
governed by the [53] explore
steric interactionsystematically
among H2 moleculesthe and
capacity
betweenofH2charged
and the tubecarbon
wall. Consequently,
[46], with permission.)
(a) Ni and (b) Al adatoms adsorbed on graphene. (From Wong, J., et al.
sorption capacity increases linearly
fullerenes Cn (20with ≤n tube
≤82)diameter (Fig. 4). But,
as H2 storage too much
media. 2 storage will cause large
TheHtheorized
2014 [46], with permission.) repulsion energies and ultimately break down the tube wall.
energy as they have greater charge which can interact with

hydrogen molecules.
2.6 Importance of dispersion corrections for

hydrogen storage
As H 2 adsorption involves weak Van der Waals
interactions, one must include dispersion corrections in
simulations as the standard DFT with GGA exchange
correlation functional can’t handle ‘long term electron
correlation’ effects. The dispersion correction increases the
binding energy of H2 molecules slightly. There exist various
schemes for incorporating the dispersion corrections in
DFT such as Grimme’s DFT-D2 [47], Grimme’s DFT-D3,
vdW –DF [48-50], optPBE-vdW etc.The binding energy
of H2 molecules will differ little bit for various dispersion
schemes.
2.7 Sensitivity of theoretical data

The data obtained from DFT simulations depend on the
exchange correlation functional, simulations parameters,
Fig. 4: Chemical adsorption of H in SWNTs: (a) the (5, 5) SWNT before the storage; (b) hydrogens adsorbed on the
dispersion correction schemes and simulation software. Fig.
outside of the tube 4:(c)Chemical
wall; adsorption
adsorption of of Hatom
a single hydrogen in on
SWNTs:
the inside (a) the
of the (5,(d)5)theSWNT
wall; initial geometry; (e) the
So, one need to be careful regarding choice of simulation before the storage; (b) hydrogens adsorbed on the outside of the tube
fully relaxed version of geometry (d); (f ) molecular hydrogen inside the (5, 5) SWNT; (g) H2 inside the (10, 0) SWNT with
an allocation of two H per C atom and with 2.4 H per C atom (f ). Bond lengths are in Å. (From Froudakis, 2002 [52],
parameters. As the binding energy is computedwithfrom wall; (c) adsorption of a single hydrogen atom on the inside of the wall;
permission.)
difference of energy, simulations should be considered (d) the initial geometry; (e) the fully relaxed version of geometry (d);
with identical setting parameters otherwise it may give (f ) molecular hydrogen inside the (5, 5) SWNT; (g) H2 inside the (10,
erroneous result. Energy cut-off and k-point grid are 0) SWNT with an allocation of two H per C atom and with 2.4 H per
C atom (f ). Bond lengths are in Å. (From Froudakis, 2002 [52], with
important parameters to be taken care of for accuracy.
permission.)
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
(a) (a)
(b) (b)
Fig. 6: (a) Simulations of hydrogen of

Fig. 6: (a) Simulations adsorption.
hydrogen Top: potential
adsorption. Top:energy changes
potential duechanges
energy to chemisorption. Centre: number
due to chemisorption. of number of
Centre:
chemisorbed H
Fig.chemi- atoms.
6: (a) Simulations Red: protocol
sorbed Hof hydrogen
atoms. Red: (i), black:
adsorption. protocol
Top: potential
protocol (ii).
energy
(i), black: Bottom:
changes due
protocol temperature
(ii).toBottom: variation
chemisorption. during
Centre: number
temperature the simulations
of chemi-
variation sorbedthe
during of
H atoms.
simulations of
protocol Red:
(i). protocol
Green dots
protocol (i),(i). indicate
black: the
protocol
Green dots potential
(ii).indicate energy
Bottom: temperature and
the potential adsorbed
variation
energy during H for full
andtheadsorbed loading.
simulationsHoffor Snapshots
protocol
full (i). from
Green dots
loading. the simulations
indicate the
Snapshots potential
from are
energy
the simulations are
reported, and
corresponding
reported, to the
adsorbed H corresponding
for full partially
loading. Snapshots loaded
to the (pink
from the
partially background)
simulations
loaded and corresponding
are reported,
(pink fully loaded
background) (green
and tofully back-loaded
the partially
loaded ground)
(green (pink configurations.
background)
background)andconfigurations.
fully
and (b) Simulations
loaded
and(green of
(b) back- hydrogen
Simulations release.
ground) configurations.
of hydrogen Theand temperature
(b) Simulations
release. (bottom), potential
of hydrogen
The temperature release.
(bottom), energy
The (top),energy
temperature
potential and number
(bottom), of energy
potential
(top), and released
number(top),H atoms
and
of number H atoms
released
of released
are reported. H atoms
Black: are reported.
inversion Black:
phase, inversion
temperaturephase, temperature
not not controlled.
controlled. Red: Red: thermalization
thermalization
are reported. Black: inversion phase, temperature not controlled. Red: thermalization with recovery to starting with recovery
with to
recovery starting
to configuration.
starting
Green:
configuration. thermalization keeping
Green:thethermalization
Green: thermalization
configuration. curvature
keeping inverted. The corresponding
the keeping
curvature theinverted.two final
curvature The configurations
Thearecorresponding
corresponding
inverted. reported in red and
two final greenfinal
boxes.configurations
configurations
two Snapshots
are are
reported of
inthe
redstarting
and and half-period
green boxes. conformations
Snapshots of are
thealso reported.and
starting (From Tozzini et al.,
half-period 2011 [54], withare
conformations permission.)
reported in red and green boxes. Snapshots of the starting and half-period conformations are also reported. (From Tozzinialso reported. (From Tozzini
et al., 2011 [54],
et al.,with
2011 permission.)
Besides the above, a number of storage mechanisms uniform binding energy of ~0.3 eV/H2 and an average
have been hypothesized by theorist over the globe. A desorption temperature of around 400 K, leading to 10 wt%
2.9 Theoretical studies aiming
2.9compendium
Theoretical hydrogen storage in functionalized CNMs
brief of studies
theoreticalaiming hydrogen
research storage of
for assessing inHfunctionalized
storage. They also CNMsidentified two possible adsorption
Efforts in assessing
Efforts inpotential
assessing ofpotential
functionalized
of carbon Nanomaterials
functionalized carbon
2
for H2 storage
Nanomaterials for are storage
H2 quite vast,
are although
quiteand notalthough not
vast,
H 2 storage by various CNMs has been presented in sites for Yttrium on graphyne: one hexagonal another
entirely exhaustive.
entirely
Table
The results
exhaustive.
2 [55-61]. However,The
are quite promising
results of
validation aresuch for room
quitetheoretical temperature
promising triangular, H
for room temperature
2 storage
capable
by CNMs.
H2 storage9 by
of adjoining
A few
andCNMs.
important
A few important
5 H 2 molecules
such works are
hypothesesdiscussed
such works below.
are discussed
is often not feasible below.
for lack of comparable respectively (Fig. 7). Authors have checked the stability
Gangan etscenario.
pragmatic al. [63]Itpredicted
Gangan is al. [63]bypredicted
et noteworthy DFT simulations
to mention that aofYtrrium
specially
by DFT simulations thatatom
the system a at attached
room
Ytrrium onattached
temperature
atom graphyne onsurface
by ab-initio cansurface can
Molccular
graphyne
adsorb upanto a maximum
interesting
adsorb up to a of 9 molecular
conjectural
maximum of 9 hydrogens
observation reported (H
molecular by2),
GaowithDynamics
hydrogens a(Huniform binding energy
simulations. of ~0.3they
Interestingly, eV/H 2 and
have an
computed
2), with a uniform binding energy of ~0.3 eV/H2 and an
average et
desorption
al. temperature
[62] about
average of around
ultrahightemperature
desorption 400
hydrogen storage K, leading
capacity
of around to
400ofK, the10 wt%
diffusion
leading of
to 10H
energystorage.
2 wt% barrier They
of Hfor also identified two
the clustering of Y atoms. It
2 storage. They also identified two
possible holey
adsorption
graphynesites for
where Yttrium
the C–C on
2D graphyne:
network is one hexagonal
alternately was and
foundanother
that
possible adsorption sites for Yttrium on graphyne: one hexagonal and another triangular, triangular,
there exist capable
substantial of adjoining
energy of9adjoining 9
barrier which
capable
and 5 H2connected
molecules respectively
between benzene(Fig.rings 7).
andAuthors
sp bondshaveleadingchecked the
to prevents stability
movement of the system
of metal
and 5 H2 molecules respectively (Fig. 7). Authors have checked the stability of the system at room temperature at
atom. room temperature
by ab-initio Molccular
a more
by ab-initio Dynamics
Molccular simulations.
open structure. Interestingly,
Dynamics simulations. they have
Interestingly, computed
they have
Chakraborty et the diffusion
alcomputed
[64] have the energy
also barrier
diffusion
reported for barrier for
energy
hydrogen
the clustering
the of Y atoms.
clusteringstudiesIt was
of Y atoms. found that
Ithydrogenthere exist
was foundstorage substantial
storage
that there exist energy barrier
capability
substantial which prevents
of Y barrier
energy doped single movement
which walled of
preventscarbon
movement of
2.9 Theoretical
metal atom.metal atom. aiming
nanotubes. They presented the structural stability, H2
in functionalized CNMs
adsorption capability and H 2 desorption kinetics of
Efforts in assessing potential of functionalized carbon Y-decorated single walled carbon nanotube (Fig. 8) through
Nanomaterials for H2 storage are quite vast, although not first principle simulations. It was found that A single Y
entirely exhaustive. The results are quite promising for atom attached on SWCNT is shown to physisorb up to
room temperature H2 storage by CNMs. A few important six H molecules. The interaction of H with metal atom is
2 2
such works are discussed below. through Kubas type of interactions.
Gangan et al. [63] predicted by DFT simulations that Zirconium is the next to Yttrium in the periodic table.
a Ytrrium atom attached on graphyne surface can adsorb Yadav et al. [65] explored the hydrogen storage capability
up to a maximum of 9 molecular hydrogens (H2), with a of Zr doped graphene. The advantage of graphene is that
19
(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.
Chakraborty et al [64] have also reported hydrogen

systemstorage
throughcapability of Ybedoped
doping may single way
an effective walled carbon
to bring
nanotubes. They presented the structural stability, H2 Tadsorption
D
capability and
in to the desired window. 2H desorption kinetics of Y-
decorated single walled carbon nanotube (Fig. 8) through first principle simulations. It was found that A single
Y atom attached on SWCNT is shown to physisorb up to Apart six H2from above, there are many more theoretical
molecules. The interaction of H2 with metal
studies reported available for predicting H2 storage of
atom is through Kubas type of interactions.
CNMs in presence of heteroatoms. A brief account of a
few such works is summarized in Table 3 [62, 66-75]. To
fortify with a few recent interesting studies, Deniz et al.
[76] showed through grand canonical Monte Carlo (GCMC)
simulations that the total gravimetric adsorption capacity
of Li-doped fullerene pillared graphene nanocomposites
(Li-FPGNs) with doping ratio of Li:C=15:100 could reach
Fig. 8: (a) Final relaxed structure of SWCNT+Y+6H complex, (b) Isosurface for charge density difference between 9.1 wt% at 77 K and 1 bar, which corresponds to about
(a) structure
Final relaxed structure of [64],
SWCNT+Y+6H for charge complex, (b) between
2
Fig. 8: (a)Fig.
Final8:relaxed of SWCNT+Y+6H complex, (b) Isosurface density difference
two times rise in the hydrogen storage performance of
SWCNT+Y+6H system;
2 iso-value −0.5e. (From Chakraborty et2 al., 2012 with permission.)
SWCNT+Y+6H2 system; iso-value −0.5e. (From Chakraborty et al., 2012 [64], with permission.) 2
Isosurface forYttrium
charge in thedensity difference between SWCNT+Y+6H
Zirconium is the next to periodic table. Yadav et al. [65] explored the hydrogen storage
Zirconium is the next to Yttrium in the periodic table. Yadav et al. [65] explored the hydrogen storage
2 pristine FPGNs.
capability of Zr system; iso-value
doped graphene. −0.5e.
The advantage of(From
grapheneChakraborty et2Dal.,
is that being 2D layer metal2012
can be[64],
loaded with
on both
capability
the surfaces. of Zrfound
It was dopedthat
graphene.
single ZrThecanadvantage
store 9H2 of grapheneleading
molecules is that to
being layerHmetal
a theoretical can be loaded on both
2 uptake of 11 wt%,
muchthe surfaces.
higher permission.)
than ItDoE’s
was found that single
requirement of 6.5Zrwt%
can (Fig.
store 9)
9H[65].
2 molecules leading tothat
It was observed a theoretical
graphene+Zr H2 is
uptake of 11 wt%,
magnetic
much
whereas its higher
magneticthan DoE’sreduces
moment requirement of 6.5 wt%
after adsorption of (Fig. 9) [65].
successive H2 It was observed
molecules. that graphene+Zr
Interestingly, they found isthat 2.10 Challenges and issues in theoretical studies
magnetic
whereasenergy
the binding its magnetic
as wellmoment
desorptionreduces after adsorption
temperature of successive
of individual H2 dependsH2 molecules. Interestingly,
on the magnetic momentthey found that
of the
the binding
system. being
Authors energy
[65] have2D layer
as well metal
desorption
presented can
an temperature be loaded
of individual
empirical relation on both
betweenH2magnetic
depends on the surfaces.
the magnetic
moment and desorptionIt
moment of the One of the significant issues for H2 storage for metal-
temperature
temperature
molecule
was
system. ofAuthors
H found
[65]system.
2 for this
of leading
is higher, H2 for this
that
have For
system.
to higher
asingle
presented
system Zr
anwith
For a system
desorption
acan
largestore
empirical
with a (T
temperature
relation
magnetic
large
9H molecules
between
moment,
magnetic
magnetic
2 moment,
leading
the charge moment
transfer
the charge
toand todesorption
the
transfer
H2
doped carbon nanomaterial is the metal-metal cluster.
to the H2
D). Controlling the magnetic character of the
system throughisa
molecule theoretical
higher,
doping mayleading toH uptake
higher
be an effective desorption
way of
to bring T11
D inwt%,
temperature (Tmuch higher
D). Controlling
to the desired window. the than
magnetic DoE’s
character ofFromthe computation of metals’ diffusion energy barrier,
2
system through doping may be an effective way to bring TD in to the desired window.
requirement of 6.5 wt% (Fig. 9) [65]. It was observed that one can get idea on possible metal loading pattern in
graphene+Zr is magnetic whereas its magnetic moment order to avoid metal-metal clustering. Secondly, oxygen
reduces after adsorption of successive H 2 molecules. interference is a great practical problem and considering
Interestingly, they found that the binding energy as well that within the model is a difficult challenge [77]. Hence,
desorption temperature of individual H2 depends on there are issues and challenges for predicting H2 storage
the magnetic moment of the system. Authors [65] have capacity in terms of wt% from theoretical simulations.
presented an empirical relation between magnetic moment Simulation results are sensitive to the replication methods
andFig.
desorption temperature
8: (a) Final relaxed of H2 for of
structure thisSWCNT+Y+6H
system. For a2 complex,
and setting(b) parameters.
Isosurface forForcharge
example, as mentioned
density differenceearlier,
between
system with a large2 magnetic
SWCNT+Y+6H moment,
system; iso-value the charge
−0.5e. (Fromtransfer
ChakrabortyLDA exchange
et al., correlation
2012 [64], [46] overbinds the H2 molecules
with permission.)
to the H2 molecule is higher, leading to higher desorption whereas GGA exchange correlation [47] underbinds the H2
temperatureZirconium
(TD). Controlling
is the the magnetic
next character
to Yttrium in theofperiodic
the molecules.
table. Yadav et al.
So, one need[65]
to explored theregarding
be cautious hydrogenchoice
storage
capability of Zr doped graphene. The advantage of graphene is that being 2D layer metal can be loaded on both
20 the surfaces. It was found that single Zr can store 9H2 molecules leading to a theoretical H2 uptake of 11 wt%,
much higher than DoE’s requirement of 6.5 wt% (Fig. 9) [65]. It was observed that graphene+Zr is magnetic
whereas its magnetic moment reduces after adsorption of successive H2 molecules. Interestingly, they found that
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]
Ambient Ambient Ti 7.5 [67]
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
in pure or decorated form,

its characterization and
finally hydrogen adsorption
and measurement of stored
hydrogen. Synthesis of graphene
involves exfoliation of graphite
through either mechanical or
chemical route. CNT is generally
synthesized adopting chemical
vapour deposition (CVD)
technique. Functionalization of
CNM involves a wet chemical
method where first carbon
arms are activated by reacting
with oxidizing chemicals. The
activated sites act as receptor
of heteroatoms. In the next
step, transition metal (TM)
10: TEM
Fig.TEM
Fig. 10: imageimage
of (a)ofpure
(a) pure graphene,
graphene, (b) graphene
(b) graphene functionalized
functionalized withwith
HNOHNO , (c) graphene
3, (c) graphene decorated
decorated with Pt and
(d) graphene
3 atoms are conjugated with the
with Ptdecorated with Pd (From
and (d) graphene Huang
decorated et al.,
with 2011 [88],
Pd (From Withetpermission.)
Huang al., 2011 [88], With permission.)
active sites of the oxygenated
2.10 Challenges and issues in theoretical studies
One of the significant issues for H2 storage for metal-doped carbon nanomaterial is the metal-metal cluster.
From computation of metals’ diffusion energy barrier, one can get idea on possible metal loading pattern in
order to avoid metal-metal clustering. Secondly, oxygen interference is a great practical problem and
considering that within the model is a difficult challenge [77]. Hence, there are issues and challenges for
predicting H2 storage capacity in terms of wt% from theoretical simulations. Simulation results are sensitive to
the replication methods and setting parameters. For example, as mentioned earlier, LDA exchange correlation
[46] overbinds the H2 molecules whereas GGA exchange correlation [47] underbinds the H2 molecules. So, one
need to be cautious regarding choice of the simulation methods and the resulting prediction from simulation
details. For adsorption of H2 molecules on carbon nanostructures, weak Van der Waals interactions are there.
So, one should carefully take into account of those interactions while computing binding energy of H2 molecules
on carbonaceous substance.
(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.)
3.of the simulation

Hydrogen methods
storage and thenanomaterials:
in carbon resulting prediction CNM using
experimental suitable chemical, composing of the TM.
studies
Experimental
from simulation hydrogen storage
details. For studies
adsorption of involve preparation
H2 molecules of CNM
on Finally, (e.g. graphene
a reduction or CNT)
reaction either inusing
is performed pure an
or
decorated form, its characterization
carbon nanostructures, and finally
weak Van der Waals hydrogenappropriate
interactions adsorptionreducing
and measurement of stored
agent to eliminate hydrogen.
oxygen [78-82].
Synthesis
are there.ofSo,graphene
one should involves exfoliation
carefully take into of graphite
account of through
This is either mechanical
followed or chemical
by purification route.toCNT
and drying is
obtain
those interactions
generally synthesizedwhileadopting
computing binding energy
chemical vapourofdeposition
H2 TM-decorated CNM. In case
(CVD) technique. of CNT, functionalization
Functionalization of CNM
molecules
involves on carbonaceous
a wet chemical method substance.
where first carbon arms are can also be performed
activated by reactingduring its synthesis
with oxidizing by CVD The
chemicals. [83-
87]. Characterization involves microscopic
activated sites act as receptor of heteroatoms. In the next step, transition metal (TM) atoms are conjugated with observation
3. Hydrogen
the active sitesstorage in carbon nanomaterials:
of the oxygenated through TEM
CNM using suitable chemical, [88], Raman
composing of thespectroscopy
TM. Finally, [89], XRD [89]
a reduction
experimental studies etc. (Fig.s 10-11), for determination
reaction is performed using an appropriate reducing agent to eliminate oxygen [78-82]. This is followed by and visualization of
Experimental hydrogen storage studies involve structure. After pressurized hydrogenation,
purification and drying to obtain TM-decorated CNM. In case of CNT, functionalization can also be performed the adsorbed
preparation
during of CNM
its synthesis by (e.g.
CVDgraphene hydrogenmicroscopic
or CNT) either involves
[83-87]. Characterization quantity is measured
observationthrough volumetric
through TEM [88],and
Raman spectroscopy [89], XRD [89] etc. (Fig.s 10-11), for determination and visualization of structure. After
22
pressurized hydrogenation, the adsorbed hydrogen quantity is measured through volumetric and gravimetric
methods [90] (Fig. 12a). For issues related with purity, clustering, agglomeration of decorating nanoparticles
and oxygen interference, experimentally observed results seldom match with theoretical predictions (Fig. 12b)
Raman spectroscopy [89], XRD [89] etc. (Fig.s 10-11), for determination and visualization of structure. After
pressurized hydrogenation, the adsorbed hydrogen quantity is measured through volumetric and gravimetric
methods [90] (Fig. 12a). For issues related with purity, clustering, agglomeration of decorating nanoparticles
and oxygen interference, experimentally observed results seldom match with theoretical predictions (Fig. 12b)
[91].
(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].
3.1 Experimental studies

aiming hydrogen storage in
pure CNMs
Chen et al. [92] synthesized
aligned (CNTs) with diameters of
50–100 nm, by plasma-assisted hot
filament chemical vapor deposition.
Using quadruple mass spectroscopy
and thermogravimetric analysis
they found a H2 storage capacity
of 5–7 wt% reproducibly at room
temperature under modest pressure
of ~10 atm. Heating the samples to
300 °C and removal of the catalyst
tips may increase the H 2 storage
capacity up to 13 wt% and decrease
the pressure required for storage
(Fig. 13).
Fig. 13: (a)
: (a) SEM picture SEMof the CNTs synthesized by plasma-assisted CVD; (b) TEM picture of the tube wall structure, structure,
picture of the CNTs synthesized by plasma-assisted CVD; (b) TEM picture of the tube wall
whichthat Fig. 13: (a) SEM picture of the CNTs synthesized by plasma-assisted CVD; (b) TEM picture of the tube
indicates thatopen-ended
there are open-ended Lueking et al. [93] exhibited
ndicates there are layers; (c) layers;
catalyst(c) catalystCNTs.
removed removed
andCNTs. and TGA
TGA spectra spectra
of the of therelease
hydrogen hydrogen
in release in
aligned wall structure,
carbon nanotubes: which indicates that
(e) as-prepared there are open-ended
samplehydrogen layers;
without uptake; (c) catalyst
hydrogen(f)uptake; removed CNTs.
(f) as-prepared and
sample TGA that selective exfoliation of a carbon
stored at room
carbon nanotubes: (e) as-prepared sample without as-prepared sample stored at room
temperature spectra
under of the hydrogen
2 atm hydrogen;release in aligned carbon
(g) catalyst-free nanotubes:
samples (e) as-prepared
storedtemperature sample
at room temperature without hydrogen
under(From
10 atm. (Fromnanofiber is a means by which
ature under 2 atm hydrogen; (g) catalyst-free samples stored at room under 10 atm. Chen et Chen et
al., 2001 uptake;
[92], with(f)permission.)
as-prepared sample stored at room temperature under 2 atm hydrogen; (g) catalyst-free H interaction with the carbon
1 [92], with permission.) 2
samples stored at room temperature under 10 atm. (From Chen et al., 2001 [92], with permission.) structure can be controlled. This
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.
(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
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]
3.2 Experimental studies aiming hydrogen storage in functionalized CNMs

Reyhani et al. [122] studied H2 storage performance of MWCNT decorated with Ca, Co, Fe, Ni, and Pd. H2
molecules are adsorbed on the defect sites and transported to the spaces between adjacent carbon via diffusion
Fig. 15:through both defect
(a) Scheme for thesites and opened
formation tips into
process thehierarchical
of the layers. Improvement in storagematerial.
graphene-based capacity through decoration
(b) Hydrogen is
adsorption and
Fig. 15: (a) through
Scheme for the formation
either process oforthedissociation
Kubas interaction hierarchical of
graphene-based
H2 moleculesmaterial.
on the (b) Hydrogen
metal adsorption
particles, and desorption
i.e., spillover. Pd is isotherms of
foundgraphene
the hierarchical to be most
and effective
pre-hierarchical for H2 storage
catalystgraphene. Hydrogenprocess. Dissociation
adsorption of H2 occurs
and desorption on the
isotherms of Pd
the particle, andgraphene
hierarchical H2 and pre-
atoms are(c)
hierarchial graphene, entered into
Isosteric theofspaces
heat between
hydrogen adjacent
sorption. and (d)carbon layers. They
Physisorption create
hydrogen loosely
storage bondscomparison
capacity of CHx species andthe hierarchical
between
graphene and Pd-C-H x complex
various which can
carbon materials. be decomposed
(From easily
Guo et al., 2013 at with
[94], lowerpermission).
temperatures as compared to C-H chemical bonds
(Fig. 16).
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
Dissociation of H2 occurs on the Pd particle, and H2 atoms

dissociative chemisorption of H2 molecules by spillover to
are entered into the spaces between adjacent carbon
achieve hydrogen storage capacity (> 4 wt %). This can be
layers. They create loosely bonds of CHx species and Pd-
three times higher than its pristine counterpart (Fig. 17).
C-Hx complex which can be decomposed easily at lower
25
Table 4 A versions of remarkable experimental works for measuring H2 storage in pure CNMs [95-119]
Carbon nanomaterial Storage condition Hydrogen storage Remarks Reference

type capacity (wt %)
Temperature Pressure
Graphite 773 K 3.5 MPa 1.6 [95]
77 K 20 bar 1.2 Exfoliated graphite [96]
Graphene 300 K 1 MPa 7.4 [97]
Activated carbon 293 K 3 MPa 0.39–0.53 [98]
Activated carbon 298 K 10 MPa 2.29 [99]

fiber
Carbon nanotube Ambient 0.067 MPa 3.5–4.5 High purity single walled [100]
Ambient 4.8 MPa 1.2 Purified SW [101]
Ambient 0.9 MPa 0 Ball-milled SW [102]
80 K ∼7 MPa 8.25 High purity SW [103]
295 K 0.1 MPa 0.93 Impure SW [104]
∼300–700 K Ambient 0.25 Purified MW [105]
300 K 1.0 MPa 13.8 Acid treated MW [106]
298 K 3.6 MPa 0.03 Low purity MER MW [107]
298 K 10 MPa 0.68 Random orientation MW [108]
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]
77 K 12 MPa 12.38 CNF [111]
93 K 10 MPa 1 CNF [112]
298 K 3.6 MPa <0.1 Vapor grown [107]
Ordered mesoporous 298 K 30 MPa 2.14 [113]

carbon
Templated carbon 298 K 10 MPa 1.43 [114]
Carbon xerogel 298 K 20 1.0 [115]
Carbon sphere 298 K 9 0.25-0.43 [116]
Carbon nanosheet 298 K 0.11 0.1-0.26 [117]
Carbon cloth 298 K 90 bar 0.5 [118]
26
Table 5 Hydrogen storage performance of functionalized CNMs experimentally observed by research-

ers worldwide [89, 91, 125-141]
Carbon Storage condition Hydrogen Remarks Reference

nanomaterial storage
Temperature Pressure Decorating
type capacity (wt %)
element
Graphene 77 K Ambient Zirconia 1.2 Reduced GO [125]
298 K 4 MPa Pt and N 4.4 [89]
298 K 100 bar P 2.2 [126]
298 K 3 MPa Pt 1.4 [127]
298 K 30 bar Pd3Co 4.6 boron doped [128]
Carbon 473–673 K 0.1 MPa Li 20 [129]
nanotube
<313 K 0.1 MPa K 21 Wet H2 [130]
473–663 0.1 MPa Li 0.7–4.2 10–40% pure [131]
Ambient 0.067 MPa Ti-Al-V 6 Sonicated [132]
Ambient 0.08 MPa Fe <0.005 Purified [91]
298 K 15.85 atm Ni 0.812 multiwalled [133]
12.64 atm Cu 2.59
15.45atm Agglomerated Fe 0.909
298 K 32 bar Pd, N 1.25 Graphene [134]
Nanoplatelets
283-335 K Ambient Ca 1.05 Multiwalled [135]
Co 1.51
Fe 0.75
Ni 0.4
Pd 7
Ambient 80 bar B <2 [136]
Moderate Ambient K 4.47 [137]
Carbon 298 50 bar Ni 0.56 decorated CNF [138]
nanofiber grown on ACF
substrate
Porous 298 K 100 bar P 1.2 [139]
carbon
Graphitic 298 K 4 MPa Pd 2.6 [140]
carbon nitride
Superactived 298 K 10 MPa Pt 1.46 [141]
carbon
27
(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
desorption , GP-Ni of
1.51GP, and
GP-Ni GP-Ni
2.41B0.69
0.83
0.83 B
GP-Ni
1.09 (adsorption data
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
data
(From data
desorption Wang
are
asetopen shown
al., 2011 [123],
shapes). aswith
(From closed shapes,
et al., 2011desorption
permission.)
Wang data as open
shapes). (From Wang et al., 2011 [123],A with

novel permission.)
inelastic neutron A
scattering based hydrogen
novel inelastic quantification
neutron scattering basedmethod hasquantification
hydrogen been developed by Liu
method has been developed by Liu
et al [124] to find advantage over traditional
et al [124] Sievert type
to find advantage over measurement. The developed
traditional Sievert method involves
type measurement. The developed method involves
temperature-cycling. Measurements on single-wall
temperature-cycling. carbon nanohorns
Measurements (SWCNHs)
on single-wall carbondecorated
nanohorns with 2–3 nm Pt
(SWCNHs) decorated with 2–3 nm Pt
nanoparticles showed 0.17% mass fraction
nanoparticles of metal-assisted
showed H2 storage
0.17% mass fraction (at ≈0.5 MPa)Hat
of metal-assisted room temperature.
2 storage (at ≈0.5 MPa) at room temperature.
When measured using Sievert’s apparatus,using
When measured a hydrogen
Sievert’s apparatus,ofa≈0.08%
adsorption hydrogenmass fraction of
adsorption at ≈0.08%
5 MPa atmass
roomfraction at 5 MPa at room
temperature is achieved. The obtained isexcess
temperature storage
achieved. Theranging 0.3-0.5
obtained excesswtstorage
% is believed
rangingto be attributed
0.3-0.5 wt % istobelieved
metal- to be attributed to metal-
assisted H2 spillover (Fig. assisted
18). H2 spillover (Fig. 18).
(d)
Fig. 17: SEM images of GP (a) pristine graphene (GP) and (b) GP-Ni0.83B1.09, (c) TEM image of GP-Ni0.83B1.09, and (d)
(d)isotherms of GP, GP-Ni2.41B0.69, GP-Ni1.51B1.39 and GP-Ni0.83B1.09 at 77 K (adsorption data
H2 adsorption and desorption
are shown as closed shapes, desorption data as open shapes). (From Wang et al., 2011 [123], with permission.)
Fig. 17: SEM images of GP (a) pristine graphene (GP) and (b) GP-Ni0.83B1.09, (c) TEM image of GP-Ni0.83B1.09, and (d)
H2 adsorption and desorption isotherms of GP, GP-Ni 2.41B0.69
A novel , GP-Ni
inelastic 1.51 B1.39scattering
neutron and GP-Ni 0.83B1.09
based at 77 Kquantification
hydrogen (adsorption data
method has been developed by Liu
are shown as closed shapes, desorption data as [124]
et al open shapes).
to find (From Wangover
advantage et al., 2011 [123],
traditional with permission.)
Sievert type measurement. The developed method involves
temperature-cycling. Measurements on single-wall carbon nanohorns (SWCNHs) decorated with 2–3 nm Pt
A novel inelastic neutron scattering based showed
nanoparticles hydrogen quantification
0.17% method
mass fraction has been developed
of metal-assisted H2 storageby
(atLiu
≈0.5 MPa) at room temperature.
et al [124] to find advantage over traditional
When measuredSievert type
using measurement.
Sievert’s apparatus, The developed
a hydrogen method
adsorption involves
of ≈0.08% mass fraction at 5 MPa at room
temperature-cycling. Measurements ontemperature
single-wall carbon nanohorns
is achieved. The obtained (SWCNHs) decorated
excess storage with 2–3
ranging 0.3-0.5 wt %nm Pt
is believed to be attributed to metal-
assistedofH2metal-assisted
nanoparticles showed 0.17% mass fraction H2 storage (at ≈0.5 MPa) at room temperature.
spillover (Fig. 18).
When measured using Sievert’s apparatus, a hydrogen adsorption of ≈0.08% mass fraction at 5 MPa at room
temperature is achieved. The obtained excess storage ranging 0.3-0.5 wt % is believed to be attributed to metal-
assisted H2 spillover (Fig. 18).
(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
systemsystem
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
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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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.
Dr. Brahmananda Chakrabortyis an Associate Professor at the Homi Bhabha National

Dr.Brahmananda
Brahmananda
institute,
Dr. Mumbai and Chakraborty
Scientist in an
Chakrabortyis is
High anPressure
Associate Associate & Professor
Professor Synchrotron
at the Homi at Radiation
theBhabha
Homi National
Bhabha National institute,
Physics
Mumbai
Division ofand Scientist
Bhabha Atomicin High
Research Pressure
Centre, & Synchrotron
Mumbai. He
institute, Mumbai and Scientist in High Pressure & Synchrotron Radiation Physics Radiation
received his Physics
PhD Division
degree in of Bhabha Atomic
Division of Bhabha Atomic Research Centre, Mumbai. He received his PhD degree infor his research topic
Research
Physics fromCentre,
IIT, Mumbai.
Bombay forHe received
his research his PhD
topic degree
on in Physics
‘Irradiation from
Effects IIT,
and Bombay
Hydrogen
on ‘Irradiation
Storage
Physics on
fromCarbonEffects
IIT, Bombayandfor
Nanotubes’ Hydrogen
under
his Storage
the
research guidance
topicononCarbon Nanotubes’
of‘Irradiation
Dr. Srikumar under
Banerjee
Effects the guidance
and and Prof.
Hydrogen of Dr. Srikumar
Banerjee
D.S.
Storage onand
Misra. DrProf. D.S.
Chakraborty
Carbon Misra.
Nanotubes’ Dr
twoChakraborty
did under years didoftwo
(2010–2012)
the guidance years (2010–2012)
Post-doctoral
Dr. Srikumar research
Banerjee Post-doctoral
Prof. research at North
at North
and
Carolina
Carolina
D.S. Misra.State
State University,
DrUniversity,
Chakraborty USA.USA.
didHis
twoHis current
current
years research
research
(2010–2012) interest
interest includes
includes
Post-doctoral DensityDensity
research Functional Theory (DFT)
Functional
at North
Theory (DFT) and Molecular Dynamics (MD) simulations for energy materials, bio-
and Molecular
Carolina DynamicsUSA.
State University, (MD) Hissimulations
current research for energy materials,
interest includesbio-sensors, reactor fuels and structural
Density Functional
sensors, reactorandfuelsMolecular
and structural materials, various 2D materials for energy storage
materials, various
Theory
devices
(DFT) 2D materials for energy
Dynamics storage
(MD) devices
simulations andHethereceived
for behaviorInternational
energy of materials
materials, bio- under high pressure.
sensors,and the behavior
reactor fuels and of materials
structural under
materials, high pressure.
various 2D materials for energy storage
He received InternationalMaterial
Association Association of Advanced Material (IAAM) HeScientist veryMedal
good in 2017. He has very
devices and oftheAdvanced
behavior of materials (IAAM) under Scientist Medal
high pressure. in He2017.received hasInternational
good experience
experience of
Associationofofteaching teaching
Advanced while while
teaching
Material teaching Density
DensityScientist
(IAAM) FunctionalFunctional
Medal Theory Theory
at North
in 2017. at North
He Carolina Carolina
good State University,
has very State
experience of teaching while teaching Density Functional Theory at North Carolina State He has more than
USA and
University, Computational
USA and Physics
Computational and
PhysicsStatistical
and Physics
Statistical at BARC
Physics at Training
BARC School.
Training
80 publications
School. has in
He USA
University, reputed
more
and than international
80 publications
Computational Physics journals. Dr. Chakraborty
in Statistical
and reputed Physics atisBARC
international also a Training
journals.regular
Dr. reviewer in reputed
international
Chakraborty
School. He is journals
hasalsomore like
a regular
thanJournal
reviewerof Physical
in reputed
80 publications Chemistry,
reputedCARBON,
in international journals
international Physical
like Chemistry
Journal
journals. of Chemical Physics,
Dr.
Journal Chemistry,
Physical
Chakrabortyof Applied Physics
a regularetc.
is also CARBON, Dr. Chakraborty
Physical
reviewer Chemistry has also contributed
in reputed Chemical
internationalPhysics, in
Journal
journals Department
like of Applied
Journal of of Atomic Energy’s
Nuclearetc.
Physics
Physical Programme
Chemistry, in physics
Dr. Chakraborty
CARBON, has designing of various
also contributed
Physical Chemistry in reactors
Department
Chemical using
Physics, Monte
AtomicCarlo
ofJournal Simulations for neutron
ofEnergy’s
Applied
Nuclear Programme in physics has designing of various reactors using MonteEnergy’s
Carlo
transport.
Physics etc. Dr. Chakraborty also contributed in Department of Atomic
Simulations for neutronintransport.
Nuclear Programme physics designing of various reactors using Monte Carlo
Simulations for neutron transport.
32
Study of vertical graphene-nanodiamond hybrid structure grown by

thermally activated chemical vapor deposition
Department of Physics, Vikram Deb (A) College, Jeypore, Koraput, Odisha-764001
E-mail: dipti.mohapatra81@gmail.com
Abstract
The report is based on a non-catalytic direct growth of few layered vertical graphene (FLVG)-nanodiamond
hybrid structure using a thermally activated hot filament CVD technique. The cross-sectional microstructural
analysis of the film−substrate interface revealed the exact steps involved for the structural transformation
of graphene from the planar structure into the two-dimensional vertical structure. The results suggest
that the formation of vertical graphene is possible only by the addition of nitrogen gas into the precursor
gas-mixture. The possible mechanisms for the onset of vertical growth of FLVG structure in a thermally
activated medium are discussed.
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
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
Fig. 2:Fig. The cross-sectional

The2:cross-sectional SEMSEM imagesof
images of the
the film
filmgrown
grownforfor
30 30
minute (a) normal
minute and (b)
(a) normal andtilted
(b)view.
tilted view.
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.
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
15. J. Yu, R. Qian, P. Jiang, Fibers and Polymers 14 (2013) 1317.

few-layered vertical graphene (FLVG) − nanodiamond
16. Y. Wu, B. Yang, G. Han, B. Zong, H. Ni, P. Luo, T. Chong, T.
hybrid structure in a single-step using a non-catalytic
Low, Z. Shen, Advance Functional Materials 12 (2002) 489.
thermally activated HFCVD technique. The Raman and
17. K. Shiji, M. Hiramatsu, A. Enomoto, M. Nakamura, H.
HRTEM observation of the hybrid film confirms the Amano, M. Hori, Diamond and Related Materials 14 (2005)
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the nitrogen gas inclusion in the precursor gas-mixture 20. J. J. Wang, M. Y. Zhu, R. A. Outlaw, X. Zhao, D. M. Manos,
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21. M. Hiramatsu, M. Hori, Japanese Journal of Applied Physics
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45 (2006) 5522.
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22. S. Kondo, M. Hori, K. Yamakawa, S. Den, H. Kano, M.
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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
Effect of nitrogen ion implantation on electron field emission property of

nanocrystalline diamond films
Department of Physics, Tamkang University, Tamsui 251, Taiwan, R. O. C.
Nuclear Science and Technology Development Center Accelerator Division, National Tsing-Hua University,
Hsinchu, Taiwan 300 R. O. C.
E-mail: upalnitkar@gmail.com
Abstract
Nanocrystalline diamond (NCD) films were grown by microwave plasma assisted chemical vapour
deposition with CH4 and H2 as precursor with varying CH4: H2. These films were implanted with Nitrogen
ions at doses of 1013 and 1015 ions/cm2 (Energy 100 keV). The structural modification has been investigated
using UV Raman spectroscopy, field emission scanning electron microscopy, near edge X-ray absorption
fine structure (NEXAFS). A systematic investigation on the films microstructure and their electron field
emission (EFE) properties are presented. The structural modification at the subsurface resulted in a
significant reduction of electric field required for field emission. It was also found that the EFE property
highly depended on the graphite/diamond mixed phase structure. Optimized condition is observed for 3
% CH4 film implanted with 1015 ions/cm2 where turn on field is observed at 14 V/µm with current density
of 1.92 mA/cm2 (at 40 V/µm).
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.
power of 1500 W for 90 mins to

a thickness around 250 nm. The
corresponding NCD films were
designated as films A and B,
respectively.
Ion implantation was
performed in HVEE500kV –
Implantor at Nuclear Science
and Technology Development
Center, National Tsing-Hua
University, Taiwan. The chamber
pressure during implantation
Fig. 1: SEM micrographs ofFig.nitrogen ion-implanted
micrographsfilms grown ation-implanted
(a) 3% and (b) 5%grown
CH4 /atH(a)
. 3% and (b) 5
was kept at 10 -6 torr. All the 1: SEM of nitrogen films 2
samples were implanted with

100 keV nitrogen ions at room temperature. NCD films other around 1360 cm (D2-band), were deconvoluted.
-1
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
Fig. 3: Carbon K-edge NAXAF spectra of as deposited and implanted

films grown at (a) 3% and (b) 5% CH4/ H2; where (aI & bI) are as-grown,
(aII & bII) are 1013 ions/cm2 nitrogen ion-implanted and (aIII & bIII) are
1015 ions/cm2 nitrogen ion-implanted films (The NEXAFs for single
crystalline diamond and highly oriented pyrolysis graphite, HOPG,
% and (b) films.were also included to facilitate the comparison).
Fig. 2: UV Raman spectra of diamond films grown at (a) 3 % and (b) 5 % CH4/ H2; where (aI & bI) are as-grown, (aII &
bII ) are 10 Fig.
13
2: UV
ions/cm 2
Raman
nitrogen spectraand
ion-implanted of diamond films
(aIII & bIII) are 10 grown
15
ions/cm at
2
(a) 3 ion-implanted
nitrogen
5 % CH4/ H2; where (aI & bI) are as-grown, (aII & bII) are 1013 ions/
While Raman spectra illustrate clearly the modification on defect
cm2 nitrogen ion-implanted and (aIII & bIIIof ) are In Fig. 4 we have shown the emission current
structure of nanocrystalline diamonds
1015 ions/cm2 nitrogen
due to N ion implantation process, the quantitative analysis the defects induced from these spectra is difficult
ion-implanted
due to the relatively films.
different
density
sensitivity of Raman scattering for sp2 and sp3 component. That initiated us to
v/s electric field (J - E) curves for the films A &
study the near edge X-ray absorption fine structure (NEXAFs) study of as deposited as well as implanted B grown films,at different methane concentrations with ion
since NEXAFs is one of the best tool to quantify the sp2 and sp3 component in diamond film. Figure implantation with varying dose. The obtained J-E data
3 displays
Fromspectra
the C K-edge NEXAFs Fig. of3,asitdeposited
can beandclearly
implantedseen thatspectra
films. The afterwere ionnormalized using the
implantation
incident beam intensity Io and the spike
keeping of under
the area C 1sthe at spectra
289.2ineV theinitially
energy range drops was
between 314 andanalyzed
335 eV using Fowler-Nordheim Theory [12]. The
fixed. The for
NEXAFs 13energy range 2for diamond generally can be divided into two regions characterized
10 ions/cm (curves aII and bII) and disappears at detailed calculation
by provided important parameters like
specific features. One is a spike of C 1s core excitation resonance at approximately 289.2 eV. Another is a
higher dose of energy
10 ions/cm turn-on field, current density (Table 1). It can be clearly
between 288.6(curves aIIIforand
the spb3 III ). This
15 2
relatively broad σ* feature in the and 302 eV bonded carbon. The relatively
decrease
small peak at ∼285 eV canis be
mainly
attributeddue to local
to graphite like modifications
* 2
π state of sp bonded ofcarbon.
diamond The peak atseen thateV,the turn-on field (E0) is decreased after N ion-
287 –288
between π* crystalline
and σ* features can be attributed to the C-H bond on the
structure caused by the formation of point diamond surface. implantation from the as grown turn-on field value for
defects, where short range crystalline order was affected. both films. In contrast, the EFE current density (Je) is
This peak seems to be most sensitive to defects introduced insignificantly altered due to low dosage (1013 ions.cm2).
by ion implantation [11]. At the10same dose very less effect N ion-implantation but is markedly increased resulted
is observed on the second band gap at 302 eV. This peak from the high dosage (1015 ions.cm2) N ion-implantation.
gradually increases with increase in ion dose indicating The EFE current density increase in larger extent for film
deterioration of diamond band structure. Moreover, the A (3% CH4), as compared with that for film B (5% CH4).
peak around 285 cm-1 is found to increase with dose. This The damage caused by N ion-implantation plays
indicates conversion of sp3 phase into sp2 in NCD film after a dominant role in the field emission enhancement of
ion implantation. diamond films. This damage can directly produce number
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).
attributed to the defects introduced in the surface regions

is in accordance with the previous observation [14].
Restated, the defects created by ion implantation seem to
be sufficient to create a defect band within the diamond
band gap. Electrons can be emitted directly into vacuum
from these defect bands or the surface states. This may be
the reason for reduction of turn-on field. The effect of N
ion-implantation on improving the EFE current density
(Je) cannot be explained in the same straight forward
mechanism as that on lowering the turn-on field (E0), which
willfilms.
deposited NCD be Such
described
an argumentshortly.
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 attributed to the defects introduced in
the surface regions is in accordance with the previous observation [14]. Restated, the defects created by ion
implantation seemTo to be more
sufficient todetailed
create a defect investigate
band within the diamond thebandeffect of can
gap. Electrons ionbe emitted
directly intoimplantation on bands
vacuum from these defect fieldor the
emission
surface states.property
This may be thefor
reasondiamond
for reduction of turn-
on field. The effect of N ion-implantation on improving the EFE current density (Je) cannot be explained in the
same straight films,
forwardthe integration
mechanism of intensities
as that on lowering the turn-on field over π*-bond
(E0), which will be between
described shortly.
To more detailed investigate the effect of ion implantation on field emission property for diamond films,
281.6 to 286.1 eV *
the integration of intensities over π -bondsp2
(I ) and σ *
-bond between *288.6 to 302.4
between 281.6 to 286.1 eV (Isp2) and σ -bond between 288.6 to 302.4
eV (Isp3) wereeVestimated,
(Isp3) were
where theestimated, where
Isp2 and Isp3 represents the absorption
enhanced Isp2 andofIX-ray represents
by electron transit from
the C 1s core state to un-occupied sp or sp3 bond, respectively. Typical
2
Guassian sp3
fitting to curve aI is shown in
enhanced absorption of X-ray by electron
Fig.5. The dotted lines in the figure indicated the Guassian fitting. Here guassian fittings transit from the used for
have been
base fitting. The inset shows the peak associated with sp22 bonding3 and C-H bonding. It is observed that
line films
Fig. 4: The electron field emission current density vs. electric field, intensity
Fig. 4: The electron field emission current density vs. electric field, J –E Plots for as deposited and implanted C 1s of core
C-H state
bondingto un-occupied spturnoronspfieldbond, respectively.
grown at (a) 3% and (b) 5% CH 4/ H2; where (aI & bI ) are as-grown, (aII & bII) are 1013 ions/cm2 nitrogenintegral ion-implanted has direct correlation to of the films. It is observed that the
and (aJIII–E
& bIIIPlots for
) are 1015 as 2deposited
ions/cm and implanted
nitrogen ion-implanted films. films grown at (a) 3% integral and intensityTypicalis moreGuassian
in case of as fitting
deposited tofilmcurve
B than asadeposited
is shown film A.inAsFig.5. The
the integral intensity is
proportional to C-H bonds present near the surface, it improves I negative electron affinity of the surface of
the
(b) 5% CH4/ measurement
Table 1 Field Emission
H2; whereAnalysis
(aI & b(*J ) are as-grown, (aII & bII)atare
I e: EFE current density measured
10 ions/
13
the film
40 V /µm applied dotted
[15].
field) lines
This in turn in the
reduces the turnfigure indicated
on field that is observed inthe Guassian
our as deposited filmsfitting.
also (Table 1). It
Sample cm2 nitrogen ion-implanted FWHM and (aIII & ∆ (IbspIII2/)Isp
are
3
) 1015 ions/cm
J (mA/ cm22)nitrogen
Ewas observed that the integral intensity associated with C-H bonding decreases with ion implantation. This may
(V/µm)
Here guassian fittings have been used for base line fitting.
3% As Grown 13 0.00449 0.151 be18due to desorption of hydrogen from the surface16.
ion-implanted films.
1013 31 0.0047 0.196 13.33
of defects 1015in the surface - region that include
0.03441 1.926 vacancies, 14
5% dislocations, As Grown stacking 19 faults, and
0.004470second phase such
0.0158 16 as
graphite1015and amorphous carbon components. These
13
21 0.004570 0.1414 13.5
10 - 0.03029 0.3312 11.33
defects alter the work function and affect the field emission
The damage caused by N ion-implantation plays a dominant role in the field emission enhancement of
diamondproperty. In can
films. This damage addition, when
directly produce number ofthe number
defects in the surfaceof defects
region that includeis
vacancies,
significant,
dislocations, the
stacking faults, electronic
and states
second phase such of
as graphitetheanddefects
amorphous could form
carbon components.
defects alter the work function and affect the field emission property. In addition, when the number of defects is
These
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
Table 1 Field Emission measurement Analysis

(*Je: EFE current density measured at
40 V /µm applied field) Fig. 5: Guassian Fitting for calculation of sp2, C-H bonding and sp3 (Dotted
Fig. 5: Guassian Fitting for calculation of sp , C-H bonding and sp 2
lines indicates Guassian fitting)3
(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
1). It was observed that the integral intensity associated

with C-H bonding decreases with ion implantation. This
may be due to desorption of hydrogen from the surface16.
It should be noted that Isp2 / Isp3 ratio for sample A 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 for sample
B was 0.004470, 0.004570 and 0.03029. This indicates that
the ratio does not cha nge much for the films for low dose
(1013 ions/cm2) but increases profoundly for the high
dose (1015 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) = (Isp2/Isp3)Ion Implanted – (Isp2/ Isp3)As
Deposited
] in Fig 5. The η is thus a measure of relative change
in sp2 and sp3 content before and after ion implantation. Fig.
6 shows that when N ion-implanted for low dosage (1013
ions/cm2), there is no much change in η, but the turn-on
field (E0) decreases drastically. On the contrary, when N
ion-implanted for high dosage (1015 ions/cm2), the η value
increases in a large extend, but there is not much change in
E0. These observations imply that the reduction in turn-on
field is not induced by the presence of sp2-bonded phase. It
is mainly caused by the formation of defects and formation
of defect bands, as discussed previously.
In contrast, this figure shows that the EFE current
density increases pronouncedly with the ∆ (Isp2/Isp3) ratio
(η). Large Je-value for the films was observed in films
containing larger proportion of sp2-bonded phases (i.e.,
Fig. 6: The electron field emission current density (Je) and turn-on field
with larger η-value). For the low-dosage N ion-implanted (E0) vs. ∆Isp2/∆Isp3 ratio
Fig. 6: The electron field emission current density (Je) and turn-on field (E0) vs. ∆Isp2/∆Isp3 ratio for as deposite
for as deposited and implanted films grown at
samples, although there induced large proportion of implanted
point and(a)
implanted films grown
(J153%
at
& Eand
)
(a)
are
3%
(b)5
10
and (b)5 % CH4/ H2 ; where (J0) are as-grown, (J13 & E13) are 1013 ions/cm2 nitroge
15 % CH2 / H ; where (J ) are as-grown, (J
ions/cm & E13) are
15 4 nitrogen
2 ion-implanted
0 films. 13
defects, the EFE current density is in significantly improved 1013 ions/cm2 nitrogen ion-implanted and (J & E ) are 1015 ions/cm2
15 15
due to the fact that the ∆Isp2/∆Isp3 ratio (η) is not changed The increase in current density is very unlikely due to the nitrogen ion acquiring dopant site. If a
nitrogen ion-implanted films.
acquires it, Nitrogen is well known deep level impurity and hence unsuitable for producing n type diamond
much. Such a result indicates that the presence ofThe point
other reason to believe this is fact that the total amount of nitrogen ions concentration varies from a
defects does not enhance the transport of electrons10from 17
cm-2 to mechanism is thatdose
1019 cm-2 for implanted theof presence
1 x 1013 ions/cmof sp-2 2-bonded
and 1 x 1015 phase,
ions/cm-2, respectively
concentrationwhich is most probably the disordered carbons, forms the
is not sufficient to convert it into highly conducting n type diamond film. Also earlier studie
the substrates through the diamond films to the emissionshown following conclusions about ion implantation [19-21]: (i) There exists a critical implantation do
sites located at the surface of the films. High conductivity diamond/ disordered carbon interfaces. The electrons were
1014 – 1015 ions/cm-2 beyond which the damage cannot be healed out by annealing and the damaged layer
paths are required for improving the EFE current density injected
to graphite (ii) fromcanthe
Graphitization
o
a-C phase
be avoided into theexceeding
for implantation diamond, rendering
the critical dose if the implantati
carried out atthe into heated
region (1400in C)
the diamond.
vicinity Fromofallinterface
of the above semiconducting,
discussion and looking at our experim
via enhancing the transport of electrons. Figure 6 implies
conditions it can be clearly concluded that the nitrogen ion implantation has very unlikely dope
clearly that larger proportion of sp2-bonded phase leads to which
nanocrystalline diamondserves
films to asgive
electron conduction
high current channels.
density. Whereas The EFE created due
the graphitization
implantation current
might have density
created can thus
conducting be increased
channels markedly.
for facilitating Provided
electron field emission prope
higher EFE current density, which is apparently owing to
nanocrystalline diamond film. The later may be the dominant phenomenon working in our films.
the increase in number density of conduction paths for the For the that
films the conduction
A grown in 3% CH4,channels
the grains are aresmaller
interconnected
(~ 200 nm) andsuch that density of el
the number
electrons. The question is how the increase in sp -bonded the
2 conduction channels electrons
are abundant can be
enough transport
to form from
conducting the
network. underlying
The increase in Si- current densi
EFE
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
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.
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17. A.Denisenko,
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Aleksov, A.A. Probil,
Probil, P. Gluche,
P. Gluche, W. W. Ebert,
Ebert, Diamond
Diamond Relat.
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18. Johan. F. Prins, Nucl. Instrum. and Methods in Physics Res A 514 (2003) 69. (2003) 69.
19. G.
19. G.Braunstein,
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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.
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SMC Bulletin Vol. 11 (No. 1) April 2020 Phys.
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21. G.Braunstein
BraunsteinandandR.R.Kalish,
Kalish, Nucl.
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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
Tapender Singh1, Padmnabh Rai1, 2, *

1
Department of Physics & Astronomical Science, Central University of Himachal Pradesh, Dharamsha
SMC Bulletin
Kangra-176206, Vol. 11 (No. 1) April 2020
HP, India
2
School of Physical Sciences, UM-DAE Centre for Excellence in Basic Sciences, Mumbai-400098, In
Temperature influenced Electroluminescence in Carbon Nano-Tube Field E-mail: padmnabh.rai@cbs.ac.in
Effect Transistors Abstract

Electroluminescent properties of (17,0) carbon nanotube (CNT) field effect transistor (FET) is studied by
Tapender Singh1, Padmnabh
the non-equilibrium Rai1,method
Green’s function
2, *
(NEGF). It is observed that temperature has significant imp
1
Department of Physics & Astronomical Science,
theCentral University
light emission of Himachal
properties Pradesh, Dharamshala,
of CNT. Depending on the differentKangra-176206, HP,
applied temperature range and thickn
oxide layer India
used the device light emission characteristics can be tuned. Increased number of electron hole
2
School of Physical Sciences, UM-DAE Centre for Excellence in Basic Sciences, Mumbai-400098, India
recombination event result in decrease of the drain current at higher temperature range.
E-mail: padmnabh.rai@cbs.ac.in
Keywords: Carbon nanotubes, Surface Plasmons, Field effect transistors, Electroluminescence, Ra
Abstract
recombination rate, Non-equilibrium Green’s function method.
Electroluminescent properties of (17,0) carbon nanotube (CNT) field effect transistor (FET) is studied by
1. Introduction
using the non-equilibrium Green’s function method (NEGF). It is observed that temperature has significant
The unique opto-electronic characteristics of carbon nanotubes (CNT) provides an alternative (over the e
impact on the light emission properties of CNT. Depending on the different applied temperature range and
silicon based-technology) it to be used in the different optoelectronic devices such as in photodetecto
thickness of oxide layer used the device light emission characteristics can be tuned. Increased number of
emitting diode and in laser devices [1-3]. Due to the possibility of fabricating the low-power consumab
electron hole pair’s recombination event result in decrease of the drain current at higher temperature range.
cost and light weighting devices CNT can be used in the future device applied application [4]. Moreo
direct band-gap nature and quasi 1-D structure made it a suitable material in the different fields due
Keywords: Carbon nanotubes, Surface Plasmons, promising Field
electrical, optical
Theand thermal properties
MOSFET [1,5]. CNTFET
like CNT-FET has also
structure been demonstrated
is considered in for an ele
source for launchingthis
effect transistors, Electroluminescence, Radiative recombination of surface
studyPlasmons
due to(SPPs) in plasmonic
its improved circuitry [6,7].as compared
performance
rate, Non-equilibrium Green’s function method. Due to the better
to thecarrier transportbarrier
schottky characteristics of CNT
(SB)-FET: MOSFEThaving
MOSFET as comparedhigh-to Si-MOSFET
be used as light emitting
on current, higher on-off current ratio and scalability that emitters are
devices [8, 9]. The field effect transistors (FET) based light
1. Introduction promising CNT based
makelight itemitting
suitabledevices
for [10,
the11]. Further, FET can beapplications
high-performance classified in two different c
planar FET [9, 12] and coaxial gated FET [13]. The coaxial gated structure is considered here due to the
The unique opto-electronic characteristics of carbon [17, 18]. As SB plays a crucial role in the operation of- +
gate control over theSB-FET
CNT channel [14]. The simultaneous injection of the
[16, 19], it is the p-n junction which is important
charge carriers (e /h ) from the
nanotubes (CNT) provides an alternative and(over the responsible for
drain are the appearance of light emission characteristics [11, 15, 16]. Thu
used in the in(EL)
existing silicon based-technology) it to beelectroluminescence MOSFET [20, 21]. The formation of the p-n junction
characteristics are achieved through the simultaneous injection of e--h+
different optoelectronic devices such as in photodetector, is the main requirement to achieve the light emission
(ambipolar transport) [16].
light emitting diode and in laser devices [1-3]. The Due to characteristics in ohmic contacted FET type structures [20].
MOSFET like CNT-FET structure is considered in this study due to its improved performa
the possibility of fabricating the low-power compared
consumable, EL can
to the schottky also(SB)-FET:
barrier be obtained through
MOSFET thehigh-on
having unipolar transport
current, by current rat
higher on-off
low cost and light weighting devices CNT can be used
scalability the impact excitation mechanism [22]. Finally, radiative
thatinmake it suitable for the high-performance applications [17, 18]. As SB plays a crucial role
the future device applied application [4]. Moreover, its recombination
operation of SB-FET [16, 19], it is the rate (RRR)which
p-n junction is calculated
is importanttoinstudy
MOSFET the [20,
light21]. The forma
direct band-gap nature and quasi 1-D structure made
the p-n emission behaviours of CNT-FET.
it a is the main requirement to achieve the light emission characteristics in ohmic contacte
junction
typepromising
suitable material in the different fields due to its structures [20]. EL can also be obtained through the unipolar transport by the impact excitation mech
[22].
electrical, optical and thermal properties [1,5]. CNTFET 2. Theory
Finally, radiative recombination andrate simulation
(RRR) is calculated to study the light emission behaviours of
FET.
has also been demonstrated for an electrical source for The uncoupled 1D mode space approach is used to
launching of surface Plasmons (SPPs) in plasmonic represent the CNT channel as a Hamiltonian (H) matrix
circuitry [6,7]. 2. Theory and simulation
[23]. Mode space approach is used for the simulation
The uncoupled 1D mode spacedue
purpose approach
to itsisreduced
used to represent the CNT channel
computational cost asascompared
a Hamiltonian (H) matri
Due to the better carrier transport characteristics of
Mode space approach is used for the simulation purpose due to its reduced computational cost as comp
to the real space approach [23, 24]. Then the self-consistent
CNT MOSFET as compared to Si-MOSFET, itthe can be used
real space approach [23, 24]. Then the self-consistent iteration procedure is used to solve the Schrod
iteration procedure is used to solve the Schrodinger-
as light emitting devices [8, 9]. The field effect transistors
Poisson’s equation to determine the electrostatic potential and carrier concentration on CNT channel
Poisson’s equation to determine the electrostatic potential
(FET) based light emitters are most promising CNT based
Simulated CNTFET structure of coaxial gated device structure is shown in the Fig. 1 below.
and carrier concentration on CNT channel region.
light emitting devices [10, 11]. Further, FET can be classified
in two different classes: planar FET [9, 12] and coaxial
gated FET [13]. The coaxial gated structure is considered
here due to the better gate control over the CNT channel
[14]. The simultaneous injection of the charge carriers
(e-/h+) from the source and drain are responsible for the
appearance of light emission characteristics [11, 15, 16].
Thus, the electroluminescence (EL) characteristics are
achieved through the simultaneous injection of e--h+ pairs
(ambipolar transport) [16]. Fig. 1: Schematic
Fig. 1: Schematic of coaxial
of coaxial gated gated
CNTFET CNTFET
device device
structure structure
with doped with
source anddoped
drain extension.
source and drain extension.
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)
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)
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
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
annihilated and hence downfall in drain current is found 16. D. L. McGuire, D. L. Pulfrey, Nanotechn. 17 (2006) 5805.
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23. J.Chen,
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semiconductorQ. Fu, J.
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33. S. K. Sinha, S. Chaudhury, IEEE Trans.on Nanotechn. 12 (2013) 958.
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.
52
Printed by:
Ebenezer Printing House
Unit No. 5 & 11, 2nd Floor, Hind Service Industries
Veer Savarkar Marg, Shivaji Park Sea-Face, Dadar (W), Mumbai - 400 028
Tel.: 2446 2632 / 2446 3872 Tel Fax: 2444 9765 E-mail: outworkeph@gmail.com
53
In this issue
Feature Articles Page

No.
1. Recent developments of CNT based supercapacitors 1

Sivaram Arepalli
2. Hydrogen storage in carbon nanomaterials 12

Gopal Sanyal and Brahmananda Chakraborty
3. Study of vertical graphene-nanodiamond hybrid 33

structure grown by thermally activated chemical vapor
deposition
4. Effect of nitrogen ion implantation on electron field 40

emission property of nanocrystalline diamond films
5. Temperature influenced electroluminescence in carbon 47

nanotube field effect transistors
Tapender Singh and Padmnabh Rai
Published by
C/o. Chemistry Division
Bhabha Atomic Research Centre, Trombay, Mumbai 40085
e-mail: socmatchem@gmail.com, Tel: 91-22-25592001
54

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SMC Bulletin Vol. 11 (No.

A Publication of the Society for Materials Chemistry

Society for Materials Chemistry

Volume 11 No. 01 April 2020

Dr. G. Kedarnath Dr. Sandeep Nigam

Dr. Rajesh V. Pai Dr.Vivek Polshettiwar

Dr. Padmnabh Rai

From the desks of the President and Secretary

Dr. V. K. Jain Dr. R. K. Vatsa

(Dr. V.K. Jain) (Dr. R.K. Vatsa)

Feature Articles Page No.

1. Recent developments of CNT based supercapacitors 1

2. Hydrogen storage in carbon nanomaterials 12

3. Study of vertical graphene-nanodiamond hybrid structure grown by 33

4. Effect of nitrogen ion implantation on electron field emission 40

5. Temperature influenced electroluminescence in carbon nanotube 47

Recent developments of CNT based supercapacitors

1. Introduction to energy U.S. energy consumption by energy source, 2018

3.2 Asymmetric capacitor

carbon filaments have been reported earlier. The reader

Table 1 The major properties of CNTs [11]

S. No. Property Computational calculations Experimental measurements

Fig. 9:Electrochemical properties of the CNTs/GNFs- and CNTs-based supercapacitors in 6 mol/LFig.

based fibers, but it is theoretically

Specific Capacitance (mF/cm2)

electrolyte, of EMI + and

Hydrogen storage in carbon nanomaterials

Trombay, Mumbai-400085, India

2.5.2 Adsorption energy

2.5.3 Charge transfer and orbital

2.8 Theoretical studies aiming hydrogen storage

energy as they have greater charge which can interact with

2.6 Importance of dispersion corrections for

2.7 Sensitivity of theoretical data

Fig. 6: (a) Simulations of hydrogen of

Chakraborty et al [64] have also reported hydrogen

Ambient Ambient Ti 7.5 [67]

SMC Bulletin Vol. 11 (No. 1) April 2020

in pure or decorated form,

3.of the simulation

3.1 Experimental studies

3.2 Experimental studies aiming hydrogen storage in functionalized CNMs

Dissociation of H2 occurs on the Pd particle, and H2 atoms

Carbon nanomaterial Storage condition Hydrogen storage Remarks Reference

Graphite 773 K 3.5 MPa 1.6 [95]

77 K 20 bar 1.2 Exfoliated graphite [96]

Graphene 300 K 1 MPa 7.4 [97]

Activated carbon 293 K 3 MPa 0.39–0.53 [98]

Activated carbon 298 K 10 MPa 2.29 [99]

Ambient 4.8 MPa 1.2 Purified SW [101]

Ambient 0.9 MPa 0 Ball-milled SW [102]

80 K ∼7 MPa 8.25 High purity SW [103]

295 K 0.1 MPa 0.93 Impure SW [104]

∼300–700 K Ambient 0.25 Purified MW [105]

300 K 1.0 MPa 13.8 Acid treated MW [106]

298 K 3.6 MPa 0.03 Low purity MER MW [107]

298 K 10 MPa 0.68 Random orientation MW [108]

77 K 12 MPa 12.38 CNF [111]

93 K 10 MPa 1 CNF [112]

298 K 3.6 MPa <0.1 Vapor grown [107]

Ordered mesoporous 298 K 30 MPa 2.14 [113]

Templated carbon 298 K 10 MPa 1.43 [114]

Carbon xerogel 298 K 20 1.0 [115]