Materials Research Express

PAPER

Enrichment of solution-processable single-walled carbon nanotubes for

flexible nanoelectronics
To cite this article: Aref Asghari et al 2019 Mater. Res. Express 6 0850b4

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 Mater. Res. Express 6 (2019) 0850b4 https://doi.org/10.1088/2053-1591/ab2514

PAPER

Enrichment of solution-processable single-walled carbon nanotubes

for flexible nanoelectronics
RECEIVED
19 March 2019
REVISED
13 May 2019
ACCEPTED FOR PUBLICATION
Aref Asghari1 , Nicolás Antanio Ulloa Castillo2, Emmanuel Segura-Cardenas2, Alan O Sustaita2,
28 May 2019 Woosung Park3, Alex Yoon4 and Ethan C Ahn1
1
PUBLISHED Department of Electrical and Computer Engineering, The University of Texas at San Antonio, San Antonio, TX, 78249, United States of
5 June 2019 America
2
Escuela de Ingeniería y Ciencias, Tecnológico de Monterrey, Monterrey, NL, 64849, Mexico
3
Department of Mechanical Systems Engineering, Sookmyung Women’s University, Seoul, 04310, Republic of Korea
4
Lam Research Corporation, Fremont, CA, 94538, United States of America
E-mail: ethan.ahn@utsa.edu

Keywords: dispersion, flexible electronics, functionalization by acids, single-walled carbon nanotubes, solution-processability, inkjet
printing
Supplementary material for this article is available online

Abstract
Here we fabricate solution-processable single-walled carbon nanotubes that feature enhanced
dispersion in solvents while still affording excellent structural integrity, which is examined by adopting
both the microscopic (scanning electron microscopy) and spectroscopic (Raman spectroscopy)
characterization techniques. The controlled functionalization is key to producing the electronic grade
carbon nanotubes that exhibit the G-to-D peak ratio easily exceeding 10 when deposited as a thin-film
by spin coating. A comparative study is conducted to further investigate the effect of the deposition
method (spin coating versus drop casting), the chemical treatment (functionalization), and the
substrate (rigid substrates such as SiO2 or glass, and flexible substrates such as polyimide) on the
structural properties of carbon nanotubes. Additionally, a low-cost inkjet printing method enables us
to study the current-voltage characteristics of carbon nanotube thin-films of varying channel lengths,
and the measured electrical resistivity values approach those of moderately doped semiconducting
materials (in the range of 10−3 Ωm). This study suggests that upon the mild acid treatment, the single-
walled carbon nanotubes possess the potential to advance flexible nanoelectronics.

Introduction

Flexible nanoelectronics [1, 2] is emerging at the forefront of the Internet of Things (IoT) and Smart Home/City
era that offers a unique opportunity for enabling a variety of wearable electronics applications, including smart
watches, glasses, fabrics, and epidermal electronic systems [3–5]. However, most of the currently available
flexible technologies aim to integrate existing, rigid electronic components onto flexible substrates (e.g.,
polymeric substrates, the human body and skin, etc) that are not readily accessible by the conventional silicon-
CMOS technology. Several organic materials, which are intrinsically soft (flexible and stretchable), have been
explored for flexible electronics, but their low charge mobility has significantly limited their prospects to certain
specific applications (e.g., low-frequency applications such as tags and control electronics for display) [6].
Carbon is one of the most abundant organic elements that can exist in various physical forms. For example,
sp -hybridized carbon [7, 8] forms covalent bonds with high bonding energies of 5.9 eV [8]. In this graphitic
2

form, carbon can create various low-dimensional nanostructures such as fullerene (C60), carbon nanotubes
(CNTs), or graphene. CNTs are cylindrical graphitic sheets, which are rolled-up into a seamless 1D
nanostructure with diameters of the order of a few to tens of nanometers. Owing to their unique one-
dimensionality, excellent electrical, thermal, mechanical and optical properties [9, 10], and manufacturability
(that has been greatly improved over the last decade in terms of large-scale growth and fabrication, transfer, and

© 2019 IOP Publishing Ltd

Mater. Res. Express 6 (2019) 0850b4 A Asghari et al

integration) [11–16], unprecedented advances in nanoelectronics has been made possible through the use of
CNTs in emerging logic [11] or memory [10, 17] devices, digital circuits [18], and even in unconventional
computing system architectures [19]. While it is recognized that CNTs can also be ideal for flexible electronics
[20, 21], the particular aspects unique to low-cost, flexible nanodevice applications still remain relatively
unexplored.
Here we demonstrate the controlled synthesis and functionalization of solution-processable single-walled
carbon nanotubes (SWCNTs), and investigate them as low-cost nanomaterials that can enable a wide range of
device applications in flexible nanoelectronics. We refer to our developed material preparation recipe as
controlled, which originates from an important finding that the SWCNT solutions fabricated in this work still
afford the excellent structural and electrical properties even after functionalization that typically involves some
chemical treatment [22]. There have been many research and development efforts on solution-processable
CNTs mainly because they can facilitate the nanodevice integration through a simple application technique
(either spin-coating or drop-casting) [23–27]. The other commonly used CVD (chemical vapor deposition)-
grown CNTs cannot be directly integrated with the device substrates due to the high processing temperature (at
around 1,000 °C) and thus require a careful, non-trivial transfer process [15]. Despite this great economic
benefit, there has been relatively sparse research on how different process parameters can lead to different
characteristics of a thin-film property of CNT random networks. This work addresses this challenge by
systematically studying the impact of the functionalization, the application method, and the substrate on the
structural properties of solution-processable SWCNTs. We also examine the electrical properties of them by
inkjet-printing the acid-functionalized SWCNTs between the metallic electrodes of varying distances (ranging
from 45 μm to 220 μm) pre-patterned on a flexible substrate.
This work is original in that the sulfuric/nitric acid-based functionalization approach is developed and
optimized to apply to ‘single-walled’ CNTs. Because sulfuric/nitric acids are relatively strong (as compared with
other approaches such as surfactant-based ones), they have only been used to tune the surface properties of
‘multi-walled’ CNTs that are more chemically stable due to multiple nanotube walls. Thus, many relevant
works, successfully enhancing the dispersion of nanotubes in solvents without significantly damaging them, are
performed upon multi-walled CNTs, while other existing works on single-walled CNTs show that this strong
acid treatment typically results in a significant degradation of CNT’s structural quality. Our work is unique and
significant because it shows for the first time that even with single-walled CNTs, the sulfuric/nitric acid-based
functionalization can be effective in attaching the oxy-functional groups (as evidenced by the enhanced
dispersion observed in scanning electron microscopy) while minimizing the creation of the unwanted defects on
the other CNT sidewall region (as evidenced by the high ratio of G to D peak intensities in Raman). The
effectiveness of this mild functionalization (and purification) technique leads directly to the success of the inkjet
printing of CNT. Our electrical characterization study demonstrates that the ‘single-print’ inkjet-printed CNT
thin films can exhibit the electrical conductivity as good as moderately doped conventional semiconductors.
Indeed, the electrical resistivity of about 10−3 Ωm (which translates into the sheet resistance on the order of kΩ/
sq.) measured in our work is smaller than those in most of the existing works on the single-printed SWCNTs by
inkjet.

Methods

The SWCNT colloidal solutions of varying concentrations (0.1 to 1.0 wt%) are prepared by the 5 h of
H2SO4/HNO3 treatment followed by the centrifugal purification (see the supplementary information for details
available online at stacks.iop.org/MRX/6/0850b4/mmedia), and are applied in the thin-film form onto three
different types of substrates (SiO2, glass, and polyimide are chosen as they are easily available and can represent
both the rigid and flexible platforms) for subsequent microscopic and spectroscopic characterizations (figure 1).
We focus on the single-walled CNT in this work because when compared with the multi-walled CNT
(MWCNT) that consists of multiple rolled graphitic sheets and thus exhibits a great degree of structural
complexity, its electrical and mechanical properties can be readily tuned by surface modification (i.e.,
functionalization). This is of practical importance for creating a useful electromechanical system [20, 21],
requiring a wide variety of specific application requirements to be met. It is noted that a relatively low range of
CNT concentration can help to enhance dispersion of CNT in solvents; we find that the SWCNTs get saturated
in DMF (dimethylformamide)-based solvents at above the concentration of 0.5–1.0 wt%. Due to this reason, the
results with SWCNT samples of the lowest possible concentration (0.1–0.2 wt%) are mainly reported and
discussed in this paper.
For functionalization, which refers to chemical treatment often employed to modify the surface-enabled
characteristics of CNT (e.g., dispersion, chemical affinity, toxicity) [22, 28], an acid-based approach using
sulfuric acid/nitric acid (H2SO4/HNO3) is found to be capable of preserving the intrinsic properties of SWCNTs

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Figure 1. The SWCNT colloidal solutions (a) and thin-films (b) prepared in this work. Different concentration samples are prepared
although the lowest concentration one (0.1 to 0.2 wt%) is mainly reported in the manuscript due to its enhanced dispersion
characteristic in the DMF-based solvent. Both functionalized and non-functionalized samples are deposited as the thin-film random
network of SWCNTs by either spin-coating or drop-casting on the three different substrates of polyimide, glass, and SiO2. The more
uniform thin-film coating could be obtained by increasing the number of drops in the case of drop-casting.

Figure 2. The microscopic (SEM) studies of functionalized (a) and non-functionalized (b) SWCNT thin-film samples spin-coated on
the SiO2 substrate. The properly functionalized SWCNTs form a randomly distributed network of thin-film layers while the non-
functionalized ones often lead to an agglomerated cluster of nanotubes. The magnified view in the inset reveals the diameter of
SWCNT bundles.

(particularly important when they are used as flexible nanoscale electrodes). This is an inspiring result because to
date, the relatively strong chemical treatment using sulfuric/nitric acids has been demonstrated mostly in
MWCNTs [29–31] having greater chemical stability due to the existence of multiple nanotube walls.

Results and discussion

Microscopic characterization and discussion

We first investigate the impact of functionalization on dispersion characteristics by examining both the acid-
functionalized and non-functionalized SWCNT thin-film samples (spin-coated on the SiO2 substrate) in the
high-resolution field-emission scanning electron microscope (Hitachi FE-SEM S-5500). As seen in figure 2, the
properly functionalized SWCNTs (figure 2(a)) form a randomly distributed network of thin-film layers while
the non-functionalized ones (figure 2(b)) often lead to an agglomerated cluster of nanotubes. This is primarily
because the presence of oxy-functional groups (e.g., carboxyl group, symbolized as COOH) in the acid-treated
SWCNTs promotes dispersion in polar solvents. It is noted that DMF is used as a polar aprotic solvent
throughout this work; a recent molecular dynamics (MD) simulation suggests DMF as one of the most favorable
solvents for dispersion of SWCNTs due to its planar molecular geometry and strong van der Waals interaction
[32]. This study clearly indicates that the effect of functionalization can be well studied by employing the
relatively simple SEM characterization technique without a more rigorous analysis of the chemical structure
of CNT.

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Figure 3. The Raman spectroscopic measurement of acid-functionalized SWCNT thin-films (red curves) drop-casted on the SiO2
substrate. The controlled mild functionalization leads to negligible changes in position and intensity of the SWCNT’s characteristic
peaks, including the RBM at below 500 cm−1 (shown in the inset). The light blue curve is the data from the reference samples (non-
functionalized SWCNTs), which is depicted only for the frequency ranges covering the D and G peaks for the purpose of clarity of
data. The relatively small (i.e., reduced) noise level of Raman spectrum in the functionalized case indicates that raw SWCNT samples
(that may contain some defective amorphous carbons) were effectively purified in the acid mixture.

Another useful insight is obtained in figure 2 (see the inset) by measuring the diameters of individual
SWCNTs and comparing between the functionalized and non-functionalized cases. While the measured CNT
diameter is in the range of 20 nm for the non-functionalized one, the acid-treated CNT exhibits about two times
smaller diameters. This experimental finding indicates that functionalization helps to unbundle the SWCNTs by
lowering their surface energies (the surface energy of graphite is directly related to the CNT’s bundling energy)
[32]. The non-functionalized SWCNTs tend to otherwise bundle (and even agglomerate) in order to minimize
their surface energy by reducing interfacial contacts to the solvent. For the clarity of terms, unbundling is
referred to as separating the individual nanotubes and dispersion means the spread of nanotubes (regardless of
the degree of bundling) throughout the solvent. We believe that even the functionalized SWCNTs still possess a
certain amount of bundling due to the strong inter-tube van der Waals forces as indicated by its relatively large
diameter (10.04 nm on average, measured with 50 bundles of nanotubes) observed in the SEM image; in general,
the diameter of individual (completely unbundled) SWCNTs ranges on the order of 1 to 4 nm [10]. A more
accurate analysis of the SWCNT’s bundling phenomenon is performed using the Raman spectroscopic
technique in the later section.
The same trend of enhancing both dispersion and unbundling by functionalization also appears in the thin-
film SWCNT samples prepared by the drop-casting technique while the drop-casting helps to minimize the
clustering for the non-functionalization case. The SEM data for drop-casted SWCNTs is available in
supplementary information.

Spectroscopic characterization and discussion

Next, we present our spectroscopic characterization data in figure 3, which shows the measured Raman
spectrum for the acid-functionalized SWCNT (drop-casted on the SiO2 substrate). The technique of Raman
spectroscopy is a well-established characterization tool used to analyze a variety of carbon nanomaterials,
including carbon nanotubes [33] and graphene [34], and many other low-dimensional nanostructures [35]. In
this work, the SWCNT thin-film samples (both functionalized and non-functionalized) are measured using a
Renishaw inVia confocal Raman microscope with wavelength of 532 nm. One key observation in figure 3 is that
our acid-treated SWCNTs feature a strong G peak (primary or first-order tangential vibrational mode of
sp2-carbon at around 1,590 cm−1) as compared with other D (defect or disorder scattering at around
1,350 cm−1) and G′ (overtone mode of the D band at around 2,700 cm−1) bands. The ratio of G to D peak
intensities (IG/ID) is as high as about 9.2, suggesting that the H2SO4/HNO3 acid treatment under controlled
conditions of the mixture ratio, temperature, and time (as described in the Methods and supplementary
information sections) can still preserve structural integrity of pristine SWCNTs. This is certainly a striking result
when compared with other similar works on functionalized SWCNTs [36–38], where the intense acid treatment

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typically involving long hours of refluxing for purification (up to 24 h) has resulted in degradation of the
SWCNT’s structural quality (i.e., generation of structural defects such as breakage of carbon bonds) dictated by
the significant increase in the D peak intensity (ID) in Raman. On the contrary, our controlled functionalization
(acid-treatment for 5 h with 1:1 ratio of HNO3:H2SO4) and purification (use of centrifugal separation followed
by microfiltration) recipe is found to be effective in attaching the oxy-functional groups (as evidenced by the
enhanced dispersion observed in SEM) while minimizing the creation of the unwanted defects on the other CNT
sidewall region (as evidenced by the high ratio of G to D peak intensities in Raman). The observed slight increase
in the G-mode wavenumber (blue shift) in acid-treated SWCNTs may also be indicative of the gentle p-type
doping effect by acid (H2SO4/HNO3)-enabled oxidation [38].
We also introduce here a few more insights on the SWCNTs fabricated in this work, by closely looking at
their RBM (radial breathing mode) peaks of Raman spectroscopy. The RBM occurs in a low frequency band,
typically at between 100 and 300 cm−1 depending on the tube diameter, and is the first-order Raman spectrum
that often serves as an indicator of the existence of the one-dimensional carbon nanostructures, including
SWCNTs [33]. While in the previous works the RBM intensities are also drastically reduced or even disappeared
after functionalization [36–38] (see also supplementary information for the surfactant-treated SWCNTs directly
experimented in this work), it is observed in figure 3 (inset) that both the low and high wavenumber RBM peaks
clearly exist in nearly the same position (at around 160 and 270 cm−1) even after the acid-functionalization
process. This suggests that the controlled, mild acid treatment developed and employed in this work offers
enrichment of CNT resonance without substantially breaking the translational symmetry of the pristine
SWCNTs. As predicted and studied by several theoretical [39–41] and experimental [42, 43] works, the presence
of two distinct RBM peaks may be attributed to the existence of both the kinds of isolated and bundled SWCNTs
(corresponding to 160 cm−1 and 270 cm−1 respectively) in our highly purified thin-film samples. As indicated
earlier by the relatively large diameter of SWCNTs observed in SEM, this RBM peak analysis supports the same
idea that our SWCNTs consist of a considerable amount of bundled SWCNTs even after acid-treatment.
Additionally, it is worthwhile to note that the RBM profile of our SWCNT samples (both functionalized and
non-functionalized) resembles more that of semiconducting tubes than metallic ones [44]. Indeed, the overall
topography of the G-band observed in figure 3 is best fitted by the Lorentzian line-shape rather than the Breit-
Wigner-Fano (BWF) model [33]; if the observed Raman spectrum resulted largely from metallic nanotubes (as
seen in several other studies that use surfactant-based techniques for functionalization [45, 46]), the G-peak
would have had a band split with the G− mode (at 1,570 cm−1) created due to the presence of free electrons in the
network of metallic nanotubes.
Figure 4 summarizes the measured ratios of G to D peak intensities (IG/ID), which is a primary measurement
of the disordered sites on nanotube walls, for both the conventional rigid (SiO2) and commercially available
flexible (DuPont’s Kapton polyimide thin-film of 1 mm in thickness) substrates. The obtained IG/ID values
resemble each other in both the absolute values and the trend with functionalization (treatment by acid or
surfactant) and deposition (spin-coated or drop-casted) details, suggesting that the polyimide offers an excellent
flexible substrate platform for thin-film deposition of solution-processable SWCNTs. A slight modification
(broadening) of the high-frequency RBM peak’s line-shape indicates that due to a higher chemical affinity of
oxy-functional groups with imide-containing compounds, the SWCNTs are unbundled more when deposited
on the polyimide substrate (see also supplementary information for the environmental SEM study on SWCNT
samples deposited on nonconducting substrates). The position of RBM peaks, however, still remains almost
unchanged (156 cm−1 and 267 cm−1) in the polyimide substrate case, implying that a possible radial
deformation due to adhesive interactions with the substrate [47] is minimized. A notable drop of IG/ID in the
SWCNT samples spin-coated on the SiO2 substrate is possibly due to the relatively high surface roughness
reported for PE-CVD (plasma enhanced-chemical vapor deposition)-grown SiO2 thin-films [48]. Although not
shown in the figure, the transparent glass substrate shares almost the same Raman characteristics as the
polyimide.

Electrical characterization and discussion

A direct consequence of CNT’s solution-processability is that CNT-based devices are fabricated with ease. For
example, electronic (e.g., thin-film transistors [24, 25]), energy conversion and storage (e.g., organic solar cells
[23] and supercapacitors [26]), and many other functional devices [20–22] can be developed through the use of
solution-processable CNTs. It is also noted that certain experimental platforms can be prepared without much
cost for the purpose of testing the fundamental properties of solution-processable CNT materials of particular
interest. Here we fabricate the simple device structures on the polyimide substrate to further investigate
electrical properties of the acid-functionalized SWCNT thin-films. Being combined with the previous
microscopic and spectroscopic studies, this electrical testing ultimately helps to explore the potential of our
SWCNT thin-films for flexible electronics (e.g., as flexible nanoscale electrodes). Because inkjet printing is

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Figure 4. The summary of impacts of various process parameters on the SWCNT’s structural integrity dictated by the ratio of G to D
peak intensities (IG/ID) (a) and the RBM profile (b) in Raman spectroscopy. SDS, ACID, SC, and DC represent functionalization by
sodium dodecyl sulfate (SDS) and H2SO4/HNO3 acid (ACID), and deposition of SWCNTs by spin-coating (SC) and drop-casting
(DC).

Figure 5. Electrical characterization of SWCNT thin-films deposited by inkjet printing on the flexible substrate. The inset in (a)
depicts the printed microdevice structure consisting of the silver (Ag) electrodes and SWCNT thin-film network channels. The
resistances measured for different SWCNT channel lengths are also shown in (b), indicating the relatively small contact resistance (on
the order of kΩ) dictated by the extrapolated trendline.

widely available to study a variety of solution-processable materials, including CNTs [49], by allowing for a rapid
patterning process at low cost and without any pre-fabrication of templates, we employ this inkjet printing
technique to create the microdevice structure consisting of the metallic (silver) electrodes of varying distances
and SWCNT bridges (channels) between them (see the inset in figure 5(a)). The devices fabricated in this study
have the following dimensions: electrode thickness of 1.6 μm, electrode width of 30 μm, and electrode spacing
(SWCNT channel length) of 45 μm to 220 μm. We vary the electrode spacing to investigate the possible impact
of the contact resistance between the SWCNT thin-film network and the silver electrode (figure 5(b)).
It is worthwhile to note that for SWCNTs, the effectiveness of inkjet printing is directly dictated by the
functionalization technique employed. This is because otherwise the pristine nanotubes are quite difficult to
disperse in a liquid (to create a CNT ink) and the functionalization needs to be conducted in such a way to

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promote dispersion while minimizing the creation of unwanted defects on the nanotube walls. By noting this,
one can naturally lead to the conclusion that our effective, albeit non-destructive, acid-functionalization
technique introduced and analyzed in the previous sections can better enable the inkjet printing of CNT. Indeed,
unlike many other existing works on SWCNTs deposited by inkjet printing [50–52], requiring multiple prints to
increase the CNT concentration and thus reach the target electrical property (e.g., up to 200 times of printing to
obtain 78 Ω sq−1 [52]), our electrical characterization study features a single-print preparation of SWCNT thin
film channels between the electrodes (see the inset of figure 5(a)).
As seen in figure 5(a), the measured current-voltage (I–V) characteristic of our inkjet-printed SWCNT thin-
film exhibits a monotonic increase of current over a wide range of voltage biases applied, possibly due to the very
weak rectifying nature of the SWCNT and electrode interface. The impact of contact is further investigated in
figure 5(b), which plots the measured resistance (R) values for different SWCNT channel lengths. Indeed, the
contact resistance extrapolated from the trend line (i.e., resistance at the channel length of zero) is found to be
relatively small (on the order of only a few kΩ’s). This is important, as it is suggested that the low-work function
metals (e.g., silver) can be well used to study solution-processable SWCNTs in a simple two-terminal device
geometry, and confirms our reasoning of negligibly small contribution of the SWCNT/Ag contact to the I–V
characteristic observed in the figure. The electrical resistivity value of the SWCNT channel is obtained to be as
low as 0.9×10−3 Ωm in this electrical measurement, implying that the SWCNT colloidal solutions fabricated
in this work may prove useful in certain flexible electronics applications that require the high degree of structural
integrity even after deposited as the thin-film form on a flexible substrate along with the moderately high
electrical conductivity.

Conclusion

This combination of microscopic, spectroscopic, and electrical characterization studies provides a

comprehensive description of the impact of various design parameters in fabricating and depositing the
solution-processable SWCNTs. The mild, albeit very effective, acid-treatment makes it possible to chemically
modify the CNT walls while minimizing the generation of unwanted defects. The acid-functionalized SWCNTs
developed in this work feature great dispersion in polar solvents as well as almost negligible degradation of the
CNT’s structural quality when deposited as the thin-film form on a flexible substrate. Therefore, this work serves
as the original demonstration of non-destructive, sulfuric/nitric (H2SO4/HNO3) acid-based functionalization,
even applicable to single-walled nanotubes that are generally considered to be chemically less stable than multi-
walled ones. The controlled recipes for both functionalization and purification are required to fabricate such
SWCNTs with properties suitable for flexible nanoelectronics. We also demonstrate that the SWCNT’s
solution-processability leads to a simple, low-cost device fabrication for electrical property measurement. The
electrical resistivity of the SWCNT thin-film network extracted from the current-voltage characteristics reaches
that of the conventional moderately doped semiconducting materials.

Acknowledgments

This work was supported by Lam Research Corporation, the University of Texas System Faculty Science and
Technology Acquisition and Retention (STARs), and the National Council of Science and Technology in Mexico
(CONACYT). The work was partly done at the Texas Nanofabrication Facility supported by NSF grant NNCI-
1542159.

Conflicts of interest

The authors declare no conflicts of interest.

ORCID iDs

Aref Asghari https://orcid.org/0000-0002-2606-960X

Ethan C Ahn https://orcid.org/0000-0002-0807-2071

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